A kind of pure color heat-insulating coated glass and preparation method thereof

Abstract

The present invention discloses a clear-color coated thermal insulation glass and a preparation method thereof, belonging to the technical field of coated glass. The method comprises the following steps: 20-40% by weight of an organosilicon oligomer with a degree of polymerization not exceeding 200, 10-45% of oxide semiconductor nanoparticles having a thermal insulation function, 0.1-5% of a thermal insulation semiconductor decolorant, 0.1-5% of a thermal insulation semiconductor high-temperature protective agent, 0-0.5% of an acetylene glycol defoamer, 15-54.9% of an organic solvent, and 0-50% of water are mixed in sequence to produce a colorless thermal insulation coating slurry; the slurry is then sprayed or roller-coated onto the ordinary glass substrate, cured by high-temperature baking, and sintered using a glass tempering process to produce the clear-color coated thermal insulation glass. The clear-color coated thermal insulation glass produced by the present invention is not only colorless and transparent, but also has high hardness, scratch resistance, and can be hot-bent, making it widely applicable to architectural and automotive glass.

Description

Technical Field

[0001] The present invention belongs to the technical field of coated glass, and in particular relates to a pure color heat-insulating coated glass and a preparation method thereof. Background Art

[0002] Currently, commercial buildings, especially high-rises, mostly use double-layer Low-E glass. While this energy-saving, heat-insulating glass offers excellent insulation, it suffers from a significant problem: a pronounced tint. Most Low-E glass, due to its use of a metal film and semiconductor layer to reflect infrared light, exhibits a distinct blue tint and exhibits a significant specular reflection effect. This can lead to light pollution and bird strikes. Furthermore, from an external perspective, the pronounced tint of Low-E glass deprives it of its inherently transparent, colorless, crystalline quality. Furthermore, when viewed from within the building, the exterior landscape is distorted, impacting both the natural environment and the overall comfort level. Large curtain wall and balcony windows, particularly those requiring a high degree of exterior beauty, completely lose their distinctive appearance if Low-E glass is used for thermal insulation.

[0003] In addition to Low-E glass, there are also heat-insulating glasses that use nano-infrared blocking agents as the infrared reflective layer coating. Nano-semiconductors such as ATO (antimony tin oxide), ITO (indium tin oxide), and GTO (cesium tungsten oxide) all have obvious coloring effects. For example, ATO and GTO appear distinctly blue, and ITO appears yellow, regardless of whether physical sputtering or slurry coating is used. Taking GTO, or cesium tungsten, as an example, it is an infrared reflective heat-insulating agent. The reason they appear distinctly blue is that they reflect the blue part of visible light. Therefore, how to adjust the absorption and reflection edges of this type of heat-insulating semiconductor has become an important factor in achieving colorless or pure color in heat-insulating glass. However, the color of semiconductors and their infrared reflection performance are often closely related, and existing magnetron sputtering coating and organic slurry coating methods are difficult to solve.

[0004] Furthermore, highly insulated float glass, which also provides thermal insulation, also suffers from severe tinting. This type of glass uses near-infrared absorbing colorants with blue or green hues, a problem similar to Low-E glass and other conventional coated glass, resulting in a pronounced blue or green tint. Therefore, existing technologies struggle to achieve both thermal insulation and colorless transparency for large curtain wall glass and conventional architectural glass, which require exterior landscapes. Furthermore, achieving a colorless and transparent appearance for architectural glass can be unsatisfactory in terms of energy conservation and emission reduction.

[0005] Therefore, in order to solve the above problems, this paper proposes to use chemical plating to achieve a pure color thermal insulation coated glass and a preparation method thereof. Summary of the Invention

[0006] The purpose of the present invention is to provide a clear-color heat-insulating coated glass that can solve the problem of difficulty in balancing thermal insulation performance and glass colorlessness in curtain walls and architectural glass that have high requirements for building appearance and external landscape.

