Antibacterial and antiviral fiber substrate and method for preparing the same

Abstract

The application belongs to the technical field of functional textiles, and particularly relates to an antibacterial and antiviral fiber base material and a preparation method thereof. The preparation method comprises the following steps: S1. mixing an aqueous solution of a block copolymer formed by copolymerization of four monomers of hydroxyethyl methacrylate, 4-hydroxyvinyl oxybenzophenone methacrylate, glycidyl methacrylate and 3-methacryloyl dopamine with an aqueous solution of copper salt and silver salt, adding ammonia water dropwise until the solution becomes turbid and then becomes clear and transparent again, adding an aqueous solution of a reducing agent to perform a reduction reaction, and obtaining a finishing liquid; S2. immersing a fabric in the finishing liquid, taking out and rolling dry, and then sequentially performing drying, thermal oxidation treatment and ultraviolet irradiation treatment to obtain the antibacterial and antiviral fiber base material. The antibacterial and antiviral fabric prepared by the application has excellent antibacterial and antiviral performance and durability.

Description

Technical Field

[0001] This invention belongs to the field of functional textile technology, specifically relating to an antibacterial and antiviral fiber substrate and its preparation method. Background Technology

[0002] Pathogenic microorganisms (including bacteria, fungi, viruses, etc.) are the main culprits causing human infections and inducing infectious diseases. Textiles are the first line of defense between the human body and the external environment; their natural fibers are prone to bacterial growth and can become a medium for cross-infection. Therefore, developing fabrics with highly effective and long-lasting antibacterial and antiviral functions has become a research hotspot in the textile and materials fields.

[0003] Currently, the core of antibacterial and antiviral material research lies in the selection of antibacterial agents. Common antibacterial agents can be divided into natural antibacterial materials, organic antibacterial materials, and inorganic antibacterial materials. Natural antibacterial materials are widely available but suffer from the drawback of being unable to withstand high temperatures, making them difficult to adapt to traditional dyeing and finishing processes. Although organic antibacterial materials have high antibacterial activity, they often have a certain degree of toxicity and are prone to inducing drug resistance in microorganisms. In contrast, inorganic antibacterial materials (such as metal ion-based, photocatalytic, and nano-metal and their oxide types) have become the mainstream research direction due to their advantages such as broad antibacterial and antiviral spectrum, low toxicity, and good stability.

[0004] Among inorganic antibacterial materials, silver-based and copper-based nanomaterials have attracted much attention. Silver-based nanomaterials have broad-spectrum and stable bactericidal capabilities, maintaining stable efficacy against clinically multidrug-resistant bacteria; copper-based nanomaterials, especially copper oxide, not only have bactericidal functions but can also actively participate in the human tissue repair process. However, single nano-copper oxides still have significant defects in practical applications: (1) Low antibacterial and antiviral efficiency. Nano-copper oxides are p-type semiconductors, and the electron-hole pairs generated after photoexcitation are easily recombine, resulting in a short effective carrier lifetime and limited photocatalytic activity; (2) Poor solution stability. Nano-copper oxides are prone to agglomeration and precipitation in aqueous systems, making it difficult to meet the requirements of textile finishing processes for the dispersion stability of finishing solutions; (3) Insufficient fabric bonding strength. The lack of a functional layer with high affinity and reactivity with cotton fibers results in poor washability of the antibacterial coating, making it difficult to achieve long-lasting antibacterial effects.

[0005] To address the aforementioned issues, two main improvement strategies are proposed in existing technologies. First, by doping with a second metal element, the electron-hole pair stripping efficiency of nano-copper oxides can be improved. For example, by doping the surface or interior of nano-copper oxides with silver, a built-in electric field is formed at the interface when elemental silver combines with copper oxide. Since the Fermi level of silver is lower than that of copper oxide, photogenerated electrons spontaneously and directionally migrate to the silver particles and are captured, while holes remain on the surface of the copper oxide. The high conductivity and surface plasmon resonance of silver can be used to enhance the photocatalytic activity of copper oxides; simultaneously, the complementary antibacterial and antiviral mechanisms of the two materials can be utilized to achieve multi-target synergistic sterilization of bacteria. This composite material design exhibits higher and more stable antibacterial and antiviral efficiency than that of a single material. Second, by modifying the surface of nano-copper oxides with antibacterial polymers, the dispersion stability can be improved. However, existing polymer modification schemes still have significant shortcomings: most modifying polymers lack sufficient affinity and chemical reactivity with cotton fabrics, making it difficult to achieve long-term fixation through conventional dyeing and finishing processes; at the same time, there is a lack of integrated functional material design that balances dispersibility, antibacterial activity, fiber bonding strength, and processing adaptability.

