Glass with coating and vehicle

Abstract

The invention provides glass with a coating and a vehicle. The surface of the glass is provided with a coating; the coating contains an ultraviolet light absorber and an infrared light absorber; the peak values of all absorption peaks of the ultraviolet light absorber are below 390nm, and the maximum absorption peak is within the wavelength range of 350nm-380nm; the peak values of all absorption peaks of the infrared absorbent are more than 900nm, and the maximum absorption peak is in the wavelength range of 950nm to 1500nm; the transmittance of the glass with the coating in the wavelength range of 300nm-400nm is less than or equal to 1%; the transmittance of the coated glass in the wavelength range of 780 nm to 2500 nm is smaller than or equal to 15%. The invention further provides a vehicle provided with the glass. The glass provided by the invention has relatively low transmittance for ultraviolet rays and infrared rays with the wavelength range of 380-400nm.

Description

Technical Field

[0001] This invention relates to coated glass and vehicles, belonging to the field of functional coating technology. Background Technology

[0002] Ultraviolet radiation with wavelengths in the range of 380nm-400nm can induce the generation of free radicals, which are associated with diseases such as melasma and photodermatitis. People with photosensitivity need to completely block UVA to reduce the triggering of these conditions.

[0003] Surface coating technology can be used to form functional coatings on the surface of substrates such as glass to block infrared and ultraviolet rays. Currently, automotive glass products on the market can only block ultraviolet rays with wavelengths in the range of 300nm to 380nm, which is insufficient to meet the requirements for blocking ultraviolet rays with wavelengths in the range of 380nm to 400nm.

[0004] CN115782323B discloses a UV-blocking glass with a UV-blocking film. This UV-blocking glass has a Tuv400 ≤ 2.0%, a transmittance of 420nm light ≥ 50%, and a visible light transmittance (YA) of the substrate glass ≥ 81.7%. After accelerated weathering testing, the difference between the 400nm UV transmittance (Tuv400) and the pre-test UV transmittance (Tuv400) is less than 2%. After abrasion testing, the UV-blocking film does not peel off, and the haze rate of the UV-blocking glass after the test is less than 5%. However, the visible light transmittance of the substrate glass must be greater than 81.7%, and the overall color is yellowish. Summary of the Invention

[0005] To solve the above-mentioned technical problems, the present invention aims to provide a coated glass, wherein the coating of the glass has a good blocking effect on infrared rays and ultraviolet rays with wavelengths in the range of 380nm-400nm.

[0006] To achieve the above objectives, the present invention first provides a coated glass, wherein the surface of the glass has a coating;

[0007] The coating contains ultraviolet absorbers and infrared absorbers;

[0008] The peak values ​​of all absorption peaks of the ultraviolet absorber are below 390 nm, and the maximum absorption peak is in the wavelength range of 350 nm to 380 nm.

[0009] The peak values ​​of all absorption peaks of the infrared absorber are above 900 nm, and the maximum absorption peak is in the wavelength range of 950 nm to 1500 nm.

[0010] The coated glass has a transmittance of less than or equal to 1% in the wavelength range of 300nm-400nm;

[0011] The coated glass has a transmittance of less than or equal to 15% in the wavelength range of 780nm-2500nm.

[0012] According to a specific embodiment of the present invention, preferably, the thickness of the coating is 2μm-12μm.

[0013] According to a specific embodiment of the present invention, preferably, the minimum transmittance of the coated glass at a wavelength of 410 nm is greater than or equal to 15%.

[0014] According to a specific embodiment of the present invention, preferably, the transmittance of the coated glass in the wavelength range of 300nm-400nm is less than or equal to 0.75%.

[0015] According to a specific embodiment of the present invention, preferably, the minimum transmittance of the coated glass at a wavelength of 410 nm is greater than or equal to 20%.

[0016] According to a specific embodiment of the present invention, preferably, the transmittance of the coated glass in the wavelength range of 300nm-400nm is less than or equal to 0.5%.

[0017] According to a specific embodiment of the present invention, preferably, the minimum transmittance of the coated glass at a wavelength of 410 nm is greater than or equal to 25%.

[0018] According to a specific embodiment of the present invention, preferably, the ratio of the transmittance T410 of the coated glass at 410 nm to its transmittance T400 at 400 nm satisfies: 15 ≤ T410 / T400 ≤ 100, more preferably 20 ≤ T410 / T400 ≤ 30.

[0019] According to a specific embodiment of the present invention, preferably, the coated glass has a transmittance of greater than or equal to 70% in the wavelength range of 380nm-780nm.

[0020] According to a specific embodiment of the present invention, preferably, before the 2000-hour xenon lamp aging test, the coated glass has a transmittance of greater than or equal to 70% in the wavelength range of 380nm-780nm.

[0021] According to a specific embodiment of the present invention, preferably, after 2000 hours of xenon lamp aging test, the coated glass has a transmittance of greater than or equal to 70% in the wavelength range of 380nm-780nm, more preferably 70%-80%.

[0022] According to a specific embodiment of the present invention, preferably, after a 1000-revolution abrasion resistance test by a planar abrasion tester, the difference between the haze of the coated glass and the haze before the test is less than or equal to 5%.

[0023] According to a specific embodiment of the present invention, preferably, the glass, in its uncoated state (raw glass), has a transmittance of greater than or equal to 74% in the wavelength range of 380nm-780nm. If the uncoated glass (raw glass) has low visible light transmittance, or if the coating has low ultraviolet or infrared absorption capacity, the coating's ability to block deep ultraviolet or infrared radiation will be insufficient.

[0024] According to a specific embodiment of the present invention, preferably, the coated glass has a transmittance of greater than or equal to 70% in the wavelength range of 380nm-780nm. The transmittance of the coated glass in the wavelength range of 380nm-780nm is strongly correlated with the thickness of the coating; the thicker the coating, the lower the lower limit of the transmittance of the glass in the wavelength range of 380nm-780nm. The transmittance (Tl) of the coated glass in the wavelength range of 380nm-780nm exhibits a certain linear relationship with the coating thickness (H); Tl = 0.80849 - 0.0058 × H.