[0007] In order to achieve the above technical effects, the present invention is realized through the following technical solutions: a clear color thermal insulation coated glass, comprising a clear color coating thermal insulation coating and an ordinary glass original sheet, characterized in that the clear color thermal insulation coated glass is formed by rolling or spraying a layer of clear color coating thermal insulation slurry on the ordinary glass original sheet and sintering it through a single glass tempering process; the clear color coating thermal insulation slurry comprises the following components by weight percentage: 20-40% of an organosilicon oligomer with a degree of polymerization not exceeding 200, 10-45% of oxide semiconductor nanoparticles with thermal insulation function, 0.1-5.0% of a decolorant for an infrared thermal insulation semiconductor, 0.1-5% of a high temperature protective agent for an infrared thermal insulation semiconductor, 0-0.5% of an acetylene glycol defoamer, 15-54.9% of an organic solvent, and 0-50% of water.

[0008] Furthermore, the oxide semiconductor nanoparticles with heat insulation function are one or more of nano-antimony tin oxide, nano-indium tin oxide or cesium tungsten, and aluminum-doped zinc oxide with an average particle size not exceeding 50 nanometers.

[0009] Furthermore, the organosilicon oligomer is one or more of methyl orthosilicate oligomer, ethyl orthosilicate oligomer, amino silicone oil oligomer, and oxazine-based organosilicon oligomer.

[0010] Furthermore, the organic silicon oligomer has a polymerization degree of 5 to 200.

[0011] Furthermore, the color remover of the infrared heat-insulating semiconductor is DuPont Tyzor TE.

[0012] Furthermore, the high temperature protective agent of the infrared heat-insulating semiconductor is DuPont Tyzor 371.

[0013] Furthermore, the organic solvent is one or more 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.

[0014] Another object of the present invention is to provide a method for preparing clear-color heat-insulating coated glass, which is characterized by:

[0015] S1. Add the heat-insulating nano-slurry to the solvent, then add the infrared heat-insulating semiconductor decolorizer and the infrared heat-insulating semiconductor infrared high-temperature protective agent, and stir for 10 to 200 minutes; then add water, organic solvent, organosilicon oligomer resin, and acetylene glycol defoamer in sequence, disperse and stir evenly, and the pure color coating film heat-insulating coating can be obtained;

[0016] S2. Clean and remove static electricity from the ordinary glass sheets prepared in advance;

[0017] S3. Apply the clear color coating film heat-insulating coating prepared in S1 to the surface of the ordinary glass sheet after cleaning and destaticization in S2 by roller coating or spraying; at this time, when both sides of the glass need to be sprayed, the thickness of the sprayed film is 200 to 600 nanometers; when only one side of the glass needs to be sprayed, the thickness of the sprayed film is 500 to 1500 nanometers;

[0018] S4. Heat the sprayed glass at 160-280 degrees Celsius for 3-5 minutes to solidify;

[0019] S5. After solidification, push the glass into the tempering furnace for tempering for 5 to 15 minutes; after cooling, a colorless, transparent, durable and high-strength pure color heat-insulating coated glass can be obtained.

[0020] The beneficial effects of the present invention are:

[0021] 1) Compared with the original technology, after the high-temperature tempering process of the decolorizer, the heat-insulating nano-semiconductor and its final coating appear to be nearly colorless, solving the serious coloring problem of Low-E glass, coated glass, high-insulation glass and other heat-insulating glass;

[0022] 2) Compared with Low-E glass and organic coated glass, the tempered clear color insulating glass disclosed in the present invention has a clear color insulating layer with high hardness and scratch resistance, can be hot-bent, and can be widely used in architectural glass and automotive glass. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the following briefly introduces the drawings required for describing the embodiments. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0024] Figure 1 This is a flow chart of the method for preparing pure color heat-insulating coated glass of the present invention. DETAILED DESCRIPTION

[0025] The following will clearly and completely describe the technical solutions in the embodiments of the present invention in conjunction with the accompanying drawings. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts shall fall within the scope of protection of the present invention.