[0006] Therefore, it is necessary to develop an antibacterial and antiviral finishing technology for fiber substrates, which can achieve high antibacterial and antiviral activity and high wash resistance through the synergistic antibacterial effect of finishing agent and substrate, strong bonding and effective dispersion and protection of nano copper oxide particles. Summary of the Invention

[0007] To better address the aforementioned technical problems, this invention provides an antibacterial and antiviral fiber substrate and its preparation method. This antibacterial and antiviral fiber substrate exhibits excellent antibacterial and antiviral properties and good washability.

[0008] Compared with existing technologies, this invention forms a stable finishing solution by compounding a multifunctional block polymer with a nano-silver-copper alloy. The BA segment in the polymer achieves long-term dispersion and stability of the nanoparticles, the GMA segment covalently bonds with the fiber hydroxyl groups for strong anchoring, the DMA segment chelates and protects the nanoparticles, and the VBP segment provides photocatalytic synergistic antibacterial function. The process route of "first preparing a stable nano-silver-copper alloy solution, then thermal oxidation and ultraviolet reduction" effectively avoids the defects of poor stability and difficulty in direct finishing of nano-copper oxides, allowing the antibacterial components to be uniformly loaded on the fiber substrate and forming Ag@Cu. x O composite structure; this fiber substrate combines block polymer photocatalysis and Ag@Cu xThe triple antibacterial and antiviral mechanism of O and Ag interface synergy enhancement and ion release achieves high-efficiency antibacterial and antiviral effects with low metal loading. After 50 washes, the antibacterial rate is ≥99% and the virus inactivation rate is >99.1%. At the same time, the BA segment in the polymer imparts good film-forming properties without affecting the original feel of the substrate, and the covalent bonding of the GMA segment imparts excellent wash resistance. The resulting fiber substrate is soft and breathable and can be widely used in medical textiles, outdoor functional fabrics, home textiles and other fields. Attached Figure Description

[0009] To more clearly illustrate the technical solutions in the embodiments of the present invention, the accompanying drawings used in the description of the embodiments will be briefly introduced below. Obviously, the accompanying drawings described below are only some embodiments of the present invention.

[0010] Figure 1 The reaction formula for the polymerization of four monomers to form a block copolymer P (BA-co-VBP-co-GMA-co-DMA);

[0011] Figure 2 A schematic diagram of the reaction process for preparing block copolymer-modified nano-silver-copper alloys;

[0012] Figure 3 A process flow diagram for preparing antibacterial and antiviral fabrics using block copolymer-modified nano-silver-copper alloy solutions;

[0013] Figure 4 Scanning electron microscope images at different magnifications of the long-lasting antibacterial and antiviral fabric prepared in Example 1. Detailed Implementation

[0014] To further understand the present invention, preferred experimental schemes of the present invention are described below with reference to embodiments. However, it should be understood that these descriptions are only for further illustrating the features and advantages of the present invention, and not for limiting the claims of the present invention.

[0015] An embodiment of the first aspect of the present invention provides a method for finishing fabrics using an antibacterial and antiviral fabric finishing solution, the preparation method comprising the following steps:

[0016] S100. Preparation of block copolymer P (BA-co-VBP-co-GMA-co-DMA)

[0017] Hydroxyethyl methacrylate (BA), 4-hydroxyvinyloxybenzone methacrylate (VBP), glycidyl methacrylate (GMA), and 3-methacrylamide (DMA) were dissolved in anhydrous ethanol. The molar ratio of hydroxyethyl methacrylate (BA), 4-hydroxyvinyloxybenzone methacrylate (VBP), glycidyl methacrylate (GMA), and 3-methacrylamide (DMA) was 20 : m : n : (80-mn), where m was 20–40 and n was 10–30. The total mass fraction of monomers in the reaction solution was adjusted to 30–60%. Azobisisobutyronitrile (AIBN) initiator was added at 0.5%–1.0% of the total monomer mass. The reaction was carried out under nitrogen protection at a constant temperature of 30–75°C for 6–8 hours. After the reaction was completed, a block copolymer solution was obtained. The solution was then evaporated at 80 degrees Celsius for 30 minutes using a rotary evaporator to remove the ethanol from the block copolymer, thus obtaining a pale yellow transparent block copolymer.

