Ultraviolet absorber chelate, coating, and coated glass

Abstract

Provided is an ultraviolet absorber chelate. Raw materials of the ultraviolet absorber chelate comprise, in parts by mass: 10-30 parts of a first solvent; 2.5-10 parts of an ultraviolet absorber A having an absorption peak at 280 nm-315 nm; 2.5-15 parts of an ultraviolet absorber B having an absorption peak at 315 nm-380 nm; 0.05-1.5 parts of a photostabilizer; 40-65 parts of a coupling agent; and 0.01-0.1 parts of a first catalyst. Also provided are a preparation method for the ultraviolet absorber chelate, a coating prepared from the ultraviolet absorber chelate and a preparation method for the coating, a coating layer formed from the coating, and coated glass comprising the coating layer. The coating layer has a transmittance of less than 2% for UVA and UVB, and has a high ultraviolet blocking capability.

Description

UV absorber chelates and coatings and coated glass

[0001] This application claims priority to Chinese Patent Application No. 202411516487.9, filed on October 29, 2024, entitled "Ultraviolet Absorber Chelates and Coatings and Coated Glass", the entire contents of which are incorporated herein by reference. Technical Field

[0002] This invention relates to the field of glass manufacturing technology, and more particularly to a chelate of ultraviolet absorbers and coatings and coated glass. Background Technology

[0003] Functional coatings can be formed on the surface of a substrate using surface coating technology. As different automotive OEMs change their requirements for optical specifications, the desired goals have become increasingly stringent, including a light incident angle of 0°-90° relative to the glass surface and UVB (280nm-315nm) and UVA (315nm-400nm) transmittance of less than 2%. This has led to new requirements for the selection and amount of optical materials added to the coating. To be usable on automotive glass, the coating must also possess properties such as abrasion resistance and weather resistance, while simultaneously ensuring adequate adhesion between the coating and the glass.

[0004] To improve the optical performance of coatings, invention application CN103613280A (application number 201310597206) discloses a coating liquid for forming an ultraviolet-absorbing coating and an ultraviolet-absorbing glass. This application discloses a coating liquid for forming an ultraviolet-absorbing coating on the surface of glass or other objects, an ultraviolet-absorbing glass having the ultraviolet-absorbing coating formed by the coating liquid, and a method for preparing the ultraviolet-absorbing glass. The coating liquid, ultraviolet-absorbing glass, and method used in this application reduce the accumulation of excited electrons in the ultraviolet absorber during ultraviolet absorption by storing and releasing electrons excited by ultraviolet light. This protects the ultraviolet absorber and the silica matrix, prevents discoloration or devitrification of the ultraviolet-absorbing glass, ensures the weather resistance of the ultraviolet-absorbing coating, and guarantees the color consistency of the ultraviolet-absorbing glass. The calculation method is based on the Tuv calculated according to the ISO9050-2003(E) standard. Although this application can achieve Tuv (300-380nm) < 1%, Tuv (300-400nm) > 1%, which cannot meet the test requirements of UVB (280nm-315nm) and UVA (315nm-400nm) < 1%. Patent CN219446360U discloses a high-strength laminated glass with UV protection, comprising an outer pressure-resistant glass layer, a first EVA film layer at the bottom of the outer pressure-resistant glass layer, a UV-resistant glass layer adhered to the end of the first EVA film layer away from the outer pressure-resistant glass layer, an SGP interlayer at the bottom of the UV-resistant glass layer, a high-temperature resistant glass layer adhered to the end of the SGP interlayer layer away from the UV-resistant glass layer, a second EVA film layer at the bottom of the high-temperature resistant glass layer, an inner sound-insulating glass layer adhered to the end of the second EVA film layer away from the high-temperature resistant glass layer, a laminated glass layer at the center of the outer pressure-resistant glass layer, and a tempered glass layer at the top of the laminated glass layer. However, the application of laminated glass in this patent, that is, the function of blocking ultraviolet rays can only be achieved through laminated glass, and cannot be applied to single-pane glass.

[0005] Therefore, there is a need for a coating liquid and related products that can block both UVA and UVB ultraviolet rays. Summary of the Invention

[0006] To address the aforementioned problems, the present invention aims to provide a UV absorber chelate, a coating, and a coated glass, wherein the coating formed by the coating solution has a transmittance of less than 2% for both UVA and UVB, and thus possesses high UV blocking capability.

[0007] To achieve the above objectives, the present invention provides an ultraviolet absorber chelate, wherein, by weight, the raw materials of the ultraviolet absorber chelate include:

[0008] First solvent: 10-30 parts, UV absorber A: 2.5-10 parts, UV absorber B: 2.5-15 parts, light stabilizer: 0.05-1.5 parts, coupling agent: 40-65 parts, first catalyst: 0.01-0.1 parts;

[0009] The absorption peak of ultraviolet absorber A is located in the range of 280nm-315nm; the absorption peak of ultraviolet absorber B is located in the range of 315nm-380nm.

[0010] In some specific embodiments, the ultraviolet absorber A and ultraviolet absorber B may each include one or more of the following reagents: benzophenone ultraviolet absorbers, benzimidazole ultraviolet absorbers, triazine ultraviolet absorbers, oxaloylaniline ultraviolet absorbers, Chiguard P, Chiguard 1033, and Chiguard 5540.

