Visible light response anti-static and oil-stain self-cleaning glass spray and preparation thereof

Abstract

This invention relates to the field of self-cleaning glass spray technology, and more specifically, to a visible light-responsive antistatic and anti-oil self-cleaning glass spray and its preparation. The raw materials for the glass spray, by mass percentage, include the following components: solvent system 85.0-93.0%, fluorosilane-modified silica nano-sol 3.0-8.0%, nitrogen-doped nano-titanium dioxide 1.5-5.0%, nano-grade antimony tin oxide 0.5-2.0%, and additives 0.5-1.5%. This invention addresses the shortcomings of existing technologies by providing a glass spray that offers all-weather visible light self-cleaning, dual anti-oil properties, and active electrostatic shielding. It overcomes dependence on ultraviolet light, efficiently decomposing pollutants indoors and on cloudy days; it combines physical anti-fouling with chemical decomposition for long-lasting oil resistance; and it eliminates electrostatic adsorption through an ATO conductive network, reducing dust at the source. The product also boasts advantages such as high light transmittance, quick drying and easy operation, and strong coating adhesion, significantly reducing cleaning costs and being environmentally friendly.

Description

Technical Field

[0001] This invention relates to the field of self-cleaning glass spray technology, and more specifically, to a visible light-responsive antistatic and anti-oil self-cleaning glass spray and its preparation. Background Technology

[0002] With the rapid development of modern architecture and transportation, the application of large-area glass products such as glass curtain walls and automotive glass is becoming increasingly widespread, and their cleaning and maintenance costs are also rising significantly. Traditional glass cleaning methods mainly rely on manual water washing combined with chemical cleaning agents, which not only consumes a lot of manpower and resources, but also easily causes environmental pollution due to the use of chemical cleaning agents, which is contrary to the current demand for green and environmentally friendly development.

[0003] Currently, the mainstream glass self-cleaning technologies on the market are mainly divided into two categories: superhydrophobic technology and photocatalytic technology. Superhydrophobic technology achieves a "lotus effect" by constructing micro-nano rough structures and incorporating low surface energy materials, allowing water droplets to carry away surface dust as they roll off. However, this technology suffers from significant "rain streaks" in practical applications, and in oily environments, oil easily fills the micro-nano rough structures, causing the superhydrophobic properties to quickly fail. Photocatalytic technology uses nano-titanium dioxide (TiO2) as its core, utilizing its catalytic properties under ultraviolet light to decompose organic pollutants. However, traditional TiO2 is only sensitive to ultraviolet light, which accounts for about 3% to 5% of the solar spectrum, and has almost no catalytic activity in environments with low ultraviolet light, such as indoors or on cloudy days. Furthermore, simple photocatalytic coatings lack effective repellency against oily pollutants, and dust still easily accumulates on the glass surface.

[0004] Furthermore, glass surfaces are highly susceptible to attracting airborne dust due to static electricity during use. This issue is often overlooked in the development of existing self-cleaning glass coatings, resulting in a significant reduction in the actual dust-proof performance of most self-cleaning products. Therefore, developing a glass self-cleaning spray that can achieve catalytic self-cleaning under visible light while also possessing excellent oil resistance and anti-static properties has become a pressing technical challenge in the field of functional coatings. Summary of the Invention

[0005] The present invention aims to at least solve one of the technical problems existing in the prior art. To this end, one aspect of the present invention is to provide a visible light responsive antistatic and anti-oil self-cleaning glass spray, wherein the raw materials of the glass spray comprise the following components by mass percentage: 85.0%-93.0% solvent system, 3.0%-8.0% fluorosilane modified silica nano sol, 1.5%-5.0% nitrogen-doped nano titanium dioxide, 0.5%-2.0% nano-grade antimony tin oxide, and 0.5%-1.5% additives.

[0006] Preferably, the nitrogen-doped nano-titanium dioxide is anatase with a particle size of 10-30 nm, used to achieve catalytic activity under visible light.

[0007] Preferably, the nano-sized antimony tin oxide has a particle size of 20-50 nm, ensuring transparency while achieving electrostatic shielding.