[0018] Figure 1 The reaction formulas for the polymerization of four monomers to form a block copolymer P (BA-co-VBP-co-GMA-co-DMA) are shown. In the block polymer, hydroxyethyl methacrylate (BA) monomer provides high molecular flexibility and hydrophilicity, allowing it to spread and form a film during baking, preventing the fabric from hardening after finishing and affecting the hand feel of the cotton fabric itself; 4-hydroxyvinyloxybenzophenone methacrylate (VBP) side chain has a dimethyl ketone photocatalytic group, providing the block polymer with photocatalytic antibacterial and antitoxic functions; glycidyl methacrylate (GMA) monomer side chain has an epoxy group, which can undergo a ring-opening reaction with the hydroxyl groups on the surface of cotton fibers to form covalent bonds, thereby improving the bonding strength of the antibacterial and antitoxic composite material on the fabric; 3-methacryloyl dopamine (DMA) side chain has a catechol group, which can form stable chelates with copper, silver, and their oxides, effectively protecting nanoparticles while ensuring good dispersibility of the particles in solution.

[0019] The molecular weight of the block copolymer P (BA-co-VBP-co-GMA-co-DMA) is controlled between 1,000 and 20,000, preferably between 1,500 and 10,000.

[0020] S200. Mix the aqueous solution of the block copolymer with the aqueous solutions of copper salt and silver salt, add ammonia dropwise until the solution first becomes turbid and then becomes clear and transparent again, then add sodium borohydride solution to carry out the reduction reaction, and the nano silver copper alloy colloidal solution, i.e., finishing solution, is obtained.

[0021] The reaction mechanism of the finishing solution preparation process is described in [reference needed]. Figure 2Using the block copolymer as a protective agent, a mixed aqueous solution of copper nitrate and silver nitrate was added. After complete dissolution, ammonia was added until the solution turned dark blue, as ammonia readily forms a silver-ammonia and copper-ammonia mixed solution with the two metal ions. Subsequently, NaBH4 reducing agent was added to the dark blue solution. Based on the reduction reaction, the high reducing power of NaBH4 was used to reduce copper and silver ions to a silver-copper alloy, thereby preparing a nano-silver-copper alloy solution with high solution stability, good dispersibility, good stability, and a particle size controllable between 0.5-80 nm, with a maximum solution concentration of 8 g / L. This avoids the problem of poor stability of nano-copper oxide solutions.

[0022] S300. Fabric Finishing

[0023] The fabric is immersed in the antibacterial and antiviral fabric finishing solution at a bath ratio of 1:30 to 1:60. After being removed, it is rubbed dry at room temperature until the liquid retention rate is 50% to 130%. Then it is dried at 60 to 80°C for 30 to 120 minutes, followed by thermal oxidation treatment at 160 to 250°C for 5 to 30 minutes. Finally, it is irradiated with ultraviolet light for 10 to 50 minutes to reduce the silver oxidized during the thermal oxidation process back to nano silver.

[0024] See the reaction mechanism of the fabric finishing process. Figure 3 The pad-dip drying process initiates a ring-opening polymerization reaction between the epoxy groups in the block polymer on the AgCu surface and the oxygen-containing groups, such as hydroxyl and carboxyl groups, on the fiber surface. This results in a strong chemical bond between the block polymer and the fiber, thereby improving the coating's durability. Then, a thermal oxidation process is used, utilizing high temperatures and oxygen in the air, to oxidize nano-AgCu into nano-copper oxide-silver (an oxide containing silver). Finally, the reducing properties of ultraviolet light are used to convert the nano-copper oxide-silver (an oxide containing silver) into elemental nano-copper oxide-silver (Ag@Cu). x O), thereby preparing Ag@Cu modified with a photocatalytic antibacterial and antitoxic block copolymer. x The O-coated long-lasting antibacterial and antiviral fabric provides high antibacterial and antiviral efficiency, high washability, and high uniformity of the surface coating.

