Antibacterial and antifogging glasses wiping cloth and preparation method thereof

Abstract

The invention provides antibacterial and antifogging glasses wiping cloth and a preparation method thereof, and relates to the technical field of glasses cleaning. Comprising a base material layer, the base material layer is a fiber fabric internally provided with a micropore structure, the fiber fabric is formed by blending sea-island fibers and bamboo charcoal fibers, an antibacterial layer is arranged on the surface of the base material layer, an anti-fog layer is sprayed on the surface of the base material layer, and the antibacterial layer is formed after the base material layer is soaked in composite antibacterial liquid and cured. The composite antibacterial liquid comprises quaternary ammonium salt modified chitosan and polyhexamethylene biguanide, the quaternary ammonium salt modified chitosan is covalently bonded with the fiber surface through an epoxy group cross-linking agent, the polyhexamethylene biguanide is dispersed in the microporous structure, and the anti-fog layer is formed by a sulfobetaine methacrylate polymer grafted on the surface of the base material layer. And a modified nano TiO2-SiO2 core-shell structure is embedded in the zwitterionic polymer. The 24-hour antibacterial rate of the glasses wiping cloth is greater than 99%; after 50 times of standard washing, the antibacterial rate is still greater than or equal to 95%; the antifogging duration is longer than or equal to 33 days and far exceeds that of a temporary coating.

Description

Technical Field

[0001] The present invention relates to the technical field of glasses cleaning, in particular to an antibacterial and anti-fog glasses wiping cloth and a preparation method thereof. Background Art

[0002] Glasses are essential tools for vision correction or eye protection, and their cleaning and maintenance directly impact the wearer's visual clarity and eye health. As one of the most commonly used cleaning tools, the performance of glasses cloths directly impacts the cleaning effect, anti-fogging capabilities, and long-term hygiene of glasses. However, most common glasses cloths currently available only provide basic wiping functions, failing to effectively inhibit bacterial growth and lacking anti-fogging capabilities. This results in a poor user experience and may even lead to eye infections due to bacterial contamination.

[0003] Existing glasses cloths have insufficient antibacterial properties. Ordinary glasses cloths are mostly made of pure cotton, microfiber or polyester. Although they have certain cleaning capabilities, their fiber structure does not have antibacterial properties. After long-term use, they are prone to accumulate sebum, dust and microorganisms (such as Staphylococcus aureus, Escherichia coli, etc.). Studies have shown that the bacterial content of glasses cloth can be as high as 10 after one week of use. 4 ~10 5 CFU / cm 2 , far higher than the sanitary standard (<100CFU / cm 2 ), which may cause eye diseases such as conjunctivitis and blepharitis. In existing technologies, the antibacterial properties of eyeglass cloths are enhanced by adding antimicrobial agents (such as silver ions and nano-zinc oxide), but the following problems still exist: high cost and the risk of allergies (such as contact dermatitis) due to metal ion migration; they are prone to agglomeration in humid environments, reducing antibacterial efficiency, and long-term use may release nanoparticles due to wear and tear, which poses potential biological toxicity; organic antimicrobial agents (such as quaternary ammonium salts) are easily removed during the wiping process, and their antibacterial properties are poorly durable, usually lasting only a few days to a week.

[0004] Glasses fog up when the lens surface temperature drops below the ambient dew point, causing water vapor to condense into tiny droplets, which scatter light. Current anti-fog solutions on the market primarily include: surfactant coatings (such as polyethylene glycol and glycerol derivatives), which spread condensed water into a film by lowering the water contact angle, but are easily destroyed by wiping or washing, and their anti-fog effect typically only lasts a few hours to a day; hydrophobic anti-fog coatings (such as fluorosilanes), which can delay fogging but cannot completely prevent it and may affect light transmittance; and physical anti-fog methods (such as heated lenses), which are not suitable for ordinary glasses cloths and consume a lot of energy.

