High-temperature-resistant coated heat-insulating tempered glass and preparation method thereof

Abstract

The application discloses a kind of heat insulation coating film toughened glass and preparation method, it is characterized in that, as follows preparation step: in oxide semiconductor nanoparticles join organosilicon oligomer, titanium coupling agent, water-soluble bismuth or zinc salt, alkyne diol type defoaming agent and organic solvent composition heat insulation coating slurry, glass original piece is cleaned, remove static electricity, again heat insulation coating slurry is roller coated or sprayed to ordinary glass matrix surface, and is heated at 160~280 degrees Celsius for 3~5 minutes to carry out solidification, then advance toughened furnace, at 650~700 degrees Celsius is heated for 5~15 minutes to carry out toughening, after cooling, obtain high-temperature-resistant heat insulation coating film toughened glass;The beneficial effects of the application: organosilicon oligomer substantially improves the mechanical strength of coating film, nitrate or acetate eliminates the existence of micropore in the sintering process, solve the problem of a large number of voids in the sintering process of organosilicon, oxide semiconductor nanoparticles are used as heat insulation material to improve the high-temperature-resistant effect of coating film.

Description

Technical Field

[0001] This invention belongs to the field of glass product technology, specifically relating to a heat-insulating coated tempered glass and its preparation method. Background Technology

[0002] The solar spectrum has a wavelength range of 300–2500 nanometers, while the heat energy generated by sunlight is mainly concentrated in the infrared portion, specifically the 800–2500 nanometer band. Therefore, for architectural glass to have heat insulation properties, it needs to allow more visible light to pass through while blocking as much of the infrared spectrum of sunlight as possible, thereby achieving energy-saving effects.

[0003] Currently, energy-saving low-emissivity glass dominates the market, including Low-E glass and high-insulation float glass. Low-E glass is a multi-layered coated thin-film glass. Its heat-insulating infrared reflective layer is mainly applied using online chemical vapor deposition or offline vacuum magnetron sputtering methods, sputtering physical barrier layers, ITO (or ATO) layers, and nano-metal layers onto the glass surface multiple times. However, Low-E glass heat-insulating coatings have some drawbacks. For example, the raw materials and equipment used for vacuum coating are expensive, the Low-E layer film has low strength, and the metallic silver film in the Low-E layer is very prone to oxidation. Therefore, to avoid damage and oxidation during use and to improve its durability, Low-E glass usually requires a double-layer vacuum structure to achieve the effect of protecting the heat-insulating layer. However, this leads to high usage and construction costs for Low-E glass.

[0004] High-insulation float glass utilizes existing mature float glass production technology, incorporating nanoparticles as glass forming agents in the glass raw materials. The resulting glass sheet, in addition to possessing the high light transmittance, good mechanical strength, and weather resistance inherent in float glass, also exhibits high heat insulation and UV blocking capabilities. Compared to Low-E glass, high-insulation float glass boasts higher mechanical strength, better weather resistance, and significantly lower manufacturing and usage costs. However, the photothermal properties of high-insulation float glass differ considerably from ordinary Low-E and float glass. The main difference lies in the fact that high-insulation float glass, through the addition of functional nanoparticles, absorbs a large amount of infrared radiation in the 800–2500 nanometer range, minimizing the transmission of the infrared portion of the solar spectrum; while ordinary float glass allows most of the infrared portion of sunlight to pass through. For example, the F-green tinted float glass commonly used in the automotive glass industry has a much higher infrared transmittance than high-barrier float glass. However, whether high-insulation float glass is used as a single pane or as the inner layer of insulated glass, its absorption of infrared heat energy from sunlight increases its secondary heat transfer coefficient. Therefore, although high-insulation float glass has good strength, its actual heat insulation performance is somewhat insufficient compared to Low-E glass, and further improvement faces significant technical challenges.

[0005] To overcome the high cost and poor weather resistance of Low-E glass for thermal insulation, and the strong infrared absorption of high-insulation float glass, Lu Ye et al. proposed a transparent temperable thermal insulation glass and its processing method (CN107935404A). They proposed a technical approach of coating the glass surface with a layer containing nano-antimony tin oxide (ATO). They used large-particle-size silica sol, high-viscosity high-molecular-weight hydroxyl silicone oil, polyether-modified silicone oil with a molecular weight exceeding 6000, organosilicon oligomers, coupling agents, and organic solvents as the coating liquid for the film-forming slurry. Then, using a roller coating process, the above coating liquid was applied to the surface of ordinary glass. Through drying and glass tempering processes, the nano-ATO and silica were retained on the glass surface, thus obtaining thermal insulation tempered glass with infrared reflection effects.