[0025] Example 1

[0026] 1. Dissolve 2 g of hydroxyethyl methacrylate, 3 g of 4-hydroxyvinyloxybenzophenone methacrylate, 3 g of glycidyl methacrylate, and 2 g of 3-methacrylamide in 10 g of anhydrous ethanol and disperse thoroughly.

[0027] 2. Add 0.1 g of azobisisobutyronitrile to the above solution, and react at a constant temperature of 75 °C for 6 h under nitrogen protection. After the reaction is completed, a light yellow transparent polymer adhesive solution is obtained for later use.

[0028] 3. Dissolve 0.45 g of copper nitrate and 0.15 g of silver nitrate in 49.5 mL of water to prepare a mixed solution of copper nitrate and silver nitrate (weighted mass concentration of copper and silver elements is 5 g / L).

[0029] 4. Dissolve 1.25 g of P(BA-co-VBP-co-GMA-co-DMA) in 100 ml of water to prepare an aqueous solution of P(BA-co-VBP-co-GMA-co-DMA) with a concentration of 12.5 g / L.

[0030] 5. Take 10 mL of a mixed solution of copper nitrate and silver nitrate and mix it with 40 mL of P(BA-co-VBP-co-GMA-co-DMA) aqueous solution. Add ammonia water dropwise at room temperature until the solution turns clear and dark blue.

[0031] 6. At 30°C, 5g of 1% sodium borohydride solution was slowly added dropwise to the above solution. The solution color gradually changed from blue to reddish-brown, indicating that nano-copper and silver were generated in situ and tightly coated by the polymer.

[0032] 7. The above solution is heated to evaporate the water, and the solution is brought to a final volume of 50 mL. The mass-volume concentration of the nano-silver copper alloy in the solution is 1 g / L.

[0033] 8. Take 1g of the washed and dried cotton fabric and immerse it in a finishing agent containing the above-mentioned compound antibacterial agent at a liquor ratio of 1:30. Then, perform the liquid-pulling process on a liquid-pulling machine, and control the liquid carry-over rate at 100±5%.

[0034] 9. Place the rolled fabric in an oven and dry at 70°C for 30 minutes to initiate the grafting reaction. Then, raise the oven temperature to 210°C and bake for 6 minutes.

[0035] 10. Finally, the thermally oxidized fabric is irradiated under a UV lamp for 30 minutes to reduce the oxidized silver back to elemental silver, thus obtaining the block polymer / AgCu. x O-coated antibacterial and antiviral fabric with silver and copper content of ~1000mg / kg.

[0036] Example 2

[0037] 1. Dissolve 2g of hydroxyethyl methacrylate, 3g of 4-hydroxyvinyloxybenzophenone methacrylate, 3g of glycidyl methacrylate, and 2g of 3-methacrylamide in 10g of anhydrous ethanol and disperse thoroughly.

[0038] 2. Add 0.1 g of azobisisobutyronitrile to the above solution, and react at a constant temperature of 75 °C for 6 h under nitrogen protection. After the reaction is completed, a light yellow transparent polymer adhesive solution is obtained for later use.

[0039] 3. Dissolve 0.45g of copper nitrate and 0.15g of silver nitrate in 49.5mL of water to prepare a mixed solution of copper nitrate and silver nitrate (weighted mass concentration of copper and silver elements is 5g / L).

[0040] 4. Dissolve 1.25g of P(BA-co-VBP-co-GMA-co-DMA) in 100ml of water to prepare a 12.5g / L aqueous solution of P(BA-co-VBP-co-GMA-co-DMA).

[0041] 5. Take 10 mL of a mixed solution of copper nitrate and silver nitrate and mix it with 40 mL of P(BA-co-VBP-co-GMA-co-DMA) aqueous solution. Add ammonia water dropwise at room temperature until the solution turns clear and dark blue.

[0042] 6. At 30°C, 5g of 1% sodium borohydride solution was slowly added dropwise to the above solution. The solution color gradually changed from blue to reddish-brown, indicating that nano-copper and silver were generated in situ and tightly coated by the polymer.

[0043] 7. The above solution is heated to evaporate the water, and the solution is brought to a final volume of 50 mL. The mass-volume concentration of the nano-silver copper alloy in the solution is 1 g / L.

[0044] 8. Take 1g of the washed and dried cotton fabric and immerse it in a finishing agent containing the above-mentioned compound antibacterial agent at a liquor ratio of 1:30. Then, perform the liquid-pulling process on a liquid-pulling machine, and control the liquid carry-over rate at 130±5%.