[0026] Example 1

[0027] This embodiment describes the principle by which this technical solution can achieve pure color and transparency, durability and high strength:

[0028] In this technical solution, nano-semiconductor infrared heat-insulating agent, infrared heat-insulating semiconductor color eliminating agent and high-temperature sintering protective agent are introduced, and organic silicon oligomer is used as film-forming agent; during the sintering process, a titanium coupling agent with chelating function at room temperature and coupling function after high-temperature reaction is used as a color-eliminating agent; this type of chelating agent can be effectively coated on the surface of semiconductor particles. At high temperature, organic titanium reacts with semiconductor particles on the surface during the inorganicization process, which can cause a slight red shift in the semiconductor absorption edge, thereby eliminating the blue light reflection of the nano-heat-insulating agent in the visible band and achieving a pure color of the heat-insulating layer; at the same time, A titanium chelating agent can decompose into titanium dioxide at high temperatures, forming a dense titanium dioxide protective layer on the surface of the heat-insulating semiconductor, thereby preventing the erosion of semiconductor particles by silicon dioxide and glass media at high temperatures, and the resulting degradation of the infrared reflectivity of the semiconductor particles. The tempered heat-insulating glass provided by the present invention basically presents the same or similar appearance and color as the original glass, while having the same infrared heat-insulating ability as ordinary coated glass. The final inorganic form of silicon dioxide in the heat-insulating coating is the main film-forming component, and the coating has high hardness and scratch resistance. It can be used as a single piece or as two pieces, and will not oxidize or age.

[0029] Example 2

[0030] In this embodiment, a pure color coating heat-insulating slurry is prepared by using, as raw materials for coating preparation, 30% of a 35% solid content nano-antimony tin oxide (particle size ≤ 50 nanometers) methanol dispersion, 10% of a 30% solid content nano-indium tin oxide (particle size ≤ 50 nanometers) ethanol dispersion, 10% of a 5% polymerization degree of ethyl orthosilicate oligomer, 10% of a 50% polymerization degree of amino silicone oil oligomer, 9.5% of ethanol, 5% of ethylene glycol ethyl ether, 4.5% of propylene glycol, 0.5% of DuPont Tyzor TE, 0.5% of DuPont Tyzor 371, and 20% of water. When preparing ordinary glass sheets and coating on one side, the final dry film thickness is controlled to be 200 nanometers.

[0031] Then clean and remove static electricity from the ordinary glass sheets;

[0032] Apply the above-mentioned pure color coating thermal insulation slurry to the surface of the ordinary glass sheet by roller coating;

[0033] Curing is achieved at 200 degrees Celsius for 6 minutes;

[0034] At a tempering temperature of 660 degrees Celsius, the clear color coating heat insulation coating can be sintered after 6 minutes to produce clear color heat insulation coated glass;

[0035] The above-mentioned clear-color thermal-insulating coated glass is nearly colorless compared to original uncoated glass. Only when carefully observed against a white background or bright sunlight does the clear-color thermal-insulating coated glass appear extremely slightly blue. When used as a window and compared with ordinary glass, the color difference of the external landscape seen through the two is difficult to distinguish with the naked eye. Compared with the same tempered liquid-coated but untempered sintered glass, the near-infrared reflectivity is almost unchanged. The hardness of the tempered film is 8H after the thin film pencil test.

[0036] Example 3

[0037] In this embodiment, a pure color coating heat-insulating slurry is prepared by using, by weight, 30% of a cesium tungsten oxide nano-dispersion (particle size ≤ 50 nanometers) in methanol with a solid content of 35%, 5% of a cesium tungsten nano-dispersion (particle size ≤ 50 nanometers) in ethanol with a solid content of 30%, 10% of a ethyl orthosilicate oligomer with a degree of polymerization of 20, 10% of an aminosilicic acid oligomer with a degree of polymerization of 50, 10% of an azine-based oligomer with a degree of polymerization of 100, 1% of DuPont Tyzor TE, 12% of DuPont Tyzor 371, 0.1% of an acetylene glycol defoamer, 12.9% of ethanol, 5% of methanol, 5% of isopropyl alcohol, 4% of ethylene glycol, and 5% of diethylene glycol ethyl ether as raw materials for coating. The coating is then prepared on a plain glass substrate. When double-sided coating is performed, the final dry film thickness is controlled to be 600 nanometers.