[0006] However, the above-mentioned technical solutions still have significant shortcomings. First, high molecular weight organosilicon is not conducive to sintering and film formation. Linear macromolecules have long molecular chains and significant steric hindrance between molecules. During high-temperature baking and curing, the cross-linking density between organosilicon molecules is low, resulting in more voids on the film surface and inside during sintering, leading to reduced film strength. Second, high molecular weight organosilicon requires higher sintering temperatures and longer sintering times. Therefore, using high molecular weight organosilicon as a precursor for peroxide films results in both low strength and the need for long sintering times.

[0007] Lu Ye et al. also noticed the problem of low film strength in this type of film. In their patented technology, they further proposed using 60-nanometer large-particle-size organosilicon sol, with hydrolysates of titanate and zirconate as crosslinking components to improve film strength. The aim was to fill the voids formed after film sintering with silica sol and increase the crosslinking density between molecules using coupling agents, thereby improving film strength. However, the adhesion between large-particle-size silica sol and the glass substrate is weak, providing limited strength to the film. Furthermore, the radius and shape of voids formed in the sintered silica film are randomly distributed, and spherical silica sol with a fixed particle size is difficult to effectively fill these voids. Additionally, regardless of whether ordinary isopropyl titanate or organozirconium is used as a crosslinking agent, current methods only improve film strength by crosslinking the hydroxyl groups in the organosilicon; however, the large molecular steric hindrance of macromolecular organosilicon results in low crosslinking density, limiting the improvement in film strength. Therefore, neither of these methods can solve the problem of large voids and low film strength left after sintering of long-chain macromolecular organosilicon.

[0008] Therefore, in order to solve the above problems, this paper proposes a heat-insulating coated tempered glass and its preparation method. Summary of the Invention

[0009] To address the aforementioned technical problems, this invention presents a heat-insulating coated tempered glass and its preparation method, which can solve the problems of insufficient coating strength and the generation of a large number of voids during the sintering of long-chain macromolecular organosilicon in high-temperature heat-insulating tempered glass using semiconductor nanoparticles as infrared blocking agents, and improve the high-temperature resistance of the coating.

[0010] To achieve the above-mentioned technical effects, the present invention is implemented through the following technical solution: In a first aspect, a heat-insulating coated tempered glass is provided, comprising ordinary glass and a heat-insulating coating slurry, characterized in that: the heat-insulating coating slurry is applied to the ordinary glass substrate by roller coating or spraying, and then sintered into transparent heat-insulating glass through a glass tempering process; the heat-insulating coating slurry, by mass percentage, comprises the following components: 30-60% organosilicon oligomer with a degree of polymerization of 5-100, 10-30% oxide semiconductor nanoparticles, 0.3-3% water-soluble bismuth or zinc salt, 0.1-5% titanium coupling agent with chelating function, 0-0.05% acetylsene diol type defoamer, and 24-70% organic solvent.

[0011] Furthermore, the oxide semiconductor nanoparticles in the oxide semiconductor nanoslurry are any one or more of the following: antimony tin oxide, indium tin oxide, cesium tungsten oxide, aluminum-doped zinc oxide, and fluorine-doped antimony oxide.

[0012] Furthermore, the organosilicon oligomer is one or more of the following: methyl orthosilicate organosilicon oligomer, ethyl orthosilicate organosilicon oligomer, propyl orthosilicate organosilicon oligomer, amino silicone oil oligomer, and azinyl organosilicon oligomer.

[0013] Furthermore, the water-soluble bismuth or zinc salt is at least one of bismuth nitrate, bismuth acetate, zinc nitrate, and zinc acetate.

[0014] Furthermore, the organic solvent is at least one selected from methanol, ethanol, isopropanol, butanol, ethylene glycol, propylene glycol, ethylene glycol monomethyl ether, ethylene glycol ethyl ether, ethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol butyl ether, and ethyl acetate.