[0045] 9. Place the rolled fabric in an oven and dry at 70°C for 30 minutes to initiate the grafting reaction. Then, raise the oven temperature to 210°C and bake for 6 minutes.

[0046] 10. Finally, the thermally oxidized fabric is irradiated under a UV lamp for 30 minutes to reduce the oxidized silver back to elemental silver, thus obtaining the block polymer / AgCu. x O-coated antibacterial and antiviral fabric with silver and copper content of ~1300mg / kg.

[0047] Example 3

[0048] 1. Dissolve 2 g of hydroxyethyl methacrylate, 3 g of 4-hydroxyvinyloxybenzophenone methacrylate, 3 g of glycidyl methacrylate, and 2 g of 3-methacrylamide in 10 g of anhydrous ethanol and disperse thoroughly.

[0049] 2. Add 0.1 g of azobisisobutyronitrile to the above solution, and react at a constant temperature of 75 °C for 6 h under nitrogen protection. After the reaction is completed, a pale yellow transparent polymer adhesive solution is obtained for later use.

[0050] 3. Dissolve 0.45 g of copper nitrate and 0.15 g of silver nitrate in 49.5 mL of water to prepare a mixed solution of copper nitrate and silver nitrate (weighted mass concentration of copper and silver elements is 5 g / L).

[0051] 4. Dissolve 1.25 g of P(BA-co-VBP-co-GMA-co-DMA) in 100 mL of water to prepare an aqueous solution of P(BA-co-VBP-co-GMA-co-DMA) with a concentration of 12.5 g / L.

[0052] 5. Take 10 mL of a mixed solution of copper nitrate and silver nitrate and mix it with 40 mL of P(BA-co-VBP-co-GMA-co-DMA) aqueous solution. Add ammonia water dropwise at room temperature until the solution turns clear and dark blue.

[0053] 6. At 30°C, 5 g of 1% sodium borohydride solution was slowly added dropwise to the above solution. The solution color gradually changed from blue to reddish-brown, indicating that nano-copper and silver were generated in situ and tightly coated by the polymer.

[0054] 7. The above solution is heated to evaporate the water, and the solution is brought to a final volume of 50 mL. The mass-volume concentration of the nano-silver copper alloy in the solution is 1 g / L.

[0055] 8. Take 1g of the washed and dried cotton fabric and immerse it in a finishing agent containing the above-mentioned compound antibacterial agent at a liquor ratio of 1:30. Then, perform the liquid-pulling process on a liquid-pulling machine, and control the liquid carry-over rate at 100±5%.

[0056] 9. Place the rolled fabric in an oven and dry at 70°C for 30 minutes to initiate the grafting reaction. Then, raise the oven temperature to 160°C and bake for 6 minutes.

[0057] 10. Finally, the thermally oxidized fabric is irradiated under a UV lamp for 30 minutes to reduce the oxidized silver back to elemental silver, thus obtaining the block polymer / AgCu. x O-coated antibacterial and antiviral fabric with silver and copper content of ~1000 mg / kg.

[0058] Comparative Example 1 (block polymer without VBP photocatalytic unit)

[0059] 1. Dissolve 5 g of hydroxyethyl methacrylate, 3 g of glycidyl methacrylate, and 2 g of 3-methacrylamide in 10 g of anhydrous ethanol and disperse thoroughly.

[0060] 2. Add 0.1 g of azobisisobutyronitrile to the above solution, and react at a constant temperature of 75 °C for 6 h under nitrogen protection. After the reaction is completed, a light yellow transparent polymer adhesive solution is obtained for later use.

[0061] 3. Dissolve 0.45 g of copper nitrate and 0.15 g of silver nitrate in 49.5 mL of water to prepare a mixed solution of copper nitrate and silver nitrate (weighted mass concentration of copper and silver elements is 5 g / L).

[0062] 4. Dissolve 1.25 g of P(BA-co-VBP-co-GMA-co-DMA) in 100 ml of water to prepare an aqueous solution of P(BA-co-VBP-co-GMA-co-DMA) with a concentration of 12.5 g / L.

[0063] 5. Take 10 mL of a mixed solution of copper nitrate and silver nitrate and mix it with 40 mL of P(BA-co-VBP-co-GMA-co-DMA) aqueous solution. Add ammonia water dropwise at room temperature until the solution turns clear and dark blue.