[0005] It is difficult to strike a balance between cleaning ability and functionality. Traditional glasses cloths usually focus on a single function: microfiber cloths have strong adsorption power but no antibacterial or anti-fog capabilities; alcohol-containing wipes have short-term sterilization capabilities but may damage the lens coating and cannot provide long-term anti-fog effects; anti-static glasses cloths can reduce dust adsorption but are ineffective against bacteria and fog. Summary of the Invention

[0006] The present invention provides an antibacterial and anti-fog glasses wiping cloth and a preparation method thereof, which optimizes the fiber base material, sets a dual antibacterial system and a covalently grafted anti-fog layer, and improves the technical problems of existing glasses cloths such as the short-lasting antibacterial performance and the difficulty in compatibility between the anti-fog function and the cleaning function.

[0007] Disclosed is an antibacterial and anti-fog glasses wiping cloth, comprising a substrate layer, wherein the substrate layer is a fiber fabric with a microporous structure provided therein, the fiber fabric being made of a blend of sea-island fibers and bamboo charcoal fibers; an antibacterial layer being provided on the surface of the substrate layer; and an anti-fog layer being sprayed on the surface of the substrate layer, wherein the antibacterial layer is formed by impregnating the substrate layer with a composite antibacterial liquid, the composite antibacterial liquid comprising quaternary ammonium salt-modified chitosan and polyhexamethylene biguanide, the quaternary ammonium salt-modified chitosan being covalently bonded to the fiber surface via an epoxy crosslinking agent, the polyhexamethylene biguanide being dispersed within the microporous structure, the anti-fog layer being composed of a sulfobetaine methacrylate polymer grafted to the surface of the substrate layer, and the zwitterionic polymer having an embedded modified nano-TiO2-SiO2 core-shell structure.

[0008] Compared to the physical adsorption of a single antimicrobial agent in the prior art, the present invention utilizes a composite antimicrobial solution composed of quaternary ammonium salt-modified chitosan and polyhexamethylene biguanide. The quaternary ammonium salt-modified chitosan is covalently bonded to the fiber surface via an epoxy crosslinker, providing long-lasting antimicrobial efficacy. The polyhexamethylene biguanide is dispersed within the microporous structure of the substrate layer, enabling real-time sterilization and effectively enhancing the durability of the antimicrobial effect. Compared to the prior art's anti-fog layer, which mechanically bonds to the substrate, the present invention's anti-fog layer is composed of a sulfobetaine methacrylate polymer grafted onto the substrate surface, chemically bonding to prevent shedding. A modified nano-TiO2-SiO2 core-shell structure is directionally embedded within the sulfobetaine methacrylate polymer, ensuring both the anti-fog and cleansing functions of the eye wipe. Compared to the prior art's substrate layer, which utilizes a conventional fiber substrate, the present invention utilizes a microporous structure blended with sea-island fibers and bamboo charcoal fibers. The micropores are used to absorb oil and grease, while the bamboo charcoal fibers enhance the antimicrobial agent loading, significantly increasing the substrate layer's specific surface area and safety.

[0009] Quaternary ammonium chitosan and polyhexamethylene biguanide are typically difficult to combine due to charge repulsion. This invention achieves synergistic antimicrobial properties through targeted curing with an epoxy crosslinker and physically oriented microporous embedding. Combining a photocatalytic TiO2 core with an inert SiO2 shell preserves the ability to degrade organic matter while preventing direct skin contact with the nanoparticles.

[0010] Furthermore, the sea-island fibers include polyester and nylon, the mass ratio of polyester to nylon in the sea-island fibers is 2-3:1, the mass ratio of the sea-island fibers to bamboo charcoal fibers is 4-5.5:1, and the fiber diameters of the sea-island fibers and bamboo charcoal fibers are ≤0.5 μm.

[0011] Furthermore, the microporous structure is honeycomb-shaped, with a pore diameter of 50 to 200 nanometers, the specific surface area of ​​the bamboo charcoal fiber is ≥800 m2 / g, and the ash content is ≤3%.