[0011] In some specific embodiments, when UV absorber A and UV absorber B are selected from one or more combinations of benzophenone UV absorbers, benzimidazole UV absorbers, triazine UV absorbers, and oxaloaniline UV absorbers, UV absorber A and UV absorber B may be selected from one or more combinations of the same or different categories of benzophenone UV absorbers, benzimidazole UV absorbers, triazine UV absorbers, and oxaloaniline UV absorbers.

[0012] In some specific embodiments, the ultraviolet absorber A and ultraviolet absorber B can be selected from the same major category of ultraviolet absorbers mentioned above (benzophenone ultraviolet absorbers, benzimidazole ultraviolet absorbers, triazine ultraviolet absorbers, oxaloylaniline ultraviolet absorbers), thereby obtaining ultraviolet absorber chelates with high purity.

[0013] Specifically, the benzimidazole ultraviolet absorber may include one or more of 2-(2'-hydroxy-5'-methylphenyl)-benzotriazole, 2-(2'-hydroxy-3',5'-bis[1,1-dimethylphenyl]phenyl)-benzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chloro-benzotriazole, Chiguard 234, and Chiguard 380.

[0014] Specifically, the benzophenone-based ultraviolet absorber may include 2-hydroxy-4-methoxybenzophenone and / or 2-hydroxy-4-octoxybenzophenone.

[0015] Specifically, the triazine ultraviolet absorber may include one or more of ethyl 2-cyano-3,3-diphenylacrylate, isooctyl 2-cyano-3,3-diphenylacrylate, Chiguard 1064, and Chiguard 5431.

[0016] Specifically, the oxaloylaniline-based ultraviolet absorber may include N-(ethyl 4-benzoate)-N',N'-(methyl,phenyl)formamidine and / or N,N'-bis(4-ethoxycarbonylphenyl)-N'-benzylformamidine.

[0017] According to a specific embodiment of the present invention, the absorption peak of the ultraviolet absorber A is generally 280-315 nm, and more preferably 290-305 nm. That is, an ultraviolet absorber with an absorption peak of 280-315 nm (e.g., an absorption peak of 290-305 nm) can be selected as ultraviolet absorber A.

[0018] According to a specific embodiment of the present invention, the absorption peak of the ultraviolet absorber B is generally 315nm-380nm, and more specifically 340nm-380nm. That is, an ultraviolet absorber with an absorption peak of 315nm-380nm (e.g., an absorption peak of 340nm-380nm) can be selected as ultraviolet absorber B.

[0019] According to a specific embodiment of the present invention, the ultraviolet absorber B generally has a certain type of functional groups for reacting with the ultraviolet absorber A and the light stabilizer. Specifically, the functional groups of the ultraviolet absorber B may include one or more combinations of hydroxyl, carbonyl, and ketone groups.

[0020] According to a specific embodiment of the present invention, the molecule of the light stabilizer has at least one hydroxyl group; further, the molecule of the light stabilizer may have two or more hydroxyl groups. The hydroxyl groups in the light stabilizer ensure that the light stabilizer reacts with UV absorber A and UV absorber B, and enable the light stabilizer to have a certain degree of solubility in water.

[0021] In some specific embodiments, the light stabilizer includes pentamethylpiperidinol, tetramethylpiperidinol, a polymer of succinic acid and (4-hydroxy-2,2,6,6-tetramethyl-1-piperidinol) (also known as light stabilizer 622), polysuccinic acid (4-hydroxy-2,2,6,6-tetramethyl-1-piperidinol) ester, and... HS-3310 One or more combinations of HS-508, etc.

[0022] According to specific embodiments of the present invention, the UV absorber A, UV absorber B, and light stabilizer are soluble in water. In some specific embodiments, the solubility of UV absorber A and UV absorber B in water at 25°C is greater than or equal to 60 g / L. The light stabilizer contains hydroxyl groups and also has good water solubility. Therefore, the above-mentioned UV absorber chelate also has good water solubility. When the above-mentioned UV absorber chelate is used to prepare coatings, it can dissolve in the water in the coating to have good compatibility with other raw materials of the coating.

[0023] According to a specific embodiment of the present invention, the mass fraction of the ultraviolet absorber A in the raw material of the ultraviolet absorber chelate is generally 2.5 parts to 10 parts, specifically 2.5 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 7.5 parts, 8 parts, 9 parts, 10 parts, etc., and a range with any two of the above specific values ​​as endpoints.

[0024] According to a specific embodiment of the present invention, the mass fraction of the ultraviolet absorber B in the raw material of the ultraviolet absorber chelate is generally 2.5 parts to 15 parts, specifically 2.5 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 7.5 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, etc., and a range with any two of the above specific values ​​as endpoints.

[0025] According to a specific embodiment of the present invention, the mass fraction of the light stabilizer in the raw material of the ultraviolet absorber chelate is generally 0.05 parts to 1.5 parts, specifically 0.05 parts, 0.1 parts, 0.2 parts, 0.3 parts, 0.4 parts, 0.5 parts, 1 part, 1.5 parts, etc., and a range with any two of the above specific values ​​as endpoints.