[0064] 6. At 30°C, 5g of 1% sodium borohydride solution was slowly added dropwise to the above solution. The solution color gradually changed from blue to reddish-brown, indicating that nano-copper and silver were generated in situ and tightly coated by the polymer.

[0065] 7. The above solution is heated to evaporate the water, and the solution is brought to a final volume of 100 mL. The mass-volume concentration of the nano-silver copper alloy in the solution is 1 g / L.

[0066] 8. Take 1 g of the washed and dried cotton fabric and immerse it in a finishing agent containing the above-mentioned compound antibacterial agent at a liquor ratio of 1:30. Then, perform the liquid-pulling process on a liquid-pulling machine, and control the liquid carry-over rate at 100±5%.

[0067] 9. Place the rolled fabric in an oven and dry at 70°C for 30 minutes to initiate the grafting reaction. Then, raise the oven temperature to 210°C and bake for 6 minutes.

[0068] 10. Finally, the thermally oxidized fabric is irradiated under a UV lamp for 30 minutes to reduce the oxidized silver back to elemental silver, thus obtaining the block polymer / AgCu. x O-coated antibacterial and antiviral fabric with silver and copper content of ~1000mg / kg.

[0069] Comparative Example 2 (without AgCu) x O nanoparticles)

[0070] 1. Dissolve 2g of hydroxyethyl methacrylate, 3g of 4-hydroxyvinyloxybenzophenone methacrylate, 3g of glycidyl methacrylate, and 2g of 3-methacrylamide in 10g of anhydrous ethanol and disperse thoroughly.

[0071] 2. Add 0.1 g of azobisisobutyronitrile to the above solution, and react at a constant temperature of 75 °C for 6 h under nitrogen protection. After the reaction is completed, a light yellow transparent polymer adhesive solution is obtained for later use.

[0072] 4. Dissolve 1.25 g of P(BA-co-VBP-co-GMA-co-DMA) in 100 mL of water to prepare a 12.5 g / L aqueous solution of P(BA-co-VBP-co-GMA-co-DMA).

[0073] 5. Take 40 mL of P(BA-co-VBP-co-GMA-co-DMA) aqueous solution.

[0074] 6. At 30°C, slowly add 5g of 1% sodium borohydride solution dropwise to the above-mentioned block polymer aqueous solution.

[0075] 7. Continue adding deionized water to bring the solution to a final volume of 100 mL.

[0076] 8. Take 1g of the washed and dried cotton fabric and immerse it in a finishing agent containing the above-mentioned compound antibacterial agent at a liquor ratio of 1:30. Then, perform the liquid-pulling process on a liquid-pulling machine, and control the liquid carry-over rate at 100±5%.

[0077] 9. Place the rolled fabric in an oven and dry it at 70°C for 30 minutes to initiate the grafting reaction. Then, raise the oven temperature to 210°C and bake for 6 minutes.

[0078] 10. Finally, the above fabric is irradiated under a UV lamp for 30 minutes to obtain a block polymer coated antibacterial and antiviral fabric.

[0079] Explanation of test and characterization results:

[0080] Scanning electron microscope image of the long-lasting antibacterial and antiviral fabric prepared in Example 1 is shown below. Figure 4 As shown, the left image is a low-magnification morphology image of the long-lasting antibacterial and antiviral fabric, and the right image is a high-magnification morphology image of the long-lasting antibacterial and antiviral fabric. The distribution of nanoparticles on the fiber surface can be observed, with no obvious aggregation. This small-particle-size, highly dispersed nano-coating exhibits excellent antibacterial and antiviral effects.

[0081] 2. Antibacterial and antiviral testing: According to GB / T 20944.3-2008 "Evaluation of antibacterial properties of textiles - Part 3: Oscillation method", the fabrics prepared in Examples 1-3 and Comparative Examples 1-2 were tested for their inhibition rates against Escherichia coli and Staphylococcus aureus. The test results are shown in Table 1.

[0082] Table 1. Antibacterial and antiviral test data of the examples and comparative examples.