[0025] According to a specific embodiment of the present invention, preferably, the ratio of the a* value to the b* value of the color of the coated glass satisfies: |a* / b*| is 0.5-1.5. Colors meeting this condition are relatively soft and not too bright. If |a* / b*| < 0.5, the color will be more yellow; if |a* / b*| > 1.5, it will appear grayish-blue.

[0026] According to a specific embodiment of the present invention, preferably, the color uniformity of the coated glass satisfies ΔE≤2;

[0027] The formula for calculating ΔE is: ∆E = [(ΔL)^2 + (Δa*)^2 + (Δb*)^2]^0.5;

[0028] ΔL, Δa*, and Δb* refer to the differences between L, a*, and b* obtained from testing any two points in a coated glass with an area of ​​300mm × 300mm.

[0029] According to a specific embodiment of the present invention, preferably, the difference ΔSI between any single-point signal of the coated glass and the base glass (uncoated glass) in the range of 1 GHz to 18 GHz is ≤1.

[0030] According to a specific embodiment of the present invention, preferably, the coating is made of paint;

[0031] The coating contains, by weight percentage, 50-84.9% silica sol, 10-30% first additive, 5-20% second additive, and 0.1-1% auxiliary agents.

[0032] The first additive contains an ultraviolet absorber;

[0033] The second additive contains an infrared absorber.

[0034] According to a specific embodiment of the present invention, preferably, the first additive comprises 5-15% ultraviolet absorber by weight percentage;

[0035] The second additive contains 10-40% infrared absorber by weight percentage.

[0036] According to a specific embodiment of the present invention, preferably, the silica sol contains, by mass percentage, 10-30% silicate ester, 5-20% first coupling agent, 30-70% first solvent, 5-20% water, and 0.01-0.5% first catalyst.

[0037] According to a specific embodiment of the present invention, preferably, by mass percentage, the first additive comprises 5-15% ultraviolet absorber, 20-50% second coupling agent, 40-80% second solvent, and 0.01-0.1% second catalyst.

[0038] According to a specific embodiment of the present invention, preferably, the second additive comprises, by mass percentage, 10-40% infrared absorber, 10-40% surfactant, and 50-70% third solvent.

[0039] According to a specific embodiment of the present invention, preferably, the mass ratio of the first additive and the second additive is 0.5-3.5.

[0040] According to a specific embodiment of the present invention, preferably, the coating comprises, by mass percentage, 65-80% silica sol, 10-20% first additive, 5-20% second additive, and 0.2-1% auxiliary agent. The sum of the mass percentages of all components is 100%.

[0041] According to a specific embodiment of the present invention, preferably, the silica sol comprises, by mass percentage, 14-20% silicate ester, 5-15% first coupling agent, 45-65% first solvent, 10-20% water, and 0.05-0.3% first catalyst. The sum of the mass percentages of all components is 100%.

[0042] According to a specific embodiment of the present invention, preferably, by mass percentage, the first additive comprises 10-15% ultraviolet absorber, 20-30% second coupling agent, 55-65% second solvent, and 0.05-0.1% second catalyst. The sum of the mass percentages of all components is 100%.

[0043] According to a specific embodiment of the present invention, preferably, the second additive comprises, by mass percentage, 15-20% infrared absorber, 20-30% surfactant, and 55-60% third solvent. The sum of the mass percentages of all components is 100%.

[0044] According to a specific embodiment of the present invention, preferably, the additive comprises, by mass percentage, 30-50% leveling agent, 10-40% wetting agent, and 10-40% defoamer; more preferably, the additive comprises 40-50% leveling agent, 30-40% wetting agent, and 10-25% defoamer. The sum of the mass percentages of each component is 100%.

[0045] According to a specific embodiment of the present invention, preferably, the silicate ester is selected from one or more combinations of methyl orthosilicate, ethyl orthosilicate, trimethoxysilane, triethoxysilane and dimethyldimethoxysilane.

[0046] According to a specific embodiment of the present invention, preferably, the first coupling agent and the second coupling agent are selected from one or more combinations of 3-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-(2,3-epoxypropoxy)propyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane and N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane.

[0047] According to a specific embodiment of the present invention, preferably, the first catalyst is selected from one or a combination of two or more of hydrochloric acid, nitric acid, and ammonia. When calculating the content of the first catalyst, it is based on the mass of the solute; for example, when the first catalyst is nitric acid, it is based on the mass of HNO3 in the nitric acid.

[0048] According to a specific embodiment of the present invention, preferably, the second catalyst is selected from one or more combinations of dibutyltin dilaurate, organobismuth catalysts, and stannous octoate.

[0049] According to a specific embodiment of the present invention, preferably, the first solvent is selected from one or more combinations of methanol, ethanol, propanol, isopropanol, butanol and propylene glycol methyl ether.

[0050] According to a specific embodiment of the present invention, preferably, the second solvent is selected from one or more combinations of butyl acetate, propylene glycol methyl ether, isobutyl acetate, and xylene.

[0051] According to a specific embodiment of the present invention, preferably, the third solvent is selected from one or more combinations of methanol, ethanol, propanol, isopropanol, butanol and propylene glycol methyl ether.

[0052] According to a specific embodiment of the present invention, preferably, the mass ratio of the ultraviolet absorber to the second coupling agent is 1:4 to 1:10. Controlling the mass ratio of the ultraviolet absorber to the second coupling agent within this range results in a first additive with a suitable viscosity, and the prepared coating exhibits good weather resistance and ultraviolet blocking ability. If the mass ratio is less than 1:4, the reaction viscosity of the first additive is too high, the reaction is incomplete, and the weather resistance of the prepared coating is poor; if the mass ratio is greater than 1:10, the ultraviolet blocking ability of the prepared coating will be insufficient.

[0053] According to a specific embodiment of the present invention, preferably, the hydroxyl content of the ultraviolet absorber is greater than or equal to 5% by mass percentage.

[0054] According to a specific embodiment of the present invention, preferably, the ultraviolet absorber is selected from one or more combinations of Tinuvin 326 (BASF), Tinuvin 1600 (BASF), Uvinul N35 (BASF), Chiguard 329 (Qitai Technology), Eversorb 109 (Eversorb, Taiwan), Cyasorb UV-1164 (Solvay), Neo Heliopan 303 (Symbex).