[0026] In some specific implementations, the ratio of the mass of the light stabilizer to the sum of the masses of UV absorber A and UV absorber B can be 0.02-0.3:1, specifically 0.02:1, 0.03:1, 0.04:1, 0.05:1, 0.06:1, 0.07:1, 0.08:1, 0.09:1, 0.1:1, 0.15:1, 0.2:1, 0.3:1, etc., and a range with any two of the above specific values ​​as endpoints, and further can be 0.04-0.2:1.

[0027] According to a specific embodiment of the present invention, the first catalyst is capable of catalyzing the reaction between ultraviolet absorber A, ultraviolet absorber B and light stabilizer.

[0028] In some specific embodiments, the first catalyst may include one or more of benzyltriethylammonium chloride (TEBA), tetrabutylammonium bromide (TBAB), tetrabutylammonium chloride, tetrabutylammonium bisulfate, trioctylmethylammonium chloride, dodecyltrimethylammonium chloride, and tetradecyltrimethylammonium chloride.

[0029] According to a specific embodiment of the present invention, the mass fraction of the first catalyst in the raw material of the ultraviolet absorber chelate is generally 0.01-0.1 parts, specifically 0.01 parts, 0.02 parts, 0.03 parts, 0.04 parts, 0.05 parts, 0.06 parts, 0.07 parts, 0.08 parts, 0.09 parts, 0.1 parts, etc., and a range with any two of the above specific values ​​as endpoints.

[0030] In some specific embodiments, the mass of the first catalyst can be 1 / 300 to 1 / 50 of the total mass of UV absorber A and UV absorber B. For example, it can be a specific value such as 1 / 300, 1 / 250, 1 / 200, 1 / 150, 1 / 100, 1 / 50, or a range with any two of the above specific values ​​as endpoints. Further, it can be 1 / 200 to 1 / 50.

[0031] According to a specific embodiment of the present invention, the coupling agent participates in the reaction between ultraviolet absorber A, ultraviolet absorber B, and light stabilizer. The coupling agent generally contains an active group capable of participating in the above reaction, such as one or more combinations of oxygen-containing hydrolyzable functional groups, hydroxyl groups, amine groups, and epoxy groups capable of ring-opening reactions; simultaneously, when the above ultraviolet absorber chelate is used to prepare coatings, the coupling agent also contains an active group that reacts with alkoxysilanes, and this group is not consumed in the reaction that generates the ultraviolet absorber chelate but is retained.

[0032] According to specific embodiments of the present invention, the coupling agent may include a silane coupling agent and / or a titanate coupling agent. Specifically, the silane coupling agent may include one or more combinations of γ-aminoethylaminopropyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, 3-(methacryloyloxy)propyltrimethoxysilane, 3-(2-aminoethyl)-aminopropyltrimethoxysilane, and 3-(methacryloyloxy)propyltriethoxysilane; and the titanate coupling agent may include one or more combinations of polybutyl titanate, tetrapropyl titanate, and isopropyltris(dioctylphosphoyloxy)titanate. The coupling agent may include one or more of the following: γ-aminoethylaminopropyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, 3-(methacryloyloxy)propyltrimethoxysilane, 3-(2-aminoethyl)-aminopropyltrimethoxysilane, 3-(methacryloyloxy)propyltriethoxysilane, polybutyl titanate, tetrapropyl titanate, and isopropyltris(dioctylphosphoyloxy)titanate.

[0033] According to a specific embodiment of the present invention, the mass fraction of the coupling agent in the raw material of the ultraviolet absorber chelate is generally 40-65 parts, specifically 40 parts, 45 parts, 50 parts, 55 parts, 60 parts, 65 parts, etc., and a range with any two of the above specific values ​​as endpoints.

[0034] According to a specific embodiment of the present invention, the boiling point of the first solvent is above 100°C. That is, the first solvent is a solvent with a boiling point above 100°C. The first solvent can reduce the viscosity of the reaction system and improve the uniformity of the reaction during the reaction of ultraviolet absorber A, ultraviolet absorber B and light stabilizer.

[0035] In some specific embodiments, the first solvent may include one or more of propylene glycol methyl ether, butyl acetate, ethyl propionate, butanol (such as n-butanol), etc.

[0036] According to a specific embodiment of the present invention, the mass fraction of the first solvent in the raw material of the ultraviolet absorber chelate is generally 10 to 30 parts, specifically 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, etc., and a range with any two of the above specific values ​​as endpoints.

[0037] This invention also provides a method for preparing the above-mentioned ultraviolet absorber chelate, the method comprising:

[0038] A light stabilizer, UV absorber A, UV absorber B, coupling agent, and a first catalyst are mixed and subjected to a first reaction to obtain the UV absorber chelate.

[0039] In the above-mentioned method for preparing ultraviolet absorber chelates, the light stabilizer, ultraviolet absorber A, ultraviolet absorber B, and coupling agent generate a chelate through a first reaction. The absorption peak of this ultraviolet absorber chelate shifts relative to the absorption peaks of the two raw material ultraviolet absorbers. The chelate exhibits strong absorption capacity for ultraviolet light with a wavelength of 380-400 nm. Simultaneously, the generated chelate also enhances the weather resistance of the product. Applying the above-mentioned ultraviolet absorber chelate to the preparation of coating solutions yields coating solutions with good ultraviolet isolation properties.