[0012] Furthermore, the epoxy crosslinking agent includes ethylene glycol diglycidyl ether or γ-glycidyl ether oxypropyl trimethoxysilane; the molecular weight of the quaternary ammonium salt modified chitosan is ≤10kDa, the quaternization degree is ≥80%, the crosslinking density with the fiber is 0.5-1.2mmol / g, and the molecular weight of the polyhexamethylene biguanide is 2000-4000Da.

[0013] Furthermore, the grafting rate of sulfobetaine methacrylate on the substrate layer is 1.5 to 3.5 mg / m2, and the thickness of the anti-fog layer is 100 to 300 nm.

[0014] Furthermore, the preparation method of the modified nano-TiO2-SiO2 core-shell structure comprises: hydrolyzing tetrabutyl titanate to generate TiO2 core, and then The SiO2 shell was coated by the method, and the shell surface was modified by KH-570 silane coupling agent.

[0015] The SiO2 shell thickness is 5 to 10 nm, and the mass ratio of the modified KH-570 to the modified nano-TiO2-SiO2 core-shell structure is 1.5 to 3.0:100. In the actual preparation process, using the following specific preparation method, the shell thickness values ​​of the modified nano-TiO2-SiO2 core-shell structure obtained all fall within the range of 5 to 10 nm. After modifying the shell surface with KH-570 silane coupling agent, the mass ratio of the KH-570 silane coupling agent on the nano-TiO2-SiO2 core-shell structure obtained by coupling to the mass ratio of the modified nano-TiO2-SiO2 core-shell structure all fall within the range of 1.5 to 3.0:100. In other words, the modified nano-TiO2-SiO2 core-shell structure obtained is a mixture of unequal particle sizes and masses.

[0016] A preparation method for preparing the antibacterial and anti-fog glasses wiping cloth comprises the following steps:

[0017] S100, pretreatment of the substrate layer: placing the substrate layer in a plasma treatment device, and treating it for 1 to 3 minutes at a power of 40 to 60 W and in an oxygen atmosphere;

[0018] S200, immersing the pretreated substrate layer in a composite antibacterial solution, adjusting the pH to 5.0-6.0, the immersion time to 15-30 minutes, and the residual rate to 70-80%;

[0019] S300, drying and curing: pre-baking at 60-70℃ for 5-10min, cross-linking at 80-90℃ for 20-40min, and setting at 100-120℃ for 1-2h;

[0020] S400, anti-fog layer construction: spray the composite anti-fog solution on the substrate layer under nitrogen protection, 200 ~ 400mJ / cm 2 UV light curing for 30 to 60 seconds.

[0021] The rolling rate refers to the mass ratio of the weight increase of the substrate layer after impregnation to the original unimpregnated substrate layer. A rolling rate of 70-80% ensures that the microporous structure of the substrate layer fully absorbs the antibacterial liquid, but does not cause surface conjunctiva due to excessive amount.

[0022] UV light curing energy 200~400mJ / cm 2 If the content is too low, the polymerization degree will be insufficient and the gel fraction will be less than 80%. If the content is too high, the fiber will turn yellow.

[0023] Compared to the existing single plasma treatment in air atmosphere, the present invention uses an oxygen atmosphere with precise power control of 40-60W, which can generate more carboxyl groups, reduce the fiber damage rate to less than 5%, and effectively improve the efficiency of subsequent covalent bonding of antimicrobial agents. Compared to the one-step drying method, the present invention adopts gradient curing, low-temperature pre-drying to remove moisture, medium-temperature cross-linking, and high-temperature setting, effectively avoiding thermal degradation of chitosan. Compared to solvent-based UV curing, the present invention uses a water-based anti-fog liquid with nitrogen protection for UV curing, effectively suppressing oxygen inhibition, reducing curing energy consumption, and achieving low-temperature rapid film formation.