[0038] Then clean and remove static electricity from the ordinary glass sheets;

[0039] Apply the above-mentioned pure color coating thermal insulation slurry to the surface of the ordinary glass sheet by spraying;

[0040] Curing is achieved at 200 degrees Celsius for 6 minutes;

[0041] At a tempering temperature of 650 degrees Celsius, the clear color coating heat insulation coating can be sintered after 7 minutes to produce clear color heat insulation coated glass;

[0042] The clear-color heat-insulating coated glass produced above is nearly colorless compared to the original uncoated glass. Only when carefully observed against a white background or bright sunlight does the clear-color heat-insulating coated glass appear extremely slightly blue. When compared with ordinary glass as a window, the color difference of the external landscape seen through the two is difficult to distinguish with the naked eye. Compared with the same tempered liquid-coated but untempered sintered glass, the near-infrared reflectivity has almost no decrease. The hardness of the tempered film is 8H after the thin film pencil test method.

[0043] Example 4

[0044] In this embodiment, a pure color coating heat-insulating slurry is prepared by using, by weight, AZO with a particle size of 50 nanometers (10%), ethyl orthosilicate oligomer with a degree of polymerization of 200 (20%), DuPont Tyzor TE (3%), DuPont Tyzor 371 (1.7%), acetylene glycol defoamer (0.3%), water (50%), ethanol glycol monomethyl ether (5%), and diethylene glycol butyl ether (10%) as coating materials. When preparing ordinary glass sheets and coating on one side, the final dry film thickness is controlled to be 1000 nanometers.

[0045] Then clean and remove static electricity from the ordinary glass sheets;

[0046] Apply the above-mentioned pure color coating thermal insulation slurry to the surface of the ordinary glass sheet by roller coating;

[0047] Curing is achieved at 280 degrees Celsius for 6 minutes;

[0048] At a tempering temperature of 680 degrees Celsius, the clear color coating heat insulation coating can be sintered after 6 minutes to produce clear color heat insulation coated glass;

[0049] The clear-color thermal-insulating coated glass produced above is nearly colorless compared to uncoated original glass. Only when carefully observed against a white background or bright sunlight does the clear-color thermal-insulating coated glass appear extremely slightly blue. When compared with ordinary glass as a window, the color difference in the external landscape seen through the two is difficult to distinguish with the naked eye. Compared with untempered sintered glass with the same tempered liquid coating, the near-infrared reflectivity is almost the same. The hardness of the tempered film is 8H when tested using a thin film pencil test method.

[0050] Example 5

[0051] In this embodiment, a pure color coating heat-insulating slurry is prepared by using, by weight, 10% nano-indium tin oxide (particle size ≤ 50 nanometers), 29.5% amino silicone oil oligomer with a degree of polymerization of 100, 5% DuPont Tyzor TE, 11% DuPont Tyzor 37, 0.5% acetylene glycol defoamer, 40% ethanol, 5% ethanol ethylene glycol monomethyl ether, 5% diethylene glycol butyl ether, and 4% ethyl acetate as raw materials for coating. When preparing ordinary glass sheets and coating on one side, the final dry film thickness is controlled to be 1500 nanometers.

[0052] Then clean and remove static electricity from the ordinary glass sheets;

[0053] Apply the above-mentioned pure color coating thermal insulation slurry to the surface of the ordinary glass sheet by spraying;

[0054] Curing is achieved at 180 degrees Celsius for 10 minutes;

[0055] At a tempering temperature of 680 degrees Celsius, the clear color coating heat insulation coating can be sintered after 10 minutes to produce clear color heat insulation coated glass;

[0056] Compared with the original uncoated glass, the above-mentioned clear color thermal insulation coated glass only appears extremely slightly yellow when carefully observed against a white background or bright sunlight. When used as a window and compared with ordinary glass, the color difference of the external landscape seen through the two is difficult to distinguish with the naked eye. Compared with the same tempered liquid coated but untempered sintered glass, the near-infrared reflectivity is almost unchanged. The hardness of the tempered film is 9H after the thin film pencil test.