[0008] Preferably, the solvent system comprises low-carbon alcohol and deionized water, wherein the mass ratio of low-carbon alcohol to deionized water is 1-4:1. The solvent system serves as a carrier for each functional component, ensuring the spreadability and quick-drying properties of the spray.

[0009] Preferably, the lower alcohol is one or a combination of ethanol and isopropanol.

[0010] Preferably, the additives, silane coupling agent and trace surfactant, are used in a mass ratio of 1 to 5:1. The silane coupling agent is used to enhance the adhesion between the coating and the glass surface, and the trace surfactant is used to adjust the wettability of the spray to ensure uniform spraying.

[0011] Preferably, the silane coupling agent is one or more combinations of KH-550, KH-560, and KH-792.

[0012] Another objective of this invention is to provide a method for preparing a visible light-responsive antistatic and anti-oil self-cleaning glass spray, the specific steps of which are as follows: S1. Pre-dispersion: Mix part of the solvent system, add nitrogen-doped nano-titanium dioxide and nano-sized antimony tin oxide under high-speed shearing, disperse at a speed of 2000-4000 rpm for 30-45 minutes to obtain nano-powder pre-dispersion slurry; S2. Compounding: Transfer the pre-dispersed slurry to the main reactor, add the remaining solvent system, and add the fluorosilane-modified silica nanosol and additives in sequence while stirring; S3. Mixing and aging: Stir continuously for 60-90 minutes to ensure that all components are mixed evenly, then seal and let stand at room temperature for 12-24 hours to age. S4. Filtration: The aged liquid is filtered through a filter with a precision of 5-10μm to obtain a visible light responsive antistatic and anti-oil self-cleaning glass spray.

[0013] Preferably, in S1, a portion of the solvent system accounts for 30% to 50% of the total solvent system, and in S2, the remaining solvent system accounts for 50% to 70% of the total solvent system.

[0014] The beneficial effects of this invention are as follows: All-weather high-efficiency self-cleaning: By using nitrogen-doped modified nano-titanium dioxide, the photocatalytic response range is extended to the visible light region, enabling the spray to continue to decompose organic pollutants on the glass surface even in low-light environments such as indoors and on cloudy days. This breaks through the traditional reliance on ultraviolet light and achieves true all-weather self-cleaning.

[0015] Dual anti-oil properties, long-lasting effect: Combining the low surface energy physical barrier of fluorosilane-modified silica nanosol with the chemical decomposition effect of nitrogen-doped titanium dioxide, it not only prevents oil stains from wetting and adhering, but also actively decomposes residual organic stains, overcoming the shortcomings of a single anti-fouling mechanism and significantly extending the service life of the anti-oil effect.

[0016] Active antistatic properties and significant dust prevention: The innovative introduction of nano-antimony tin oxide (ATO) transparent conductive material constructs a micro-conductive network, reducing the glass surface resistance to 10. 8 -10 10 Ω effectively eliminates static electricity buildup, reducing static adsorption of dust at the source and significantly improving dustproof performance.

[0017] High light transmittance, quick drying, and easy operation: All functional components are nanoscale, the coating is extremely thin and dense, and has almost no impact on the light transmittance of glass, maintaining the original light transmission performance; the alcohol-based solvent system evaporates quickly, and dries naturally in 5-10 minutes after spraying, without the need for wiping, making operation convenient and efficient.

[0018] Strong bonding and long-lasting durability: By using silane coupling agents to achieve chemical bonding between the coating and the glass surface, a stable inorganic-organic hybrid protective film is formed, which has excellent weather resistance, wear resistance and chemical resistance. The protective effect can last for several years and is widely applicable to various indoor and outdoor glass scenarios.

[0019] Additional aspects and advantages of the invention will become apparent from the description which follows, or may be learned by practice of the invention. Detailed Implementation

[0020] To better understand the above-mentioned objectives, features, and advantages of the present invention, the present invention will be further described in detail below with reference to specific embodiments. It should be noted that, unless otherwise specified, the embodiments and features described in these embodiments can be combined with each other.