[0024] The present invention uses plasma treatment to increase the carboxyl density on the fiber surface by 3 times, forming covalent bonds with the subsequent epoxy crosslinker rather than physical adsorption; during gradient drying, the 80-90°C crosslinking temperature just matches the epoxy ring-opening temperature of quaternary ammonium salt chitosan, while the traditional process causes excessive brittle crosslinking due to the high temperature (>100°C).

[0025] Furthermore, in step S200, the solvent of the composite antibacterial liquid is deionized water, the mass ratio of the quaternary ammonium salt-modified chitosan to deionized water is 0.01-0.02:1, and the mass ratio of the quaternary ammonium salt-modified chitosan to polyhexamethylene biguanide is 5-40:1.

[0026] Furthermore, the composite antibacterial liquid also includes polyethylene glycol 400, a penetrant JFC and an epoxy crosslinker. The mass fraction of the polyethylene glycol 400 in the composite antibacterial liquid is 0.01 to 0.1%, the mass fraction of the penetrant JFC in the composite antibacterial liquid is 0.01 to 0.1%, and the added amount of the epoxy crosslinker is 5 to 15% of the mass of the quaternary ammonium salt-modified chitosan.

[0027] Furthermore, the composite anti-fog solution comprises the following components in parts by weight:

[0028] 5-10 parts of sulfobetaine methacrylate monomer, 11731-3 parts of photoinitiator, 0.5-2 parts of embedded modified nano-TiO2-SiO2 core-shell structure, 70-80 parts of ethanol, 20-30 parts of deionized water, 1-3 parts of propylene glycol methyl ether, and 0.5-1 part of polyethylene glycol 4000.

[0029] Advantageous Effects of the Invention

[0030] The eyeglass cleaning cloth has excellent antibacterial properties, achieving a 24-hour inhibition rate of >99% against Escherichia coli and Staphylococcus aureus. Even after 50 standard washes, the inhibition rate remains at ≥95%. No metal ions are released. The cloth also exhibits significant anti-fog properties, lasting for ≥30 days, far exceeding that of temporary coatings. It remains effective in environments with humidity >90%.

[0031] Silane coupling agent KH-570: γ-methacryloxypropyltrimethoxysilane;

[0032] Da is the unit of relative molecular mass, the abbreviation of Dalton. DETAILED DESCRIPTION

[0033] Example 1

[0034] The substrate layer is a fiber fabric with a honeycomb-like microporous structure of 100 nm. The fabric is made from a blend of island-in-the-sea fibers and bamboo charcoal fibers in a 5:1 mass ratio. The mass ratio of polyester to nylon in the island-in-the-sea fibers is 2.5:1. The fiber diameters of the island-in-the-sea fibers and bamboo charcoal fibers are 0.3 μm. The microporous structure is honeycomb-like with pores of 100 nm. The bamboo charcoal fibers have a specific surface area of ​​1000 m2 / g and an ash content of 2%.

[0035] A method for preparing an antibacterial and anti-fog glasses wiping cloth comprises the following steps:

[0036] S100, pretreatment of the substrate layer: placing the substrate layer in a plasma treatment device and treating it for 2 minutes at a power of 50W and in an oxygen atmosphere;

[0037] S200, immersing the pretreated substrate layer in a composite antibacterial solution, adjusting the pH to 5.5, the immersion time to 25 minutes, and the residual rate to 75%;

[0038] The composite antibacterial solution comprises 60g of quaternary ammonium salt-modified chitosan, 3g of polyhexamethylene biguanide, 6g of ethylene glycol diglycidyl ether, 4000g of deionized water, 2g of polyethylene glycol 400, and 2g of penetrant JFC, and the mixture is uniformly mixed. The molecular weight of the polyhexamethylene biguanide is 4000Da.