[0040] In the above method for preparing the ultraviolet absorber chelate, the temperature of the first reaction is 120-150℃, specifically 120℃, 125℃, 130℃, 135℃, 140℃, 145℃, 150℃, or any two of the above values ​​as endpoints; the time of the first reaction is 2h-6h, specifically 2h, 3h, 4h, 5h, 6h, or any two of the above values ​​as endpoints. In some specific embodiments, the first reaction can be a reflux reaction.

[0041] According to a specific embodiment of the present invention, in the process of preparing an ultraviolet absorber chelate by means of a first solvent, ultraviolet absorber A, ultraviolet absorber B, light stabilizer, coupling agent, and a first catalyst through a reflux reaction, the first solvent is retained in the ultraviolet absorber chelate and presents a uniform liquid phase. Under the action of the catalyst, one end of the chemical bond of the coupling agent (containing an oxygen-containing hydrolyzable functional group, such as hydroxyl, amino, or epoxy group that can undergo ring-opening reaction, etc.) reacts and combines with the hydroxyl groups of the ultraviolet absorber and the light stabilizer to form a viscous, flowable polymer.

[0042] According to a specific embodiment of the present invention, the above preparation method may specifically include: adding ultraviolet absorber A, ultraviolet absorber B, coupling agent, first solvent, light stabilizer and first catalyst to a reaction device (generally an oil bath with stirring and reflux), adjusting the heating power and constant temperature of the reaction device, and turning on the stirring and heating function of the oil bath, and carrying out the reaction under constant temperature stirring and reflux (i.e., the first reaction), and turning off the heating function after completion; after cooling to room temperature, taking out the reaction product, which is the ultraviolet absorber chelate, for later use.

[0043] The present invention also provides a coating liquid, wherein the raw materials of the coating liquid, based on the total mass of the coating liquid as 100%, include:

[0044] The composition comprises 10%-30% alkoxysilane, 30%-60% second solvent, 10%-25% of the above-mentioned ultraviolet absorber chelate provided by the present invention, 0.01%-1% second catalyst, 0.5%-3% auxiliary agent, and 10%-30% water, wherein the total mass of the above components is 100%.

[0045] According to a specific embodiment of the present invention, the alkoxysilane can generate silicon oxide through a hydrolysis reaction under the catalysis of a second catalyst. The alkoxysilane may include one or a combination of two or more of methyl orthosilicate, tetraethyl orthosilicate, trimethoxysilane, triethoxysilane, and dimethyldimethoxysilane.

[0046] According to a specific embodiment of the present invention, the alkoxysilane generally accounts for 10%-30% of the mass percentage of the raw materials in the coating solution, specifically 10%, 12.5%, 15%, 17.5%, 20%, 22.5%, 25%, 27.5%, 30%, etc., and ranges with any two of the above specific values ​​as endpoints. According to a specific embodiment of the present invention, molecules derived from the coupling agent in the ultraviolet absorber chelate can react with the alkoxysilane, thereby improving the weather resistance and abrasion resistance of the coating formed by the coating solution. The present invention has found that by controlling the mass ratio of the coupling agent (one of the raw materials of the ultraviolet absorber chelate) to the alkoxysilane, the weather resistance and abrasion resistance of the coating formed by the coating solution can be adjusted; when the amount of coupling agent added increases, the weather resistance of the coating can be improved, but the abrasion resistance of the coating will decrease. Specifically, when the mass ratio of coupling agent to alkoxysilane is less than 0.3:1, the coating formed by the coating solution has a radiation resistance of <100h; when the mass ratio of coupling agent to alkoxysilane is greater than 1.2:1, the haze difference of the coating formed by the coating solution before and after the wear resistance test is >5%; controlling the mass ratio of coupling agent to alkoxysilane to 0.3-1.2:1 can achieve both good weather resistance and wear resistance, and the resulting coating formed by the coating solution has a radiation resistance of ≥100h, and the haze difference before and after the wear resistance test is ≤5%.

[0047] The ultraviolet absorber chelate contained in the above coating liquid has an absorption peak located in the range of 280-400 nm, has two or more absorption peaks, and is made of at least two kinds of ultraviolet absorbers (ultraviolet absorber A and ultraviolet absorber B).

[0048] According to a specific embodiment of the present invention, UV absorber A and UV absorber B, which are raw materials for the UV absorber chelate, have two absorption peaks before the reaction; after the reaction, the obtained UV absorber chelate, in addition to having the two absorption peaks of the two raw material UV absorbers, also generates a new absorption peak at 380-400 nm, and the UV absorption capacity is significantly improved (see Figure 3). In some specific embodiments, the absorption peaks (two or more) of the UV absorber chelate are located at 280-400 nm.

[0049] According to a specific embodiment of the present invention, the mass percentage of the ultraviolet absorber chelate in the raw materials of the coating liquid is generally 10%-25%, specifically 10%, 12.5%, 15%, 17.5%, 20%, 22.5%, 25%, etc., and a range with any two of the above specific values ​​as endpoints.