[0021] Many specific details are set forth in the following description in order to provide a full understanding of the invention. However, the invention may also be implemented in other ways different from those described herein. Therefore, the scope of protection of the invention is not limited to the specific embodiments disclosed below. Example

[0022] Formula: Based on a total mass of 1 kg, the components and amounts are as follows: N-TiO2 powder (anatase crystal form, particle size 20 nm) 30 g, ATO powder (nano-grade antimony tin oxide) (particle size 30 nm) 10 g, fluorosilane modified silica nanosol (solid content 30%) 50 g, silane coupling agent KH-550 5 g, ethanol 600 g, deionized water 305 g.

[0023] preparation S1. Pre-dispersion: Mix 200g of ethanol and 100g of deionized water, add to a high-speed shear mill, turn on the shearing speed of 3000rpm, slowly add 30g of N-TiO2 powder and 10g of ATO powder, and continue shearing and dispersing for 40 minutes to obtain a nano-powder pre-dispersion slurry; S2. Compounding: Transfer the pre-dispersed slurry to the main reactor, add the remaining 400g ethanol and 205g deionized water, stir at 400rpm at room temperature, and then add 50g fluorosilane-modified silica nanosol and 5g silane coupling agent KH-550 in sequence. S3. Mixing and aging: Stir at 400 rpm for 90 minutes, then let it stand at room temperature for 24 hours in a sealed container. S4. Filtration: The aged liquid is filtered through a 5μm precision filter bag, and then filled to obtain the finished product.

[0024] Performance testing: The finished product of this embodiment was sprayed onto a clean and dry automotive windshield surface and allowed to dry naturally before performance testing. The results were: water droplet contact angle > 110°, oil droplet contact angle > 85°, and surface resistivity of 10 Ω·cm. 9 Ω; Compared with the original glass, the light transmittance has no significant change; After 30 days of outdoor exposure, the amount of dust adhering to the glass surface is reduced by 80% compared with ordinary glass, and there are no obvious water marks or oil residues after rain. Example

[0025] Formula: Based on a total mass of 1 kg, the components and amounts are as follows: N-TiO2 powder (anatase crystal form, particle size 10 nm) 20 g, ATO powder (nano-grade antimony tin oxide) (particle size 20 nm) 5 g, fluorosilane modified silica nanosol (solid content 30%) 30 g, silane coupling agent KH-560 5 g, ethanol 700 g, deionized water 240 g.

[0026] preparation S1. Pre-dispersion: Mix 300g of ethanol and 80g of deionized water, add N-TiO2 and ATO powder under high-speed shear at 3000rpm, and disperse for 30 minutes; S2. Compounding: Add the remaining 400g ethanol and 160g deionized water, and add fluorosilane-modified silica nanosol and KH-560 while stirring at 300rpm. S3. Mixing and aging: Stir at 300 rpm for 60 minutes, then age in a sealed container at room temperature for 12 hours; S4. Filtration: The finished product is obtained after filtration through an 8μm precision filter and filling.

[0027] Performance testing: When sprayed onto the surface of building curtain wall glass, after drying, the water droplet contact angle is >105°, the oil droplet contact angle is >80°, and the surface resistivity is 10. 8 Ω; After being placed indoors for 60 days, there is no obvious dust accumulation on the surface, and organic stains such as fingerprints can decompose on their own under natural light. Example

[0028] Formula: Based on a total mass of 1 kg, the components and amounts are as follows: N-TiO2 powder (anatase crystal form, particle size 30 nm) 50 g, ATO powder (nano-grade antimony tin oxide) (particle size 50 nm) 15 g, fluorosilane modified silica nanosol (solid content 30%) 80 g, silane coupling agent KH-792 15 g, ethanol 650 g, deionized water 200 g.