[0055] According to a specific embodiment of the present invention, preferably, the particle size of the particles in the coating is less than or equal to 200 nm, more preferably less than or equal to 150 nm. When the particle size of the particles in the coating exceeds 200 nm, it will seriously affect the visible light transmittance of the coating made from the obtained coating, and the haze of the coating will also increase.

[0056] According to a specific embodiment of the present invention, preferably, the infrared absorber is selected from one or more combinations of indium tin oxide, tungsten oxide, antimony tin oxide, lanthanum hexaboride, titanium carbide, neodymium-doped yttrium aluminum garnet, cesium tungsten bronze, graphene oxide, etc.

[0057] According to a specific embodiment of the present invention, preferably, the surfactant is selected from one or more combinations of BYK-111 (BYK Chemical), BYK-163 (BYK Chemical), BYK-190 (BYK Chemical), SN-E102 (Sinno New Materials), SN-P605 (Sinno New Materials), SN-D501 (Sinno New Materials).

[0058] According to a specific embodiment of the present invention, preferably, the leveling agent is selected from one or more combinations of BYK-333, TegoWet 270, TegoFlow 425, Siltech E-2140, Dow Corning DC-57, KF-351, and KF-352.

[0059] According to a specific embodiment of the present invention, preferably, the wetting agent is selected from one or more combinations of BYK-345 (BYK Chemical), BYK-349 (BYK Chemical), Tego Wet 260 (Tego), Dow Corning DC-5200 (Dow), Silok-1210 (Silok Chemical), KF-6001 (Shin-Etsu Chemical).

[0060] According to a specific embodiment of the present invention, preferably, the defoamer is selected from one or more combinations of BYK-028 (BYK Chemical), BYK-044 (BYK Chemical), Tego Foamex 810 (Tego), Tego Foamex 7447 (Tego), Dow Corning DC-1638 (Dow), Silok-2300 (Silok Chemical), etc.

[0061] The present invention also provides a method for preparing the above-mentioned coated glass, which includes the following steps:

[0062] The coating is obtained by mixing silica sol, first additive, second additive, and auxiliary agents.

[0063] The coating is applied to at least one surface of glass and cured at 80-120°C to obtain glass with a coating.

[0064] According to a specific embodiment of the present invention, preferably, the silica sol is prepared by mixing silicate ester, first coupling agent, first solvent, water and first catalyst to obtain silica sol.

[0065] According to a specific embodiment of the present invention, preferably, the first additive is prepared by mixing an ultraviolet absorber, a second coupling agent, a second solvent, and a second catalyst to obtain the first additive.

[0066] According to a specific embodiment of the present invention, preferably, the second additive is prepared by mixing an infrared absorber, a surfactant, and a third solvent to obtain the second additive.

[0067] According to a specific embodiment of the present invention, preferably, in the process of preparing silica sol, the mixing is carried out by stirring, the stirring time is 3-12 hours, and the stirring temperature is 20℃-50℃.

[0068] According to a specific embodiment of the present invention, preferably, in the preparation of the first additive, the mixing is carried out by reflux stirring for 2-8 hours at a temperature of 80°C-130°C. During the preparation process, the ultraviolet absorber, by reacting with the second coupling agent within the aforementioned temperature range for the aforementioned time, can obtain good weather resistance. When the temperature exceeds 130℃, the barrier properties of the resulting coating will decrease and the viscosity will increase. When the temperature is below 80℃, the reaction between the UV absorber and the second coupling agent cannot proceed completely, resulting in poor weather resistance of the resulting coating. If the reaction time (i.e., the reflux stirring time) is less than 2 hours, the reaction will be incomplete, resulting in a coating that cannot provide good weather resistance. If the reaction time exceeds 8 hours, the viscosity of the coating will be too high, making it difficult to add and prone to gelation. In addition, during the coating curing process, when the temperature exceeds 180℃ (generally, the coating's abrasion resistance is better when the curing temperature reaches 180℃-190℃), the barrier properties of the coating will decrease, thus failing to balance abrasion resistance and barrier properties.

[0069] According to a specific embodiment of the present invention, preferably, in the process of preparing the second additive, the mixing is carried out by ball milling and homogenization, wherein the ball milling time is 5-24 hours, the ball milling temperature is 20℃-50℃, and the homogenization time is 2-8 hours. More preferably, this step further includes filtration after homogenization, wherein the filter size is 0.5-1μm. By using a two-step operation of ball milling and homogenization to prepare the second additive, the second additive can have a suitable particle size, will not aggregate or settle during long-term storage, and the resulting coating can have low haze and high visible light transmittance. When the two-step operation of ball milling and homogenization is not used, the resulting coating will have excessive haze and will also have a significant adverse effect on visible light transmittance. Furthermore, in order to ensure the extent of the reaction and avoid affecting the haze and visible light transmittance of the coating, a long reaction time is required during the preparation process, during which the second additive is prone to sedimentation. The ball milling, homogenization, and filtration operations described above can be performed using existing ball mills, homogenizers, and filters that meet the usage requirements.

[0070] According to a specific embodiment of the present invention, preferably, in the process of mixing silica sol, the first additive, the second additive, and the auxiliary agent, the mixing is carried out by stirring, the stirring time is 2 hours to 12 hours, and the stirring temperature is 20°C to 50°C.

[0071] According to a specific embodiment of the present invention, preferably, the additive is prepared by mixing a leveling agent, a wetting agent, and a defoamer. Preferably, stirring is performed during the mixing process for 5 to 30 minutes.

[0072] According to a specific embodiment of the present invention, preferably, in step five, before curing at 80-120°C, a pre-drying process is also included for the coating applied to the surface of the glass, wherein the pre-drying temperature is 20-60°C, the humidity is 45%-65%, and the time is 20-40 minutes.

[0073] According to a specific embodiment of the present invention, preferably, the curing time is 30-75 minutes.