[0015] Secondly, a method for preparing heat-insulating coated tempered glass is provided, characterized by comprising the following steps: S1: An insulating coating slurry is prepared by adding organosilicon oligomers, titanium coupling agents, water-soluble bismuth or zinc salts, acetylenol-type defoamers, and organic solvents to oxide semiconductor nanoparticles. S2: Clean the original glass sheet and remove static electricity; apply the heat insulation coating slurry by roller or spray onto the surface of the ordinary glass substrate, and heat it at 160-280 degrees Celsius for 3-5 minutes to cure it; S3: After curing, push it into the tempering furnace and heat it at 650-700 degrees Celsius for 5-15 minutes to temper it. After cooling, you can get the heat-insulating coating tempered glass.

[0016] Furthermore, in S1, the average particle size of the oxide semiconductor nanoparticles is ≤50 nanometers.

[0017] Furthermore, in S3, the final thickness of the heat-insulating coating is controlled between 300 and 1300 nanometers.

[0018] The beneficial effects of this invention are: 1. This invention uses organosilicon oligomers, especially oligomers with a degree of polymerization of 5 to 100. Compared with small molecules and organosilicon, they have stronger adhesion to glass and better film-forming properties. Compared with high molecular weight organosilicon, they can solve the problems of low strength and difficulty in densification during the sintering process of organosilicon films.

[0019] In the heat-insulating coating slurry of this invention, water-soluble bismuth or zinc nitrates or acetates are used. These nitrates or acetates can rapidly transform and decompose into highly dispersed and uniform bismuth oxide or zinc oxide in the film, serving as low-melting-point components of silica glass, thereby eliminating the presence of micropores in the film during sintering. Therefore, in this invention, oligomeric organosilicon, along with water-soluble bismuth and zinc salts as low-melting-point components, works synergistically to solve the problem of low film strength caused by voids generated during organosilicon sintering. Attached Figure Description

[0020] To more clearly illustrate the technical solutions of the embodiments of the present invention, the accompanying drawings used in the description of the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0021] Figure 1 This is a schematic diagram of the overall process of the present invention; Detailed Implementation The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0022] Example 1: See Figure 1As shown, by weight, the heat insulation coating slurry formulation 1 consists of: 25% tin antimony oxide slurry with a solid content of 40% (particle size ≤ 50 nm), 10% tetraethyl orthosilicate silicone oligomer with a degree of polymerization of 5, 20% propyl orthosilicate silicone oligomer with a degree of polymerization of 50, 0.3% bismuth nitrate, 1% titanium coupling agent, 0.01% acetylsene glycol defoamer, 27.69% ethanol, 6% ethylene glycol ethyl ether, and 10% propylene glycol; the dry film thickness is controlled at 1500 nm. The heat insulation coating slurry of the above formulation cured at 200°C for 5 minutes and tempered at 680°C for 10 minutes, at which point the film surface was sintered.

[0023] The above-mentioned film was tested using the pencil test method for thin films and the hardness was 7H or higher.

[0024] Example 2: By weight, the heat insulation coating slurry formulation 2 consists of: 30% cesium tungsten oxide slurry (particle size ≤ 50 nm) with a solid content of 30%, 10% tetraethyl orthosilicate silicone oligomer with a degree of polymerization of 20, 20% methyl orthosilicate silicone oligomer with a degree of polymerization of 50, 10% aziridine silicone oligomer with a degree of polymerization of 100, 1% bismuth acetate, 2% titanium coupling agent, 0.1% acetylsadiol-type defoamer, 9.9% ethanol, 5% methanol, 5% isopropanol, and 7% ethylene glycol. The dry film thickness is controlled at 1200 nm.

[0025] The heat-insulating coating slurry formulated above cured at 200 degrees Celsius for 6 minutes and tempered at 650 degrees Celsius for 8 minutes, allowing the film surface to be sintered. The film's hardness was measured to be above 7H using a pencil test.

[0026] Example 3: By weight, the heat insulation coating slurry formulation 3 consists of: 30% aluminum-doped zinc oxide slurry (particle size ≤ 50 nm) with a solid content of 30%, 20% tetraethyl orthosilicate organosilicon oligomer with a degree of polymerization of 200, 20% methyl orthosilicate organosilicon oligomer with a degree of polymerization of 200, 3% titanium coupling agent, 0.05% acetylenol-type defoamer, 7% ethanol, 9.95% ethylene glycol monomethyl ether, 5% diethylene glycol butyl ether, and 5% ethyl acetate. The dry film thickness is controlled at 800 nm.