[0039] S300, drying and curing: pre-baking at 65℃ for 8min, cross-linking at 85℃ for 30min, setting at 110℃ for 1.5h;

[0040] S400, anti-fog layer construction: spray the composite anti-fog solution on the substrate layer under nitrogen protection, 300mJ / cm 2 UV light curing for 45s;

[0041] The composite anti-fog solution contains 70g of sulfobetaine methacrylate monomer, 117320g of photoinitiator, 12g of modified nano-TiO2-SiO2 core-shell structure, 750g of ethanol, 250g of deionized water, 20g of propylene glycol methyl ether, and 8g of polyethylene glycol 400.

[0042] The quaternization degree of the prepared antibacterial and anti-fog glasses wiping cloth is 90%, the cross-linking density with the fiber is 0.9 mmol / g, and the grafting rate of sulfobetaine methacrylate on the substrate layer is 2.5 mg / m 2 , anti-fog layer thickness 200nm.

[0043] Example 2

[0044] The substrate layer is a fiber fabric with a honeycomb-shaped 50nm microporous structure inside. The fiber fabric is made of a blend of sea island fiber and bamboo charcoal fiber in a mass ratio of 4:1. The mass ratio of polyester and nylon in the sea island fiber is 2:1. The fiber diameter of the sea island fiber and bamboo charcoal fiber is 0.3μm. The specific surface area of ​​the bamboo charcoal fiber is 800㎡ / g, and the ash content is 1%.

[0045] A method for preparing an antibacterial and anti-fog glasses wiping cloth comprises the following steps:

[0046] S100, pretreatment of the substrate layer: placing the substrate layer in a plasma treatment device and treating it for 1 minute at a power of 40W and in an oxygen atmosphere;

[0047] S200, immersing the pretreated substrate layer in a composite antibacterial solution, adjusting the pH to 5.0, the immersion time to 15 to 30 minutes, and the residual rate to 70 to 80%;

[0048] The composite antibacterial solution contains 60g of quaternary ammonium salt modified chitosan, 12g of polyhexamethylene biguanide, 3g of γ-glycidyloxypropyltrimethoxysilane, 6000g of deionized water, 4g of polyethylene glycol 400, and 4g of penetrant JFC, and is mixed evenly. The molecular weight of the polyhexamethylene biguanide is 2000Da.

[0049] S300, drying and curing: pre-baking at 60℃ for 10min, cross-linking at 80℃ for 40min, and setting at 100℃ for 2h;

[0050] S400, anti-fog layer construction: spray the composite anti-fog solution on the substrate layer under nitrogen protection, 200mJ / cm 2 UV light curing for 60s;

[0051] The composite anti-fog solution includes the following components: 50g of sulfobetaine methacrylate monomer, 10g of photoinitiator 1173, 5g of modified nano-TiO2-SiO2 core-shell structure, 700g of ethanol, 200g of deionized water, 10g of propylene glycol methyl ether, and 5g of polyethylene glycol 400.

[0052] The prepared antibacterial and anti-fog glasses wiping cloth has a quaternization degree of 80% for the quaternary ammonium salt-modified chitosan, a cross-linking density of 0.5 mmol / g with the fiber, and a grafting rate of sulfobetaine methacrylate on the substrate layer of 1.5 mg / m 2 , anti-fog layer thickness is 100nm.

[0053] Example 3

[0054] The substrate layer is a fiber fabric with a honeycomb-like microporous structure (200 nm in diameter). The fabric is made from a blend of island-in-the-sea fibers and bamboo charcoal fibers in a 5.5:1 weight ratio. The weight ratio of polyester to nylon in the island-in-the-sea fibers is 3:1. The fiber diameters of the island-in-the-sea fibers and bamboo charcoal fibers are 0.5 μm. The bamboo charcoal fibers have a specific surface area of ​​1200 m2 / g and an ash content of 3%.