[0057] Example 6

[0058] In this embodiment, a pure color film-based heat-insulating coating is prepared by using, by weight, 20% tungsten-doped vanadium dioxide (particle size ≤ 50 nanometers), 25% cesium tungsten (particle size ≤ 50 nanometers), 20% ethyl orthosilicate oligomer with a degree of polymerization of 10, 20% methyl orthosilicate oligomer with a degree of polymerization of 5, 0.1% DuPont Tyzor TE, 15% DuPont Tyzor 37, 0.3% acetylene glycol defoamer, 4.6% ethanol glycol monomethyl ether, and 5% ethylene glycol butyl ether as raw materials for coating. A plain glass substrate is prepared; when coating on one side, the final dry film thickness is controlled to be 500 nanometers. The plain glass substrate is then cleaned and static-free.

[0059] Apply the above-mentioned pure color coating film heat insulation paint to the surface of the ordinary glass sheet by roller coating;

[0060] Curing is achieved at 180 degrees Celsius for 6 minutes;

[0061] At a tempering temperature of 700 degrees Celsius, the clear color coating heat insulation coating can be sintered after 6 minutes to produce clear color heat insulation coated glass;

[0062] The above-mentioned clear-color thermal-insulating coated glass is nearly colorless compared to original uncoated glass. Only when carefully observed against a white background or bright sunlight does the clear-color thermal-insulating coated glass appear extremely slightly blue. When compared with ordinary glass as a window, the color difference in the external landscape seen through the two is difficult to distinguish with the naked eye. Compared with the same tempered liquid-coated but untempered sintered glass, the near-infrared reflectivity is almost unchanged. The toughened film has a hardness of 9H using the thin film pencil test method.

[0063] Example 7

[0064] This embodiment, as a comparative embodiment, uses 30% by weight of an aqueous dispersion of nano-antimony tin oxide (particle size ≤ 50 nanometers) with a solid content of 30%, 10% of an ethanol dispersion of nano-tin indium oxide (particle size ≤ 50 nanometers) with a solid content of 30%, 10% of an ethyl orthosilicate oligomer with a degree of polymerization of 5, 10% of an amino silicone oligomer with a degree of polymerization of 50, 0.01% of an acetylene glycol defoamer, 28.69% of ethanol, 5% of ethylene glycol ethyl ether, and 6.3% of propylene glycol as raw materials for preparing a coating; a coating slurry is prepared; and when coating on one side of an ordinary glass sheet, the final dry film thickness is controlled to be 1500 nanometers.

[0065] Then clean and remove static electricity from the ordinary glass sheets;

[0066] Apply the coating slurry to the surface of ordinary glass sheet by spraying;

[0067] Curing is achieved at 200 degrees Celsius for 5 minutes;

[0068] At a tempering temperature of 640 degrees Celsius, the thermal insulation coating can be sintered after 12 minutes to produce coated glass;

[0069] Compared with the original uncoated glass, the above-mentioned coated glass appears obviously blue to the naked eye due to the lack of the effect of the decolorizer; compared with the coated but untempered sintered glass, due to the lack of infrared protective agent, the nano-semiconductor particles are sintered at high temperatures, and the near-infrared reflectivity decreases by about 20%; the hardness of the tempered film is 5H after the thin film pencil test method.

[0070] Example 8

[0071] This embodiment, as a comparative embodiment, uses 30% by weight of a nano-indium tin oxide (particle size ≤ 50 nanometers) aqueous dispersion with a solid content of 30%, 5% of a cesium tungsten (particle size ≤ 50 nanometers) ethanol dispersion with a solid content of 30%, 10% of a tetraethyl orthosilicate oligomer with a degree of polymerization of 20, 10% of an amino-organic silicon oligomer with a degree of polymerization of 50, 10% of an azine-based organosilicone oligomer with a degree of polymerization of 100, 15% of ethanol, 5% of methanol, 10% of water, and 5% of ethylene glycol ethyl ether as raw materials for preparing a coating; a coating is prepared; and when coating on both sides of an ordinary glass sheet, the final dry film thickness is controlled to be 500 nanometers.