[0027] The heat-insulating coating slurry formulated above cured at 180 degrees Celsius for 6 minutes and tempered at 680 degrees Celsius for 6 minutes, allowing the film surface to be sintered. The film's hardness was determined to be 6H using a pencil test.

[0028] Example 4: By weight, the heat insulation coating slurry formulation 4 consists of 40% tin antimony oxide slurry (particle size ≤ 50 nm) with a solid content of 50%, 10% aziridine organosilicon oligomer with a degree of polymerization of 200, 20% amino silicone oil oligomer with a degree of polymerization of 10, 5% titanium coupling agent, 1% acetylsadiol type defoamer, 4% ethanol glycol monomethyl ether, 10% diethylene glycol butyl ether, and 10% ethyl acetate, with the dry film thickness controlled at 300 nm.

[0029] The heat-insulating coating slurry formulated above cured at 180 degrees Celsius for 6 minutes and tempered at 700 degrees Celsius for 5 minutes, allowing the film surface to be sintered. The film's hardness was measured to be above 8H using a pencil test.

[0030] Example 5: By weight, the heat insulation coating slurry formulation 5 consists of: 10% fluorine-doped antimony oxide slurry (particle size ≤ 50 nm) with a solid content of 30%, 10% methyl orthosilicate organosilicon oligomer with a degree of polymerization of 200, 7% aziridine organosilicon oligomer with a degree of polymerization of 15, 3% titanium coupling agent, 10% ethanol, 10% ethanol-ethylene glycol monomethyl ether, 20% diethylene glycol butyl ether, and 30% ethyl acetate, with the dry film thickness controlled at 1000 nm.

[0031] The heat-insulating coating slurry formulated above cured at 180 degrees Celsius for 6 minutes and tempered at 700 degrees Celsius for 6 minutes, allowing the film surface to be sintered. The film's hardness was measured to be above 8H using a pencil test.

[0032] The titanium coupling agent in Examples 1-5 can be DuPont Tyzor TE crosslinking agent.

[0033] Comparative Example 1: The composition consists of 20% tin-antimony oxide slurry (particle size ≤ 50 nm) with a solid content of 30%, 20% organosilicon prepolymer with a viscosity of 5-50 mPa•s, 3% silanol-terminated polydimethylsiloxane with a hydroxyl content of 4% and a viscosity of 20 mPa•s, 3% polyether-modified silicone oil with a molecular weight of 6000, 20% organosilicon sol with a SiO2 content, 5% isopropanol and tert-butanol (average particle size 60 nm) solvent system, 5% tetrabutyl titanate, and 40% ethanol. The dry film thickness is controlled at 100 nm.

[0034] The above-mentioned heat-insulating coating slurry has a dry film thickness controlled at 1200 nm. It requires 15 minutes to cure at 200°C and 25 minutes to temper at 620°C for sintering to achieve surface sintering. The film hardness is 3H according to the pencil test. This technical solution indicates that, due to the lack of DuPont Tyzor TE crosslinking agent and silicone oligomers, as well as the absence of bismuth nitrate and zinc nitrate to help eliminate film porosity, even with the use of silica sol and tetrabutyl titanate for film reinforcement, the effect is limited.

[0035] Comparative Example 2: The mixture consists of 20% aluminum-doped zinc oxide slurry (particle size ≤ 50 nm) with a solid content of 30%, 10% tetraethyl orthosilicate oligomer with a degree of polymerization of 20, 20% organosilicon sol with SiO2 content, 5% isopropanol and tert-butanol (average particle size 60 nm) solvent system, 5% zirconate coupling agent, and 40% ethanol.

[0036] The above-mentioned heat-insulating coating slurry has a dry film thickness controlled at 1300 nm. It requires 10 minutes to cure at 200°C and 20 minutes to temper at 650°C for sintering to achieve surface sintering. The film hardness is 4H according to the pencil test. This technical solution indicates that, due to the absence of DuPont Tyzor TE crosslinking agent and silicone oligomers, as well as the lack of bismuth nitrate and zinc nitrate to help eliminate film porosity, even with silica sol reinforcement and a large dose of zirconate coupling agent, the improvement in film strength is very limited.