[0029] preparation S1. Pre-dispersion: Mix 250g of ethanol and 50g of deionized water, add N-TiO2 and ATO powder under high-speed shear at 3000rpm, and disperse for 45 minutes; S2. Compounding: Add the remaining 400g ethanol and 150g deionized water, and add fluorosilane-modified silica nanosol and KH-792 while stirring at 500rpm; S3. Mixing and aging: Stir at 500 rpm for 90 minutes, then age in a sealed container at room temperature for 20 hours; S4. Filtration: The finished product is obtained after filtration through a 10μm precision filter and filling.

[0030] Performance testing: When sprayed onto the surface of tempered glass in a bathroom, after drying, the water droplet contact angle is >115°, the oil droplet contact angle is >90°, and the surface resistivity is 10¹⁰. 0 Ω; Even when exposed to oil fumes and water vapor for extended periods, the glass surface remains free of oil stains and water vapor condensation, requiring only a light wipe with water to maintain cleanliness.

[0031] The above description is merely a preferred embodiment of the present invention and is not intended to limit the invention. Various modifications and variations can be made to the invention by those skilled in the art. Any modifications, equivalent substitutions, or improvements made within the spirit and principles of the invention should be included within the scope of protection of the invention.

Claims

1. A visible light-responsive antistatic and anti-oil self-cleaning glass spray, characterized in that: The raw materials for the glass spraying agent comprise the following components by mass percentage: 85.0%-93.0% solvent system, 3.0%-8.0% fluorosilane-modified silica nanosol, 1.5%-5.0% nitrogen-doped nano titanium dioxide, 0.5%-2.0% nano-grade tin antimony oxide, and 0.5%-1.5% additives.

2. The visible light-responsive antistatic and anti-oil self-cleaning glass spray according to claim 1, characterized in that: The nitrogen-doped nano-titanium dioxide is anatase with a particle size of 10-30 nm.

3. The visible light-responsive antistatic and anti-oil self-cleaning glass spray according to claim 1, characterized in that: The nano-sized antimony tin oxide has a particle size of 20-50 nm.

4. The visible light-responsive antistatic and anti-oil self-cleaning glass spray according to claim 1, characterized in that: The solvent system includes a low-carbon alcohol and deionized water, wherein the mass ratio of the low-carbon alcohol to the deionized water is 1-4:

1.

5. The visible light-responsive antistatic and anti-oil self-cleaning glass spray according to claim 4, characterized in that: The lower alcohol is one or a combination of ethanol and isopropanol.

6. The visible light-responsive antistatic and anti-oil self-cleaning glass spray according to claim 1, characterized in that: The additives are a silane coupling agent and a trace amount of surfactant, wherein the mass ratio of the silane coupling agent to the trace amount of surfactant is 1~5:

1.

7. The visible light-responsive antistatic and anti-oil self-cleaning glass spray according to claim 6, characterized in that: The silane coupling agent is one or more combinations of KH-550, KH-560, and KH-792.

8. A method for preparing a visible light-responsive antistatic and anti-oil self-cleaning glass spray according to any one of claims 1-7, characterized in that: The specific steps of the preparation method are as follows: S1. Pre-dispersion: Mix part of the solvent system, add nitrogen-doped nano-titanium dioxide and nano-sized antimony tin oxide under high-speed shearing, disperse at a speed of 2000-4000 rpm for 30-45 minutes to obtain nano-powder pre-dispersion slurry; S2. Compounding: Transfer the pre-dispersed slurry to the main reactor, add the remaining solvent system, and add the fluorosilane-modified silica nanosol and additives in sequence while stirring; S3. Mixing and aging: Stir continuously for 60-90 minutes to ensure that all components are mixed evenly, then seal and let stand at room temperature for 12-24 hours to age. S4. Filtration: The aged liquid is filtered through a filter with a precision of 5-10μm to obtain a visible light responsive antistatic and anti-oil self-cleaning glass spray.

9. The preparation method of a visible light-responsive antistatic and anti-oil self-cleaning glass spray according to claim 8, characterized in that: In S1, a portion of the solvent system accounts for 30% to 50% of the total solvent system, and in S2, the remaining solvent system accounts for 50% to 70% of the total solvent system.