[0050] According to a specific embodiment of the present invention, the second solvent may include one or more of ethanol, isopropanol, butanol (such as n-butanol), and propylene glycol methyl ether.

[0051] According to a specific embodiment of the present invention, the second solvent generally accounts for 30%-60% of the mass of the raw materials in the coating liquid, specifically 30%, 35%, 40%, 45%, 50%, 55%, 60%, etc., and ranges with any two of the above specific values ​​as endpoints. According to a specific embodiment of the present invention, the second catalyst comprises an inorganic acid capable of catalyzing the hydrolysis and polycondensation of alkoxysilanes. Specifically, the second catalyst comprises one or a combination of two or more of hydrochloric acid, nitric acid, sulfuric acid, and acetic acid.

[0052] According to a specific embodiment of the present invention, the mass percentage of the second catalyst in the raw materials of the coating solution is generally 0.01%-1%, specifically it can be 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, etc., and a range with any two of the above specific values ​​as endpoints.

[0053] According to a specific embodiment of the present invention, the mass percentage of the additive in the raw materials of the coating liquid is generally 0.5%-3%, specifically it can be 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, etc., and a range with any two of the above specific values ​​as endpoints.

[0054] According to a specific embodiment of the present invention, the additives include one or a combination of two or more of leveling agents, defoamers, and wetting agents.

[0055] Among the above-mentioned additives, the leveling agent may include one or a combination of two or more of BYK-332, BYK-333, BYK-341 and BYK-348.

[0056] Among the above-mentioned additives, the defoamer includes one or more of BYK-020, BYK-022, BYK-028 and BYK-080A.

[0057] Among the above-mentioned additives, the lubricant includes one or more of BYK-110, BYK-170, BYK-171 and BYK-180.

[0058] According to a specific embodiment of the present invention, the water content in the raw materials of the coating liquid is generally 10%-30%, specifically 10%, 12.5%, 15%, 17.5%, 20%, 22.5%, 25%, 27.5%, 30%, etc., and a range with any two of the above specific values ​​as endpoints.

[0059] The present invention also provides a method for preparing the above-mentioned coating liquid, the method comprising: mixing an ultraviolet absorber chelate with an alkoxysilane, a second solvent, a second catalyst, an auxiliary agent and water, and carrying out a second reaction to obtain the coating liquid.

[0060] In the above method for preparing the coating solution, the second reaction is a hydrolysis reaction of alkoxysilane catalyzed by a second catalyst to generate silicon oxide. The temperature of the second reaction is 20℃-50℃, specifically 20℃, 25℃, 30℃, 35℃, 40℃, 45℃, 50℃, etc., or any two of the above specific values ​​as endpoints; the time of the second reaction is 30min-120min, specifically 30min, 40min, 50min, 60min, 70min, 80min, 90min, 100min, 110min, 120min, etc., or any two of the above specific values ​​as endpoints.

[0061] According to a specific embodiment of the present invention, the reaction product obtained after the second reaction is silica sol, and the water in the above coating can ensure that the silica sol evaporates at a suitable rate to form a uniform coating.

[0062] According to a specific embodiment of the present invention, the method for preparing the above-mentioned coating may specifically include:

[0063] In a conical flask, add the weighed second solvent, alkoxysilane, UV absorber chelate, second catalyst, water, and additives in sequence. Stir at a certain temperature (20℃-50℃) for a period of time (30min-120min) to carry out the second reaction. Then, remove the stirred product and filter it (using a filter with a certain mesh size) to obtain the coating. The coating can be stored in a light-proof sealed container (such as a light-proof sealed plastic bottle) for later use.

[0064] According to a specific embodiment of the present invention, during the preparation of the coating from components such as alkoxysilane, a second solvent, a UV absorber chelate, a second catalyst, an additive, and water, the alkoxysilane and the siloxane in the UV absorber chelate undergo partial hydrolysis. In the presence of the second solvent, water, and the second catalyst, the alkoxysilane and the siloxane in the UV absorber chelate in the system are in a state of hydrolysis (forward reaction) and condensation (reverse reaction), which is a sol state.

[0065] The present invention also provides a coating formed by drying and curing the above-mentioned coating solution. The coating comprises a chelate of silica and an ultraviolet absorber, exhibiting a transmittance of less than or equal to 2% for both UVB (wavelength 280-315nm) and UVA (wavelength 315-400nm), and further reaching less than or equal to 1%, thus possessing high ultraviolet blocking capability. In some specific embodiments, the curing temperature can be 80℃-200℃, specifically 80℃, 90℃, 100℃, 150℃, 200℃, etc., or a range with any two of the above specific values ​​as endpoints; the curing time is 10min-200min, specifically 10min, 50min, 100min, 150min, 200min, etc., or a range with any two of the above specific values ​​as endpoints.

[0066] According to a specific embodiment of the present invention, in the coating formed by curing the coating, the first solvent and the second solvent evaporate, which disrupts the equilibrium state of hydrolysis and condensation in the coating. The coating mainly undergoes hydrolysis reaction. As curing proceeds, the solvents (organic solvent and water) completely evaporate, forming a coating of organic-inorganic hybrid silicon oxide compound with ultraviolet absorption capability.