[0074] According to a specific embodiment of the present invention, preferably, the process of coating a coating on at least one surface of glass can utilize curved surface coating technology, such as spraying, wiping, flow coating, brushing or dipping, as well as composite coating methods formed by combining ultrasonic, centrifugal or rotational technologies.

[0075] The present invention also provides a vehicle having the aforementioned coated glass.

[0076] According to a specific embodiment of the present invention, preferably, the glass is a vehicle's windshield, side window glass, rear windshield, etc.

[0077] According to a specific embodiment of the present invention, preferably, when the coated glass has a transmittance of greater than or equal to 70% in the wavelength range of 380nm-780nm, it is suitable for use as a windshield or front door glass.

[0078] According to a specific embodiment of the present invention, preferably, when the coated glass has a transmittance of less than or equal to 70% in the wavelength range of 380nm-780nm, it is suitable for use as side window glass or rear windshield glass.

[0079] The technical solution of the present invention has the following beneficial effects:

[0080] The glass surface provided by this invention has a coating that can reduce the transmittance of ultraviolet rays in the wavelength range of 380nm-400nm and the transmittance of infrared rays, thereby simultaneously meeting the requirements of blocking ultraviolet rays and infrared rays in the wavelength range of 380nm-400nm. It is a coating that deeply blocks ultraviolet and infrared rays, and also has excellent aging resistance, wear resistance and other properties, which can extend the normal service life of the glass.

[0081] The coating used in this invention has extremely low VOC emissions, and has advantages such as being green and environmentally friendly and having good construction performance. The resulting coating can also meet the regulations for automotive glass. When applied to laminated glass containing dimming or luminous structures, it can not only block ultraviolet and infrared rays from outside the vehicle, extending the normal service life of the dimming and luminous structures, but also protect the dimming structure, better protect the eyes, and achieve sunshade, privacy, and intelligent energy saving. Attached Figure Description

[0082] Figure 1 This is a schematic diagram of a first structure of a coated glass according to the present invention.

[0083] Figure 2 This is a schematic diagram of a second structure of a coated glass according to the present invention.

[0084] Figure 3 This is a schematic diagram of a third structure of the coated glass of the present invention.

[0085] Figure 4 This is a schematic diagram of a fourth structure of the coated glass of the present invention. Detailed Implementation

[0086] In order to provide a clearer understanding of the technical features, objectives and beneficial effects of the present invention, the technical solution of the present invention will now be described in detail below, but it should not be construed as limiting the scope of implementation of the present invention.

[0087] The coated glass provided by this invention can have the following structure:

[0088] The first structure, such as Figure 1 As shown, the surface of glass 1 is provided with a coating 12; when the glass 11 is automotive glass, the coating 12 is provided on the side surface of glass 11 facing the interior of the vehicle.

[0089] The second structure, such as Figure 2 As shown, the structure is a laminated glass, which includes a first glass plate 21, an intermediate adhesive layer 22, a second glass plate 23, and a coating 24. The intermediate adhesive layer 22 is sandwiched between the first glass plate 21 and the second glass plate 23, and the coating 24 is disposed on the inner surface of the first glass plate 21.

[0090] The third structure, such as Figure 3 As shown, the structure is a laminated glass, which includes a first glass plate 31, an intermediate adhesive layer 32, a second glass plate 33, and a coating 34. The intermediate adhesive layer 32 is sandwiched between the first glass plate 31 and the second glass plate 33, and the coating 34 is disposed on the outer surface of the second glass plate 33.

[0091] The fourth structure, such as Figure 4 As shown, the structure is a laminated glass, which includes a first glass plate 41, an intermediate adhesive layer 42, a second glass plate 43, and a coating 44. The intermediate adhesive layer 42 is sandwiched between the first glass plate 41 and the second glass plate 43, and the coating 44 is disposed on the inner surface of the second glass plate 43.

[0092] Example 1

[0093] This embodiment provides a coated glass, the preparation method of which is as follows:

[0094] 15g of tetraethyl orthosilicate, 60g of anhydrous ethanol, 13g of γ-methacryloyloxypropyltrimethoxysilane, 2g of 10% nitric acid and 12g of deionized water were stirred in a water bath at 40°C for 240 minutes to obtain silica sol A1.

[0095] 10.5g Eversorb 109 UV absorber, 55g butyl acetate, 0.05g dibutyltin dilaurate and 25g γ-methacryloyloxypropyltrimethoxysilane were mixed and refluxed in a 100℃ constant temperature oil bath for 4 hours, and then naturally cooled to room temperature to obtain the first additive U1.

[0096] 15g of cesium tungsten bronze, 20g of SN-D501 and 50g of isopropanol were mixed and ball-milled in a ball mill at room temperature for 8 hours, then homogenized for 3 hours and filtered through a 0.5μm filter to obtain the second additive R1.

[0097] Mix 20g BYK-333, 15g BYK-345 and 5g BYK-044 and stir at room temperature for 20 minutes to obtain additive Z1;

[0098] Weigh 50.5g of silica sol A1, 15.2g of first additive U1, 10.3g of second additive R1, and 0.5g of auxiliary agent Z1, mix and stir for 120 minutes to obtain coating B1;

[0099] In a cleanroom environment, a suitable amount of coating B1 is weighed and applied to the surface of a curved glass plate (visible light transmittance Tl=83.16%, solar transmittance Te=63.14%, ultraviolet transmittance Tuv=42.96%, near-infrared radiation transmittance Tir=47.15%; the same applies to other embodiments and comparative examples) using a wire bar coater. After standing and leveling, the coating B1 is pre-dried with an infrared lamp and then cured at 110°C for 55 minutes to obtain glass C1 with a coating.

[0100] Example 2

[0101] This embodiment provides a coated glass, the preparation method of which is as follows:

[0102] 13.56g of tetraethyl orthosilicate, 22g of anhydrous ethanol, 28g of isopropanol, 5.18g of γ-methacryloyloxypropyltrimethoxysilane, 1g of 10% nitric acid and 12.5g of deionized water were stirred in a water bath at 40°C for 240 minutes to obtain silica sol A2.