[0083]

[0084] The test results of Examples 1-3 and Comparative Examples 1-2 show that combining the photocatalytic antibacterial block polymer with nano-copper Cu@Cu x O-coupling significantly improves the antibacterial and antiviral efficiency of fabrics. The prepared fabrics achieve a 100% inhibition rate against Escherichia coli and Staphylococcus aureus, and an inactivation rate of over 99.9% against H1N1 virus. After 30 washes, the inhibition rate against Escherichia coli and Staphylococcus aureus remains at 100%, and the inactivation rate against H1N1 virus remains above 91.7%, showing a significant improvement compared to the control group, indicating its excellent wash resistance.

[0085] Compared to Examples 1 and 2, the H1N1 virus inactivation rate of the fabric after washing in Example 3 was significantly reduced, indicating that the thermal oxidation temperature has a significant impact on the wash fastness of the fabric. This is because nano-copper can only be completely converted into Cu with extremely low water solubility at temperatures above 200°C. x However, below 200°C, due to insufficient reaction temperature, a large amount of water-soluble basic copper carbonate intermediates are generated. After repeated washing, a large amount of basic copper carbonate intermediates are washed out, leading to a decrease in antiviral performance. Therefore, based on the data before and after washing in Example 3, the thermal oxidation temperature needs to reach 200°C.

[0086] Conversely, in Comparative Example 1, if the block polymer lacks photocatalytic antibacterial and antiviral groups, its E. coli inhibition rate will decrease from 100% to 98%, and the H1N1 virus inactivation rate will decrease from 99.9% to 88%; after 30 washes, the E. coli inhibition rate will decrease from 100% to 83%, and the H1N1 virus inactivation rate will decrease from 94% to 71.8%. Similarly, Cu@Cu x Removing O from the fabric coating will also significantly reduce the fabric's antibacterial and antiviral properties.

[0087] Finally, it should be noted that although the present invention has been described in detail above with general descriptions and specific embodiments, the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit it. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features therein; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for preparing an antibacterial and antiviral fiber substrate, characterized in that, The preparation method includes the following steps: S1. Mix the aqueous solution of the block copolymer with the metal salt solution, add ammonia dropwise until the solution first becomes turbid and then becomes clear and transparent again, then add the aqueous solution of the reducing agent to carry out the reduction reaction to obtain the finishing solution; The block copolymer is composed of four monomers: hydroxyethyl methacrylate, 4-hydroxyvinyloxybenzophenone methacrylate, glycidyl methacrylate, and 3-methacryloyldopamine. The metal salt solution is an aqueous solution of copper salt and silver salt; S2. The fabric is immersed in the finishing solution, taken out and squeezed dry, and then successively dried, thermally oxidized and irradiated with ultraviolet light to obtain antibacterial and antiviral fiber substrate.

2. The preparation method according to claim 1, characterized in that, In step S1, the concentration of the block copolymer in the aqueous solution is 1 g / L to 100 g / L; the total mass content of silver and copper in the metal salt solution is 1 to 50 g / L; and the aqueous solution of the block copolymer and the metal precursor solution are mixed at a volume ratio of 4:

1.

3. The preparation method according to claim 1, characterized in that, In step S1, the mass ratio of copper to silver in the metal precursor solution is (1-10):

1.

4. The preparation method according to claim 1, characterized in that, In step S1, the ratio of the total mass of silver and copper to the mass of the reducing agent is 1:(0.5-5); the aqueous solution of the reducing agent is sodium borohydride solution; the temperature of the reduction reaction is 30℃-80℃; and the reduction time is 20-40 min.

5. The preparation method according to claim 1, characterized in that, In step S2, the fiber substrate is a fiber or fabric containing oxygen groups.

6. The preparation method according to claim 1, characterized in that, In step S2, the bath ratio for impregnation is 1:(30-60).

7. The preparation method according to claim 1, characterized in that, In step S2, the rolling drying is performed at room temperature until the liquid content is 50% to 130%; the drying is performed at 60 to 80°C for 30 to 120 minutes.

8. The preparation method according to claim 1, characterized in that, In step S2, the thermal oxidation treatment is performed at 160–250°C for 5–30 min.

9. The preparation method according to claim 1, characterized in that, In step S2, the ultraviolet light irradiation treatment is as follows: ultraviolet light irradiation for 10 to 50 minutes is used to reduce the silver oxidized during the thermal oxidation process back to nano-silver.

10. The antibacterial and antiviral fiber substrate prepared by the preparation method according to any one of claims 1-9.

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