[0055] A method for preparing an antibacterial and anti-fog glasses wiping cloth comprises the following steps:

[0056] S100, substrate layer pretreatment: placing the substrate layer in a plasma treatment device and treating it for 3 minutes at a power of 60W and in an oxygen atmosphere;

[0057] S200, immersing the pretreated substrate layer in a composite antibacterial solution, adjusting the pH to 6.0, the immersion time to 30 minutes, and the residual rate to 80%;

[0058] The composite antibacterial solution contains 60g of quaternary ammonium salt modified chitosan, 1.5g of polyhexamethylene biguanide, 9g of ethylene glycol diglycidyl ether, 3kg of deionized water, 0.4g of polyethylene glycol 400, and 0.4g of penetrant JFC, and is mixed evenly. The molecular weight of the polyhexamethylene biguanide is 3000Da.

[0059] S300, drying and curing: pre-baking at 70℃ for 5min, cross-linking at 90℃ for 20min, and setting at 120℃ for 1h;

[0060] S400, anti-fog layer construction: spray the composite anti-fog solution on the substrate layer, and cure it under 400mJ / cm2 UV light for 30 to 60s under nitrogen protection;

[0061] The composite anti-fog solution comprises the following components:

[0062] 100g sulfobetaine methacrylate monomer, 30g photoinitiator 1173, 20g modified nano-TiO2-SiO2 core-shell structure, 800g ethanol, 300g deionized water, 30g propylene glycol methyl ether, and 10g polyethylene glycol 400.

[0063] The antibacterial and anti-fog glasses cleaning cloth has a quaternization degree of ≥91% for the quaternary ammonium salt-modified chitosan, a fiber crosslinking density of 1.2 mmol / g, a grafting rate of sulfobetaine methacrylate on the substrate layer of 3.5 mg / m2, and an anti-fog layer thickness of 300 nm.

[0064] Comparative Example 1

[0065] The antibacterial liquid only uses chitosan modified with a single quaternary ammonium salt, and other parameters are the same as those in Example 1.

[0066] Comparative Example 2

[0067] The anti-fog layer is not embedded with the modified nano-TiO2-SiO2 core-shell structure, and other parameters are the same as those in Example 1.

[0068] Comparative Example 3

[0069] In the preparation method, the plasma treatment in step S100 is omitted, and other parameters are the same as those in Example 1.

[0070] Comparative Example 4

[0071] In the preparation method, step S300 is changed to constant temperature curing at 110° C., and other parameters are the same as those in Example 1.

[0072] The performance parameters of the antibacterial and anti-fog glasses wiping cloths prepared in Examples 1-3 and Comparative Examples 1-4 are shown in Table 1.

[0073] Table 1 Performance parameters of antibacterial anti-fog glasses wiping cloths prepared in Examples 1-3 and Comparative Examples 1-4

[0074]

[0075] As shown in Table 1, the antibacterial and anti-fog glasses wipes prepared by the raw material ratios and methods of Examples 1-3 have broad-spectrum antibacterial properties, with a 24-hour antibacterial rate of 99.9% against Escherichia coli and Staphylococcus aureus, and have long-lasting antibacterial properties, with an antibacterial rate exceeding 95% after 50 washes; the anti-fog effect can be sustained for ≥33 days, far exceeding that of temporary coatings; and the antibacterial agent residual rate is <10 μg / cm 2 , far surpassing similar products in supermarkets.

[0076] In Comparative Example 1, the antibacterial solution used only chitosan modified with a single quaternary ammonium salt, resulting in an antibacterial rate reduced to 58.6% after 50 washes. In Comparative Example 2, the modified nano-TiO2-SiO2 core-shell structure was not embedded, resulting in an anti-fog effect on the lenses for only 7 days after wiping, far less than the 35 days in Example 1. In Comparative Example 3, the substrate layer was not plasma-treated, preventing the generation of carboxyl groups on the substrate surface. This significantly reduced the bonding between the substrate layer and the antibacterial layer, and the connection between the antibacterial agent and the substrate was primarily physical adsorption, resulting in an anti-fog effect of only 18 days, far less than the 35 days in Example 1. In Comparative Example 4, step S300 was cured at 110°C, resulting in decomposition of the chitosan and an antibacterial effect of only 15 days, at which point the anti-fog layer cracked.