[0103] 12.5g Cyasorb UV-1164, 50g butyl acetate, 0.05g dibutyltin dilaurate and 25g γ-methacryloyloxypropyltrimethoxysilane were mixed and refluxed in a constant temperature oil bath at 100℃ for 4 hours, and then naturally cooled to room temperature to obtain the first additive U2.

[0104] 15g of cesium tungsten bronze, 20g of SN-D501 and 50g of isopropanol were mixed and ball-milled in a ball mill at room temperature for 8 hours, then homogenized for 3 hours and filtered through a 0.5μm filter to obtain the second additive R2.

[0105] Mix 20g BYK-333, 15g BYK-345 and 5g BYK-044 and stir at room temperature for 20 minutes to obtain additive Z1;

[0106] Weigh 50.5g of silica sol A2, 15.2g of first additive U2, 10.3g of second additive R2, and 0.5g of auxiliary agent Z1, mix and stir for 120 minutes to obtain coating B2;

[0107] In a dust-free environment, weigh an appropriate amount of coating B2 and apply it to the surface of a curved glass plate using a wire bar applicator. After allowing it to stand and level, pre-dry the coating B2 with an infrared lamp and then cure it at 110°C for 55 minutes to obtain glass C2 with a coating.

[0108] Example 3

[0109] This embodiment provides a coated glass, the preparation method of which is as follows:

[0110] 15.5g of tetraethyl orthosilicate, 30g of anhydrous ethanol, 30g of isopropanol, 6.5g of 3-aminopropyltrimethoxysilane, 1g of 10% nitric acid and 15g of deionized water were stirred in a water bath at 40°C for 240 minutes to obtain silica sol A3.

[0111] 10g Uvinul N35, 50g butyl acetate, 0.05g dibutyltin dilaurate and 20g γ-methacryloyloxypropyltrimethoxysilane were mixed and refluxed in a constant temperature oil bath at 100℃ for 4 hours, and then naturally cooled to room temperature to obtain chelating agent U3.

[0112] 15g of cesium tungsten bronze, 20g of SN-D501 and 50g of isopropanol were mixed and ball-milled in a ball mill at room temperature for 8 hours, then homogenized for 3 hours and filtered through a 0.5μm filter to obtain the second additive R3.

[0113] Mix 10g BYK-333, 8g KF-6001 and 5g BYK-044 and stir at room temperature for 20 minutes to obtain additive Z2;

[0114] Weigh 65.5g of silica sol A3, 10.5g of first additive U3, 6g of second additive R3, and 0.5g of auxiliary agent Z2, mix and stir for 120 minutes to obtain coating B3;

[0115] In a dust-free environment, weigh an appropriate amount of coating B3 and apply it to the surface of a curved glass plate using a wire bar applicator. After allowing it to stand and level, pre-dry the coating B3 with an infrared lamp and then cure it at 110°C for 55 minutes to obtain glass C3 with a coating.

[0116] Example 4

[0117] This embodiment provides a coated glass, the preparation method of which is as follows:

[0118] Weigh 65.5g of silica sol A1, 10.5g of first additive U1, 6g of second additive R1, and 0.5g of auxiliary agent Z1, mix and stir for 240 minutes to obtain coating B4;

[0119] In a dust-free environment, weigh an appropriate amount of coating B4 and apply it to the surface of a curved glass plate using a wire bar applicator. After allowing it to stand and level, pre-dry the coating B4 with an infrared lamp and then cure it at 110°C for 55 minutes to obtain glass C4 with a coating.

[0120] Example 5

[0121] This embodiment provides a coated glass, the preparation method of which is as follows:

[0122] Weigh 55g of silica sol A1, 10g of first additive U1, 15g of second additive R1, and 0.5g of auxiliary agent Z1, mix and stir for 240 minutes to obtain coating B5;

[0123] In a dust-free environment, weigh an appropriate amount of coating B5 and apply it to the surface of a curved glass plate using a wire bar applicator. After allowing it to stand and level, pre-dry the coating B5 with an infrared lamp and then cure it at 110°C for 55 minutes to obtain glass C5 with a coating.

[0124] Comparative Example 1

[0125] This comparative example provides a coated glass, the preparation method of which is as follows:

[0126] In a cleanroom environment, weigh an appropriate amount of silica sol A1 and apply it to the surface of a curved glass plate using a wire bar coater. After allowing it to stand and level, pre-dry the silica sol A1 with an infrared lamp and then cure it at 110°C for 55 minutes to obtain the control glass D1.

[0127] Comparative Example 2

[0128] This comparative example provides a coated glass, the preparation method of which is as follows:

[0129] Weigh 46.5g of silica sol A1, 32.5g of first additive U1, 10.8g of second additive R1, and 0.5g of auxiliary agent Z1, mix and stir for 120 minutes to obtain coating B6;

[0130] In a dust-free environment, weigh an appropriate amount of coating B6 and apply it to the surface of a curved glass plate using a wire bar applicator. After allowing it to stand and level, pre-dry the coating B6 with an infrared lamp and then cure it at 110°C for 55 minutes to obtain glass D2 with a coating.

[0131] Comparative Example 3

[0132] This comparative example provides a coated glass, the preparation method of which is as follows:

[0133] Weigh 54.5g of silica sol A1, 22.5g of first additive U1, 22.8g of second additive R1, and 0.5g of auxiliary agent Z1, mix and stir for 240 minutes to obtain coating B7;

[0134] In a dust-free environment, weigh an appropriate amount of coating B7 and apply it to the surface of a curved glass plate using a wire bar applicator. After allowing it to stand and level, pre-dry the coating B7 with an infrared lamp and then cure it at 110°C for 55 minutes to obtain glass D3 with a coating.

[0135] Comparative Example 4

[0136] This comparative example provides a coated glass, the preparation method of which is as follows:

[0137] 15g of tetraethyl orthosilicate, 60g of anhydrous ethanol, 13g of γ-methacryloyloxypropyltrimethoxysilane, 2g of 10% nitric acid and 12g of deionized water were stirred in a water bath at 40°C for 240 minutes to obtain silica sol A1.