[0067] The present invention also provides a coated glass comprising a glass substrate and a coating, wherein the coating is disposed on at least one surface of the glass substrate; the coating is formed by drying and curing the coating liquid provided by the present invention.

[0068] In the above-mentioned coated glass, the thickness of the coating is generally controlled to be 5μm-10μm, specifically 5μm, 6μm, 7μm, 8μm, 9μm, 10μm, etc., and the range of any two of the above-mentioned specific values ​​as endpoints, and can be further controlled to be 6μm-8μm.

[0069] In the above-mentioned coated glass, the glass substrate can be curved glass, and the original sheet of the glass substrate can include one type of float glass such as float clear glass, float grey glass, and float dark clear glass.

[0070] According to a specific embodiment of the present invention, the transmittance of the coated glass for light with an incident angle of 0°-90° and a wavelength of 280-315nm is less than or equal to 2%, and further less than or equal to 1%; the transmittance of the coated glass for light with an incident angle of 0°-90° and a wavelength of 315-400nm is less than or equal to 2%, and further less than or equal to 1%. The transmittance can be calculated based on the spectrophotometer scanning results of the coated glass, and the calculation method can be any one of the automotive glass optical testing standards such as ISO 9050, ISO 13837, average transmittance, or arbitrary single-point transmittance.

[0071] The coating formed by the above-mentioned coating liquid provided by the present invention can effectively block ultraviolet light. The coated glass containing the coating has a high ultraviolet blocking ability and can be used as a high ultraviolet blocking coated glass.

[0072] According to specific embodiments of the present invention, the ultraviolet blocking capability of the coated glass is increased compared to the uncoated glass substrate, while the visible light transmittance does not decrease significantly. In some specific embodiments, the coated glass has a T400nm (400nm single-point transmittance) ≤1%, and the difference between the visible light transmittance of the coated glass and the visible light transmittance of the uncoated glass substrate is less than or equal to 5%. T400nm can be calculated based on the spectrophotometric scanning results of the coated glass, and the calculation method can be any of the automotive glass optical testing standards such as ISO9050, ISO13837, average transmittance, and arbitrary single-point transmittance.

[0073] According to specific embodiments of the present invention, the coating in the above-mentioned coated glass has high adhesion to the glass substrate; applying the above-mentioned coated glass as automotive glass can ensure driving safety. In some specific embodiments, the cross-cut adhesion test result of the coated glass can reach level 0.

[0074] According to a specific embodiment of the present invention, the coated glass has high abrasion resistance. For example, the haze difference of the coating before and after the abrasion resistance test can be controlled within 5%. The abrasion resistance test can be specifically performed as follows: the coated glass is placed in a plane abrasion tester with the coating facing upward, the test pressure is 4.9N, and a plane abrasion test is performed for 1000 revolutions. The haze H1 is obtained by testing the area of ​​the sample that has not undergone the abrasion resistance test, and the haze H2 is obtained by testing the area that has undergone the abrasion resistance test. The haze difference before and after the test is equal to H2 - H1.

[0075] According to specific embodiments of the present invention, the above-mentioned coated glass has good weather resistance. In some specific embodiments, after 100 hours of irradiation, the coating of the coated glass remains intact and does not crack, and the difference in ultraviolet transmittance of the coated glass before and after irradiation can be controlled to be less than 1%, and further controlled to be less than 0.94%.

[0076] The present invention also provides a method for preparing the above-mentioned coated glass, the method comprising: applying a coating to the surface of a glass substrate and leveling it, and then drying and curing the coating to obtain the glass.

[0077] In the above-mentioned method for preparing coated glass, the curing temperature is 80℃-200℃ and the curing time is 10min-200min.

[0078] In the above-mentioned method for preparing coated glass, the leveling temperature can be 15℃-30℃, the leveling humidity is 45%RH-75%RH, and the leveling time is 1min-20min.

[0079] In the above-mentioned method for preparing coated glass, the coating method may include one of spin coating, roller coating, dip coating, flow coating, curtain coating or spray coating.

[0080] The beneficial effects of this invention include:

[0081] The coating formed by the coating liquid provided by this invention has high ultraviolet blocking performance, especially the transmittance of ultraviolet light for UVB and UVA can be as low as 2% or less, thereby improving customer satisfaction with the product; at the same time, the high ultraviolet blocking coating also has excellent wear resistance; and the coating liquid has extremely low VOC emissions, with advantages such as green environmental protection and good construction performance; applying the coating to glass can improve the ultraviolet blocking ability of the glass, which can meet the regulations for automotive glass. Attached Figure Description

[0082] Figure 1 is a schematic diagram of the structure of the coated glass of Embodiments 1 to 3 and Comparative Examples 1 to 4 of the present invention.

[0083] Figure 2 shows the infrared characterization results of Test Example 1.

[0084] Figure 3 shows the absorbance test results of Test Example 1.

[0085] Explanation of main reference numerals: Glass substrate 100, coating 101. 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] In the following experiments, UV absorber A was Chiguard 1033, UV absorber B was the triazine UV absorber Chiguard 1064, the light stabilizer was bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, and the first catalyst was dodecyltrimethylammonium chloride.