[0077] The present invention adopts quaternary ammonium salt modified chitosan and polyhexamethylene biguanide as the composite antibacterial liquid, and uses sulfobetaine methacrylate polymer grafted on the surface of the substrate layer and embedded modified nano-TiO2-SiO2 core-shell structure as the composite anti-fog layer. In combination with plasma treatment of the substrate layer and gradient temperature curing of the antibacterial layer, the present invention has excellent antibacterial performance and significant anti-fog performance.

[0078] The modified nano-TiO2-SiO2 core-shell structures used in Examples 1-3 and Comparative Examples 1 and 3-4 were all prepared using the following preparation method. The specific preparation method includes the following:

[0079] Raw materials: titanium source: tetrabutyl titanate (TBOT, ≥99%), titanium tetrachloride (TiCl4); silicon source: tetraethyl orthosilicate (TEOS, ≥98%); surface modifier: silane coupling agent KH-570; solvent: anhydrous ethanol, deionized water; catalyst: ammonia (25-28%), hydrochloric acid (0.1M).

[0080] Equipment: magnetic stirring reactor, constant temperature water bath, centrifuge (≥10000rpm), vacuum drying oven, ultrasonic disperser.

[0081] Preparation steps:

[0082] Step 1: Synthesis of TiO2 nanocores (sol-gel method)

[0083] 1. Slowly drop 10 ml of tetrabutyl titanate (TBOT) into 40 ml of anhydrous ethanol and stir magnetically (500 rpm) to form solution A.

[0084] 2. Mix 20 ml of deionized water with 5 ml of concentrated hydrochloric acid (pH ≈ 1), add solution A dropwise, and react at room temperature for 2 hours to generate a transparent TiO2 sol;

[0085] 3. Transfer the sol to a hydrothermal reactor and react at 180°C for 12 h. Collect the white TiO2 nanoparticles by centrifugation, wash them with ethanol three times, and dry them in a vacuum at 60°C.

[0086] Step 2: SiO2 shell coating ( Law)

[0087] 1. Disperse 0.5 g of TiO2 nanoparticles in 100 ml of ethanol / water mixture (volume ratio 4:1) and sonicate for 30 min.

[0088] 2. Add 2 ml of ammonia water, slowly add 1 ml of TEOS dropwise (drop rate 0.1 ml / min) while stirring, and react at 40°C for 6 h;

[0089] 3. Centrifuge to obtain nano-TiO2-SiO2 core-shell structure, wash with ethanol to remove unreacted TEOS, and dry at 80℃.

[0090] Step 3: Surface modification (KH-570 grafting)

[0091] 1. Disperse 0.3g of nano-TiO2-SiO2 core-shell structure in 50ml of ethanol, add 1ml of KH-570, and reflux at 70℃ for 4h;

[0092] 2. Collect the modified core-shell structure by centrifugation, wash with ethanol three times, and dry at 60°C for later use.

Claims

1. An antibacterial and anti-fog glasses wiping cloth, characterized in that: The substrate layer comprises a fiber fabric with a microporous structure inside, the fiber fabric is made of a blend of sea-island fiber and bamboo charcoal fiber, an antibacterial layer is provided on the surface of the substrate layer, and an anti-fog layer is sprayed on the surface of the substrate layer. The antibacterial layer is formed by impregnating a substrate layer with a composite antibacterial liquid and curing the resulting liquid. The composite antibacterial liquid comprises quaternary ammonium salt-modified chitosan and polyhexamethylene biguanide. The quaternary ammonium salt-modified chitosan is covalently bonded to the fiber surface via an epoxy crosslinker. The polyhexamethylene biguanide is dispersed within the microporous structure. The anti-fog layer is composed of a sulfobetaine methacrylate polymer grafted onto the surface of the substrate layer. The zwitterionic polymer is embedded in a modified nano-TiO2-SiO2 core-shell structure.