[0138] 10.5g Eversorb 109 line absorbent, 55g butyl acetate solvent, 0.05g dibutyltin dilaurate catalyst and 25g γ-methacryloyloxypropyltrimethoxysilane were mixed and refluxed in a constant temperature oil bath at 100℃ for 1 hour, and then naturally cooled to room temperature to obtain the first additive U1.

[0139] 15g of cesium tungsten bronze, 20g of SN-D501 and 50g of isopropanol were mixed and ball-milled in a ball mill at room temperature for 8 hours, then homogenized for 3 hours and filtered through a 0.5μm filter to obtain the second additive R1.

[0140] Mix 20g BYK-333, 15g BYK-345 and 5g BYK-044 and stir at room temperature for 20 minutes to obtain additive Z1;

[0141] Weigh 50.5g of silica sol A1, 15.2g of first additive U1, 10.3g of second additive R1, and 0.5g of auxiliary agent Z1, mix and stir for 120 minutes to obtain coating B1;

[0142] In a dust-free environment, weigh an appropriate amount of coating B1 and apply it to the surface of a curved glass plate using a wire bar applicator. After allowing it to stand and level, pre-dry the coating B1 with an infrared lamp and then cure it at 110°C for 55 minutes to obtain glass D4 with a coating.

[0143] Comparative Example 5

[0144] This comparative example provides a coated glass, the preparation method of which is as follows:

[0145] 15g of tetraethyl orthosilicate, 60g of anhydrous ethanol, 13g of γ-methacryloyloxypropyltrimethoxysilane, 2g of 10% nitric acid and 12g of deionized water were stirred in a water bath at 40°C for 240 minutes to obtain silica sol A1.

[0146] 10.5g Eversorb 109 UV absorber, 55g butyl acetate, 0.05g dibutyltin dilaurate and 25g γ-methacryloyloxypropyltrimethoxysilane were mixed and refluxed in a 100℃ constant temperature oil bath for 10 hours, and then naturally cooled to room temperature to obtain the first additive U1.

[0147] 15g of cesium tungsten bronze, 20g of SN-D501 and 50g of isopropanol were mixed and ball-milled in a ball mill at room temperature for 8 hours, then homogenized for 3 hours and filtered through a 0.5μm filter to obtain the second additive R1.

[0148] Mix 20g BYK-333, 15g BYK-345 and 5g BYK-044 and stir at room temperature for 20 minutes to obtain additive Z1;

[0149] Weigh 50.5g of silica sol A1, 15.2g of first additive U1, 10.3g of second additive R1, and 0.5g of auxiliary agent Z1, mix and stir for 120 minutes to obtain coating B1;

[0150] In a dust-free environment, weigh an appropriate amount of coating B1 and apply it to the surface of a curved glass plate using a wire bar applicator. After allowing it to stand and level, pre-dry the coating B1 with an infrared lamp and then cure it at 110°C for 55 minutes to obtain glass D5 with a coating.

[0151] Comparative Example 6

[0152] This comparative example provides a coated glass, the preparation method of which is as follows:

[0153] 15g of tetraethyl orthosilicate, 60g of anhydrous ethanol, 13g of γ-methacryloyloxypropyltrimethoxysilane, 2g of 10% nitric acid and 12g of deionized water were stirred in a water bath at 40°C for 240 minutes to obtain silica sol A1.

[0154] 10.5g Eversorb 109 UV absorber, 55g butyl acetate, 0.05g dibutyltin dilaurate and 25g γ-methacryloyloxypropyltrimethoxysilane were mixed and refluxed in a 100℃ constant temperature oil bath for 1 hour, and then naturally cooled to room temperature to obtain the first additive U4.

[0155] 15g of cesium tungsten bronze, 20g of SN-D501 and 50g of isopropanol were mixed and ball-milled in a ball mill at room temperature for 8 hours. The mixture was then filtered through a 0.5μm filter to obtain the second additive R1.

[0156] Mix 20g BYK-333, 15g BYK-345 and 5g BYK-044 and stir at room temperature for 20 minutes to obtain additive Z1;

[0157] Weigh 50.5g of silica sol A1, 15.2g of first additive U1, 10.3g of second additive R1, and 0.5g of auxiliary agent Z1, mix and stir for 120 minutes to obtain coating B1;

[0158] In a dust-free environment, weigh an appropriate amount of coating B1 and apply it to the surface of a curved glass plate using a wire bar applicator. After allowing it to stand and level, pre-dry the coating B1 with an infrared lamp and then cure it at 110°C for 55 minutes to obtain glass D6 with a coating.

[0159] Comparative Example 7

[0160] This comparative example provides a coated glass, the preparation method of which is as follows:

[0161] 15g of tetraethyl orthosilicate, 60g of anhydrous ethanol, 13g of γ-methacryloyloxypropyltrimethoxysilane, 2g of 10% nitric acid and 12g of deionized water were stirred in a water bath at 40°C for 240 minutes to obtain silica sol A1.

[0162] 10.5g Eversorb 109 UV absorber, 55g butyl acetate, 0.05g dibutyltin dilaurate and 25g γ-methacryloyloxypropyltrimethoxysilane were mixed and refluxed in a 100℃ constant temperature oil bath for 1 hour, and then naturally cooled to room temperature to obtain the first additive U1.

[0163] 15g of cesium tungsten bronze, 20g of SN-D501 and 50g of isopropanol were mixed and ball-milled in a ball mill at room temperature for 8 hours, then homogenized for 10 hours and filtered through a 0.5μm filter to obtain the second additive R4.

[0164] Mix 20g BYK-333, 15g BYK-345 and 5g BYK-044 and stir at room temperature for 20 minutes to obtain additive Z1;

[0165] Weigh 50.5g of silica sol A1, 15.2g of first additive U1, 10.3g of second additive R1, and 0.5g of auxiliary agent Z1, mix and stir for 120 minutes to obtain coating B1;

[0166] In a dust-free environment, weigh an appropriate amount of coating B1 and apply it to the surface of a curved glass plate using a wire bar applicator. After allowing it to stand and level, pre-dry the coating B1 with an infrared lamp and then cure it at 110°C for 55 minutes to obtain glass D7 with a coating.