[0088] Preparation Example 1

[0089] This preparation example provides a UV absorber chelate, which is prepared by the following method:

[0090] Weigh 20g of n-butanol, 5g of UV absorber A, 10g of UV absorber B, 0.3g of light stabilizer, 65g of γ-methacryloyloxypropyltrimethoxysilane, and 0.05g of the first catalyst and add them to a round-bottom flask. Place the conical flask in an oil bath, turn on the stirring and heating, set the oil bath temperature to 120℃, and reflux for 120min. Turn off the heating of the oil bath and let it cool naturally to room temperature while stirring to obtain approximately 100g of chelate A1.

[0091] Preparation Example 2

[0092] This preparation example provides a UV absorber chelate, which is prepared by the following method:

[0093] Weigh 30g of n-butanol, 5g of UV absorber A, 0.3g of light stabilizer, 65g of γ-methacryloxypropyltrimethoxysilane, and 0.05g of the first catalyst and add them to a round-bottom flask. Place the conical flask in an oil bath, turn on the stirring and heating, set the oil bath temperature to 120℃ and reflux for 120min. Turn off the heating of the oil bath and let it cool naturally to room temperature while stirring to obtain approximately 100g of chelate A2.

[0094] Preparation Example 3

[0095] This preparation example provides a UV absorber chelate, which is prepared by the following method:

[0096] Weigh 25g of n-butanol, 10g of UV absorber B, 0.3g of light stabilizer, 65g of γ-methacryloxypropyltrimethoxysilane, and 0.05g of the first catalyst and add them to a round-bottom flask. Place the conical flask in an oil bath, turn on the stirring and heating, set the oil bath temperature to 120℃ and reflux for 120min. Turn off the heating of the oil bath and let it cool naturally to room temperature while stirring to obtain approximately 100g of chelate A3.

[0097] Preparation Example 4

[0098] This preparation example provides a UV absorber chelate, which is prepared by the following method:

[0099] Weigh 20g of n-butanol, 5g of UV absorber A, 10g of UV absorber B, 65g of γ-methacryloxypropyltrimethoxysilane, and 0.05g of the first catalyst and add them to a round-bottom flask. Place the conical flask in an oil bath, turn on the stirring and heating, set the oil bath temperature to 120℃ and reflux for 120min. Turn off the heating of the oil bath and let it cool naturally to room temperature while stirring to obtain approximately 100g of chelate A4.

[0100] Preparation Example 5

[0101] This preparation example provides a UV absorber chelate, which is prepared by the following method:

[0102] Weigh 20g of n-butanol, 5g of UV absorber A, 10g of UV absorber B, 0.3g of light stabilizer, 131.9g of γ-methacryloyloxypropyltrimethoxysilane, and 0.05g of the first catalyst and add them to a round-bottom flask. Place the conical flask in an oil bath, turn on the stirring and heating, set the oil bath temperature to 120℃, and reflux for 120min. Turn off the heating of the oil bath and let it cool naturally to room temperature while stirring. About 167g of chelate A5 was obtained.

[0103] Example 1

[0104] This embodiment provides a coating, the preparation method of which includes:

[0105] Weigh out 54g of propylene glycol methyl ether, 15g of tetraethyl orthosilicate, 15g of chelate A1, 0.3g of acetic acid, 15g of deionized water, 0.5g of BYK-333, and 0.2g of BYK-180; stir the above components in a 40℃ water bath for 60 minutes to obtain coating B1.

[0106] This embodiment also provides a coated glass, as shown in FIG1. ​​The coated glass includes a glass substrate 100 and a coating 101. The coating 101 is located on at least one surface of the glass substrate 100 and is formed by curing paint B1. In this embodiment, the glass substrate 100 is curved glass.

[0107] The preparation method of the above-mentioned coated glass is as follows:

[0108] In a Class 10,000 cleanroom environment with a temperature of 22℃±3℃ and a humidity of 65%RH±5%RH, coating B1 was applied to the surface of a cleaned curved glass substrate using a manual spray gun. After standing for 10 minutes and allowing the coating to level on the surface of the curved glass substrate, the coating was pre-dried with an infrared lamp to form a high UV-blocking coating with a thickness of 5μm-6μm. The coated curved glass substrate was then placed in 120℃ for curing for 60 minutes. After the curved glass substrate cooled naturally to room temperature, it was removed to obtain coated glass C1, which can be used as a high UV-blocking coating for automotive glass.

[0109] Example 2

[0110] This embodiment provides a coating liquid, the preparation method of which includes:

[0111] Weigh out 49g of propylene glycol methyl ether, 15g of tetraethyl orthosilicate, 20g of chelate A1, 0.3g of acetic acid, 15g of deionized water, 0.5g of BYK-333, and 0.2g of BYK-180; stir the above components in a 40℃ water bath for 60min to obtain coating B2.

[0112] This embodiment also provides a coated glass, as shown in FIG1. ​​The coated glass includes a glass substrate 100 and a coating 101. The coating 101 is located on at least one surface of the glass substrate 100 and is formed by curing paint B2. In this embodiment, the glass substrate 100 is curved glass.