[0037] Comparative Example 3: The composition consists of: 20% cesium tungsten oxide slurry (particle size ≤ 50 nm) with a solid content of 30%; 12% organosilicon prepolymer with a viscosity of 5–50 mPa; 3% silanol-terminated polydimethylsiloxane with a hydroxyl content of 4% and a viscosity of 20 mPa·s; 3% polyether-modified silicone oil with a molecular weight of 6000; 10% organosilicon sol with a SiO2 content; 5% isopropanol and tert-butanol (average particle size 60 nm) solvent system; 3% DuPont Tyzor TE crosslinking agent; and 40% ethanol. The dry film thickness is controlled at 1000 nm.

[0038] The above-mentioned heat-insulating coating slurry has a dry film thickness controlled at 1200 nm. It requires 10 minutes to cure at 200°C and 15 minutes to temper at 700°C for sintering to achieve surface sintering. The film hardness is 4H according to the pencil test. This technical solution demonstrates that even with the use of DuPont Tyzor TE crosslinking agent, the improvement in film strength is very limited without the assistance of bismuth nitrate and zinc nitrate to eliminate film porosity.

Claims

1. A heat-insulating coated tempered glass, comprising ordinary glass and a heat-insulating coating paste, characterized in that: The heat-insulating coating slurry is applied to ordinary glass substrates by roller coating or spraying, and then sintered into transparent heat-insulating glass through a glass tempering process. The heat-insulating coating slurry, by mass percentage, contains the following components: 30-60% organosilicon oligomer with a degree of polymerization of 5-100, 10-30% oxide semiconductor nano-slurry, 0.3-3% water-soluble bismuth or zinc salt, 0.1-5% titanium coupling agent with chelating function, 0-0.05% acetylenic diol type defoamer, and 24-70% organic solvent.

2. The heat-insulating coated tempered glass according to claim 1, characterized in that, The oxide semiconductor nanoparticles in the oxide semiconductor nanoslurry are any one or more of the following: antimony tin oxide, indium tin oxide, cesium tungsten oxide, aluminum-doped zinc oxide, and fluorine-doped antimony oxide.

3. The heat-insulating coated tempered glass according to claim 1, characterized in that, The organosilicon oligomer is one or more of the following: methyl orthosilicate organosilicon oligomer, ethyl orthosilicate organosilicon oligomer, propyl orthosilicate organosilicon oligomer, amino silicone oil oligomer, and azinyl organosilicon oligomer.

4. The heat-insulating coated tempered glass according to claim 1, characterized in that, The water-soluble bismuth or zinc salt is at least one of bismuth nitrate, bismuth acetate, zinc nitrate, and zinc acetate.

5. The heat-insulating coated tempered glass according to claim 1, characterized in that, The organic solvent is at least one of methanol, ethanol, isopropanol, butanol, ethylene glycol, propylene glycol, ethylene glycol monomethyl ether, ethylene glycol ethyl ether, ethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol butyl ether, and ethyl acetate.

6. A method for preparing a heat-insulating coated tempered glass according to any one of claims 1 to 5, characterized in that, Includes the following steps: S1: An insulating coating slurry is prepared by adding organosilicon oligomers, titanium coupling agents, water-soluble bismuth or zinc salts, acetylenol-type defoamers, and organic solvents to oxide semiconductor nanoparticles. S2: Clean the original glass sheet and remove static electricity; apply the heat insulation coating slurry by roller or spray onto the surface of the ordinary glass substrate, and heat it at 160-280 degrees Celsius for 3-5 minutes to cure it; S3: After curing, push it into the tempering furnace and heat it at 650-700 degrees Celsius for 5-15 minutes to temper it. After cooling, you can get the heat-insulating coating tempered glass.

7. The method for preparing a heat-insulating coated tempered glass according to claim 6, characterized in that, In S1, the average particle size of the oxide semiconductor nanoparticles is ≤50 nanometers.

8. The method for preparing a heat-insulating coated tempered glass according to claim 6, characterized in that, In S3, the final thickness of the heat-insulating coating is controlled between 300 and 1300 nanometers.

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