[0167] Comparative Example 8

[0168] This comparative example provides a coated glass, the preparation method of which is as follows:

[0169] 15g of tetraethyl orthosilicate, 60g of anhydrous ethanol, 13g of γ-methacryloyloxypropyltrimethoxysilane, 2g of 10% nitric acid and 12g of deionized water were stirred in a water bath at 40°C for 240 minutes to obtain silica sol A1.

[0170] 10.5g Eversorb 109 UV absorber, 55g butyl acetate, 0.05g dibutyltin dilaurate and 25g γ-methacryloyloxypropyltrimethoxysilane were mixed and refluxed in a 100℃ constant temperature oil bath for 1 hour, and then naturally cooled to room temperature to obtain the first additive U1.

[0171] 15g of cesium tungsten bronze, 20g of SN-D501 and 50g of isopropanol were mixed and ball-milled in a ball mill at room temperature for 8 hours, then homogenized for 1 hour, and filtered through a 0.5μm filter to obtain the second additive R1.

[0172] Mix 20g BYK-333, 15g BYK-345 and 5g BYK-044 and stir at room temperature for 20 minutes to obtain additive Z1;

[0173] Weigh 50.5g of silica sol A1, 15.2g of first additive U1, 10.3g of second additive R1, and 0.5g of auxiliary agent Z1, mix and stir for 120 minutes to obtain coating B1;

[0174] In a dust-free environment, weigh an appropriate amount of coating B1 and apply it to the surface of a curved glass plate using a wire bar applicator. After allowing it to stand and level, pre-dry the coating B1 with an infrared lamp and then cure it at 110°C for 55 minutes to obtain glass D8 with a coating.

[0175] Comparative Example 9

[0176] This comparative example provides a coated glass, the preparation method of which is as follows:

[0177] 15g of tetraethyl orthosilicate, 60g of anhydrous ethanol, 13g of γ-methacryloyloxypropyltrimethoxysilane, 2g of 10% nitric acid and 12g of deionized water were stirred in a water bath at 40°C for 240 minutes to obtain silica sol A1.

[0178] 12g of RIASORB® UV-329 ultraviolet absorber, 50g of butyl acetate, 0.05g of dibutyltin dilaurate and 28g of γ-methacryloyloxypropyltrimethoxysilane were mixed and refluxed in a 100°C constant temperature oil bath for 4 hours, and then naturally cooled to room temperature to obtain the first additive U9.

[0179] 15g of cesium tungsten bronze, 20g of SN-D501 and 50g of isopropanol were mixed and ball-milled in a ball mill at room temperature for 8 hours, then homogenized for 3 hours and filtered through a 0.5μm filter to obtain the second additive R1.

[0180] Mix 20g BYK-333, 15g BYK-345 and 5g BYK-044 and stir at room temperature for 20 minutes to obtain additive Z1;

[0181] Weigh 50.5g of silica sol A1, 15.2g of first additive U1, 10.3g of second additive R1, and 0.5g of auxiliary agent Z1, mix and stir for 120 minutes to obtain coating B9;

[0182] In a dust-free environment, an appropriate amount of coating B9 was weighed and coated onto the surface of a curved glass plate (the visible light transmittance of the glass is Tl=83.16%, solar transmittance is Te=63.14%, ultraviolet transmittance is Tuv=42.96%, and near-infrared radiation transmittance is Tir=47.15%; the same applies to other embodiments and comparative examples) using a wire bar coater. After standing and leveling, the coating B9 was pre-dried with an infrared lamp and then cured at 110°C for 55 minutes to obtain glass C9 with a coating.

[0183] Comparative Example 10

[0184] This comparative example provides a coated glass, the preparation method of which is as follows:

[0185] 15g of tetraethyl orthosilicate, 60g of anhydrous ethanol, 13g of γ-methacryloyloxypropyltrimethoxysilane, 2g of 10% nitric acid and 12g of deionized water were stirred in a water bath at 40°C for 240 minutes to obtain silica sol A1.

[0186] 10.5g Eversorb 109 UV absorber, 55g butyl acetate, 0.05g dibutyltin dilaurate and 25g γ-methacryloyloxypropyltrimethoxysilane were mixed and refluxed in a 100℃ constant temperature oil bath for 4 hours, and then naturally cooled to room temperature to obtain the first additive U1.

[0187] 18g of tungsten trioxide, 23g of SN-D501 and 54g of isopropanol were mixed and ball-milled in a ball mill at room temperature for 8 hours, then homogenized for 3 hours and filtered through a 0.5μm filter to obtain the second additive R10.

[0188] Mix 20g BYK-333, 15g BYK-345 and 5g BYK-044 and stir at room temperature for 20 minutes to obtain additive Z1;

[0189] Weigh 50.5g of silica sol A1, 15.2g of first additive U1, 10.3g of second additive R1, and 0.5g of auxiliary agent Z1, mix and stir for 120 minutes to obtain coating B10;

[0190] In a cleanroom environment, weigh an appropriate amount of coating B10 and apply it to the surface of a curved glass plate (visible light transmittance Tl=83.16%, solar transmittance Te=63.14%, ultraviolet transmittance Tuv=42.96%, near-infrared radiation transmittance Tir=47.15%; the same applies to other embodiments and comparative examples). After allowing it to level, pre-dry the coating B10 with an infrared lamp and then cure it at 110°C for 55 minutes to obtain glass C10 with a coating.

[0191] Test Evaluation:

[0192] The glasses obtained in Examples 1-5 and Comparative Examples 1-10 were subjected to the following tests and evaluations. The evaluation results are shown in Tables 1 and 2.

[0193] Transmittance: Transmittance spectra in the wavelength range of 250-2550 nm were measured using a spectrophotometer;

[0194] The transmittance of ultraviolet light in the 300nm-400nm range is calculated according to ISO13837 standard, and the transmittance of visible light in the 380nm-780nm range and infrared light in the 780nm-2500nm range are calculated according to ISO9050 standard. The single-point transmittance at 400nm and 410nm is obtained from the transmission spectrum. The color a* and b* values ​​are calculated according to D6510. The transmittance mentioned in this invention refers to the value calculated by measuring the midpoint of a glass sample.