[0072] Then clean and remove static electricity from the ordinary glass sheets;

[0073] Apply the above coating to the surface of ordinary glass sheet by roller coating;

[0074] Curing is achieved at 200 degrees Celsius for 6 minutes;

[0075] At a tempering temperature of 650 degrees Celsius, the thermal insulation coating can be sintered after 6 minutes to produce coated glass;

[0076] The above-mentioned coated glass appears light yellow compared to uncoated glass due to the lack of a decolorizer. Compared with coated but untempered sintered glass, the near-infrared reflectivity decreases by about 25% due to the lack of an infrared protective agent and the melting of the nano-semiconductor particles at high temperatures. The hardness of the tempered film is 6H after a thin film pencil test.

[0077] In summary, the clear color insulating coated glass produced by this technical solution has the advantages of being colorless, transparent, hard, scratch-resistant, and capable of hot bending, compared to coated insulating glass produced by other methods, and is widely used in architectural glass and automotive glass.

Claims

1. A clear color heat-insulating coated glass, comprising ordinary glass and a clear color heat-insulating coating layer, characterized in that: A pure color heat-insulating coating layer is rolled or sprayed on an ordinary glass sheet and sintered once using a glass tempering process; the pure color heat-insulating coating layer comprises the following components by weight: 20-40% of an organosilicon oligomer with a degree of polymerization not exceeding 200, 10-45% of oxide semiconductor nanoparticles having a heat-insulating function, 0.1-5.0% of a heat-insulating semiconductor decolorizer, 0.1-5% of a heat-insulating semiconductor high-temperature protective agent, 0-0.5% of an acetylene glycol defoamer, 15-54.9% of an organic solvent, and 0-50% of water; The heat-insulating semiconductor decolorizer is DuPont Tyzor TE; The high temperature protective agent of the heat-insulating semiconductor is DuPont Tyzor 371.

2. The clear color heat-insulating coated glass according to claim 1, characterized in that: The oxide semiconductor nanoparticles with heat insulation function are one or more of nano antimony tin oxide, nano indium tin oxide or cesium tungsten, and aluminum-doped zinc oxide with an average particle size not exceeding 50 nanometers.

3. The clear color heat-insulating coated glass according to claim 1, characterized in that: The organosilicon oligomer is one or more of methyl orthosilicate oligomer, ethyl orthosilicate oligomer, amino silicone oil oligomer, and oxazine-based organosilicon oligomer.

4. The clear color heat-insulating coated glass according to claim 1, characterized in that: The organic silicon oligomer has a polymerization degree of 5 to 200.

5. The clear color heat-insulating coated glass according to claim 1, characterized in that: The organic solvent is one or more 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. The method for preparing clear-color thermal-insulating coated glass according to any one of claims 1 to 5, characterized in that: S1. Add the heat-insulating nano-slurry to the solvent, then add the infrared heat-insulating semiconductor decolorizer and the semiconductor infrared protective agent, and stir for 10 to 200 minutes; then add water, organic solvent, organosilicon oligomer resin, and acetylene glycol defoamer in sequence, disperse and stir evenly, and the pure color heat-insulating coating layer can be obtained; S2. Clean and remove static electricity from the ordinary glass sheets prepared in advance; S3. Applying the pure color heat-insulating coating layer prepared in S1 to the surface of the ordinary glass sheet after cleaning and destaticization in S2 by roller coating or spraying; at this time, when both sides of the glass need to be sprayed, the thickness of the sprayed film is 200 to 600 nanometers; when only one side of the glass needs to be sprayed, the thickness of the sprayed film is 500 to 1500 nanometers; S4. Heat the sprayed glass at 160-280 degrees Celsius for 3-5 minutes to solidify; S5. After solidification, push the glass into the tempering furnace for tempering for 5 to 15 minutes. At this time, the double-sided coated glass only needs to be tempered for more than 5 minutes; the single-layer coated glass only needs to be tempered for more than 10 minutes. After cooling, a colorless, transparent, durable and high-strength clear color insulating coated glass can be obtained.

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