2. The antibacterial anti-fog glasses wiping cloth according to claim 1, characterized in that: The sea-island fibers include polyester and nylon, the mass ratio of polyester to nylon in the sea-island fibers is 2-3:1, the mass ratio of the sea-island fibers to bamboo charcoal fibers is 4-5.5:1, and the fiber diameters of the sea-island fibers and bamboo charcoal fibers are ≤0.5 μm.

3. The antibacterial anti-fog glasses wiping cloth according to claim 1, characterized in that: The microporous structure is honeycomb-shaped, with a pore diameter of 50 to 200 nanometers. The specific surface area of ​​the bamboo charcoal fiber is ≥800 m2 / g, and the ash content is ≤3%.

4. The antibacterial anti-fog glasses wiping cloth according to claim 1, characterized in that: The epoxy crosslinking agent includes ethylene glycol diglycidyl ether or gamma-glycidyl ether oxypropyl trimethoxysilane; the quaternization degree of the quaternary ammonium salt modified chitosan is greater than or equal to 80%, and the crosslinking density with the fiber is 0.5-1.2 mmol / g.

5. The antibacterial anti-fog glasses wiping cloth according to claim 1, characterized in that: The grafting rate of sulfobetaine methacrylate on the substrate layer is 1.5-3.5 mg / m 2 , the thickness of the anti-fog layer is 100~300nm.

6. The antibacterial anti-fog glasses wiping cloth according to claim 1, characterized in that: The preparation method of the modified nano-TiO2-SiO2 core-shell structure comprises: hydrolyzing tetrabutyl titanate to generate TiO2 core, and then The SiO2 shell is coated by a method, and finally the shell surface is modified with KH-570 silane coupling agent; the thickness of the SiO2 shell is 5 to 10 nm, and the mass ratio of KH-570 to the modified nano-TiO2-SiO2 core-shell structure is 1.5 to 3.0:

100.

7. A preparation method, characterized in that: The method for preparing the antibacterial and anti-fog glasses wiping cloth according to any one of claims 1 to 6 comprises the following steps: S100, pretreatment of the substrate layer: placing the substrate layer in a plasma treatment device, and treating it for 1 to 3 minutes at a power of 40 to 60 W and in an oxygen atmosphere; S200, immersing the pretreated substrate layer in a composite antibacterial solution, adjusting the pH to 5.0-6.0, the immersion time to 15-30 minutes, and the residual rate to 70-80%; S300, drying and curing: pre-baking at 60-70℃ for 5-10min, cross-linking at 80-90℃ for 20-40min, and setting at 100-120℃ for 1-2h; S400, anti-fog layer construction: spray the composite anti-fog solution on the substrate layer under nitrogen protection, 200 ~ 400mJ / cm 2 UV curing for 30 to 60 seconds.

8. The preparation method according to claim 7, characterized in that In step S200, the solvent of the composite antibacterial liquid is deionized water, the mass ratio of the quaternary ammonium salt-modified chitosan to deionized water is 0.01-0.02:1, and the mass ratio of the quaternary ammonium salt-modified chitosan to polyhexamethylene biguanide is 5-40:

1.

9. The preparation method according to claim 8, characterized in that The composite antibacterial liquid also includes polyethylene glycol 400, a penetrant JFC and an epoxy crosslinking agent. The mass fraction of the polyethylene glycol 400 in the composite antibacterial liquid is 0.01 to 0.1%, the mass fraction of the penetrant JFC in the composite antibacterial liquid is 0.01 to 0.1%, and the added amount of the epoxy crosslinking agent is 5 to 15% of the mass of the quaternary ammonium salt-modified chitosan.

10. The preparation method according to claim 7, characterized in that The composite anti-fog solution comprises the following components in parts by weight: 5-10 parts of sulfobetaine methacrylate monomer, 1-3 parts of photoinitiator 1173, 0.5-2 parts of modified nano-TiO2-SiO2 core-shell structure, 70-80 parts of ethanol, 20-30 parts of deionized water, 1-3 parts of propylene glycol methyl ether, and 0.5-1 part of polyethylene glycol 4000.

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