[0195] Coating thickness: Measured using a profilometer.

[0196] Aging resistance: The aging resistance test method involves placing the sample in a xenon lamp aging tester calibration lamp equipment (model: CI4000, USA) for continuous dry irradiation at 300nm-400nm: 60±2w / m 2To determine the radiation intensity, the test duration was 2000 hours, the blackboard temperature was 65±3℃, and the relative humidity was 50±10% for the aging resistance test. After the aging resistance test, the appearance of the coating was observed to see if cracks appeared, and the optical properties were tested.

[0197] Abrasion resistance: Measured using a surface abrasion tester. The glass sample is placed on the instrument with the coating facing up, and a surface abrasion test is performed at 1000 revolutions.

[0198] Haze: The haze meter was used to test the sample after the abrasion resistance test. The area that had not undergone the abrasion resistance test was tested to obtain Haze1. The sample was moved and the area that had undergone the abrasion resistance test was tested to obtain Haze2. The haze difference before and after the test = |Haze2-Haze1|.

[0199] Inorganic nanoparticle size: measured using a laser nanoparticle size analyzer.

[0200] Table 1: Evaluation results of Examples 1-5

[0201]

[0202] Table 2: Evaluation results of comparative examples 1-10

[0203]

[0204] The particle size of a coating refers to the particle size of the particles in the final coating product.

[0205] The test results shown in Tables 1 and 2 show that:

[0206] Comparative Example 1 forms a silica sol coating on a curved glass plate. Although its aging resistance and wear resistance meet the requirements, it does not have the ability to block ultraviolet rays in the wavelength range of 380nm-400nm and block infrared rays.

[0207] The amount of the first additive in the coating used in Comparative Example 2 exceeded the scope of the present invention, resulting in the visible light transmittance of the coated glass being <70%, a* / b* being <0.5, the coating color being yellowish, and the coating having poor wear resistance.

[0208] The amount of the second additive in the coating used in Comparative Example 3 exceeded the scope of the present invention, resulting in the visible light transmittance of the coated glass being <70%, a* / b* being >1.5, and the coating color being grayish-blue.

[0209] The coating used in Comparative Example 4 had insufficient reaction time during the preparation of the first additive, resulting in insufficient weather resistance of the coated glass.

[0210] The coating used in Comparative Example 5 had an excessively long reaction time during the preparation of the first additive, resulting in the initial TUV of the coated glass being substandard, i.e., its ability to block ultraviolet rays in the wavelength range of 380nm-400nm was poor.

[0211] The coating used in Comparative Example 6 was not homogenized during the preparation of the second additive, resulting in a visible light transmittance of the coated glass of <70%, a* / b*>1.5, and a grayish-blue coating color.

[0212] The homogenization process of the coating used in Comparative Example 7 was too long during the preparation of the second additive, resulting in poor wear resistance of the coated glass and low ability to block infrared rays.

[0213] The cesium tungsten bronze inorganic nanoparticles used in Comparative Example 8 have a relatively large particle size. When the same amount of addition is used as in Example 1, the heat insulation effect is similar, but the visible light transmittance is reduced and does not meet the requirement of being greater than 70%, and the aging resistance is also unqualified.

[0214] The UV absorber used in Comparative Example 9 has an absorption peak of less than 350nm, resulting in insufficient UV absorption capacity of the coating and unqualified UV blocking performance.

[0215] The infrared absorber used in Comparative Example 10 has an absorption peak between 1700-1900nm, which makes the heat insulation performance unsatisfactory and the heat insulation performance unqualified.

[0216] The glass in Examples 1-5 has good blocking ability for ultraviolet and infrared rays in the wavelength range of 380nm-400nm, and also has excellent weather resistance and wear resistance. The coating color is also relatively soft and not particularly bright.

Claims

1. A type of glass with a coating, wherein, The surface of the glass has a coating; The coating contains ultraviolet absorbers and infrared absorbers; The peak values ​​of all absorption peaks of the ultraviolet absorber are below 390 nm, and the maximum absorption peak is in the wavelength range of 350 nm to 380 nm. The peak values ​​of all absorption peaks of the infrared absorber are above 900 nm, and the maximum absorption peak is in the wavelength range of 950 nm to 1500 nm. The coated glass has a transmittance of less than or equal to 1% in the wavelength range of 300nm-400nm; The coated glass has a transmittance of less than or equal to 15% in the wavelength range of 780nm-2500nm.

2. The glass according to claim 1, wherein, The thickness of the coating is 2μm-12μm.

3. The glass according to claim 1, wherein, The coated glass has a minimum transmittance of 15% or greater at a wavelength of 410 nm.

4. The glass according to claim 1, wherein, The ratio of the transmittance T410 of the coated glass at 410 nm to its transmittance T400 at 400 nm satisfies: 15 ≤ T410 / T400 ≤ 100.

5. The glass according to claim 1, wherein, The coated glass has a transmittance of 70% or higher in the wavelength range of 380nm-780nm.

6. The glass according to claim 1, wherein, After undergoing a 2000-hour xenon lamp aging test, the coated glass exhibits a transmittance of 70% or higher in the wavelength range of 380nm-780nm.

7. The glass according to claim 1, wherein, After undergoing a 1000-revolution abrasion test using a planar abrasion tester, the difference in haze between the coated glass and the haze before the test is less than or equal to 5%.

8. The glass according to claim 1, wherein, The ratio of the a* value to the b* value of the color of the coated glass satisfies the following condition: |a* / b*| is 0.5-1.

5.

9. The glass according to claim 1, wherein, The coating is made of paint; By weight percentage, the coating contains 50-84.9% silica sol, 10-30% first additive, 5-20% second additive, and 0.1-1% auxiliary agents; The first additive contains an ultraviolet absorber; The second additive contains an infrared absorber.

10. The glass according to claim 9, wherein, The first additive contains 5-15% ultraviolet absorber by weight percentage; The second additive contains 15-40% infrared absorber by weight percentage.

11. A vehicle having a coated glass as described in any one of claims 1-10.

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