[0113] The preparation method of the above-mentioned coated glass is as follows:

[0114] In a Class 10,000 cleanroom environment with a temperature of 22℃±3℃ and a humidity of 65%RH±5%RH, coating B2 was applied to the surface of a cleaned curved glass substrate using a manual spray gun. After standing for 10 minutes and allowing the coating to level on the surface of the curved glass substrate, the coating was pre-dried with an infrared lamp to form a high UV-blocking coating with a thickness of 5μm-6μm. The coated curved glass substrate was then placed in 120℃ for curing for 60 minutes. After the curved glass substrate cooled naturally to room temperature, it was removed to obtain coated glass C2, which can be used as a high UV-blocking coating for automotive glass.

[0115] Example 3

[0116] This embodiment provides a coating liquid, the preparation method of which includes:

[0117] Weigh out 44g of propylene glycol methyl ether, 15g of tetraethyl orthosilicate, 25g of chelate A1, 0.3g of acetic acid, 15g of deionized water, 0.5g of BYK-333, and 0.2g of BYK-180; stir the above components in a 40℃ water bath for 60 minutes to obtain coating B3.

[0118] This embodiment also provides a coated glass, as shown in FIG1. ​​The coated glass includes a glass substrate 100 and a coating 101. The coating 101 is located on at least one surface of the glass substrate 100 and is formed by curing paint B3. In this embodiment, the glass substrate 100 is curved glass.

[0119] The preparation method of the above-mentioned coated glass is as follows:

[0120] In a Class 10,000 cleanroom environment with a temperature of 22℃±3℃ and a humidity of 65%RH±5%RH, coating B3 was applied to the surface of a cleaned curved glass substrate using a manual spray gun. After standing for 10 minutes and allowing the coating to level on the surface of the curved glass substrate, the coating was pre-dried with an infrared lamp to form a high UV-blocking coating with a thickness of 5μm-6μm. The curved glass substrate with the high UV-blocking coating was then placed in 120℃ for curing for 60 minutes. After the curved glass substrate cooled naturally to room temperature, it was removed to obtain coated glass C3, which can be used as a high UV-blocking coating for automotive glass.

[0121] Example 4

[0122] This embodiment provides a coating, the preparation method of which includes:

[0123] Weigh out 48g of propylene glycol methyl ether, 12g of tetraethyl orthosilicate, 24g of chelate A1, 0.3g of acetic acid, 15g of deionized water, 0.5g of BYK-333, and 0.2g of BYK-180; stir the above components in a 40℃ water bath for 60 minutes to obtain coating B4.

[0124] This embodiment also provides a coated glass, as shown in FIG1. ​​The coated glass includes a glass substrate 100 and a coating 101. The coating 101 is located on at least one surface of the glass substrate 100 and is formed by curing paint B4. In this embodiment, the glass substrate 100 is curved glass.

[0125] The preparation method of the above-mentioned coated glass is as follows:

[0126] In a Class 10,000 cleanroom environment with a temperature of 22℃±3℃ and a humidity of 65%RH±5%RH, coating B4 was applied to the surface of a cleaned curved glass substrate using a manual spray gun. After standing for 10 minutes and allowing the coating to level on the surface of the curved glass substrate, the coating was pre-dried with an infrared lamp to form a high UV-blocking coating with a thickness of 5μm-6μm. The coated curved glass substrate was then placed in 120℃ for curing for 60 minutes. After the curved glass substrate cooled naturally to room temperature, it was removed to obtain coated glass C4, which can be used as a high UV-blocking coating for automotive glass.

[0127] Example 5

[0128] This embodiment provides a coating, the preparation method of which includes:

[0129] Weigh out 40g of propylene glycol methyl ether, 15g of tetraethyl orthosilicate, 15g of chelate A1, 0.02g of acetic acid, 30g of deionized water, 0.5g of BYK-333, and 0.2g of BYK-180; stir the above components in a 40℃ water bath for 60min to obtain coating B5.

[0130] This embodiment also provides a coated glass, as shown in FIG1. ​​The coated glass includes a glass substrate 100 and a coating 101. The coating 101 is located on at least one surface of the glass substrate 100 and is formed by curing paint B5. In this embodiment, the glass substrate 100 is curved glass.

[0131] The preparation method of the above-mentioned coated glass is as follows:

[0132] In a Class 10,000 cleanroom environment with a temperature of 22℃±3℃ and a humidity of 65%RH±5%RH, coating B5 was applied to the surface of a cleaned curved glass substrate using a manual spray gun. After standing for 10 minutes and allowing the coating to level on the surface of the curved glass substrate, the coating was pre-dried with an infrared lamp to form a high UV-blocking coating with a thickness of 5μm-6μm. The coated curved glass substrate was then placed in 120℃ for curing for 60 minutes. After the curved glass substrate cooled naturally to room temperature, it was removed to obtain coated glass C5, which can be used as a high UV-blocking coating for automotive glass.

[0133] Example 6

[0134] This embodiment provides a coating, the preparation method of which includes:

[0135] Weigh out 40g of propylene glycol methyl ether, 29g of tetraethyl orthosilicate, 14.5g of chelate A1, 0.9g of acetic acid, 15g of deionized water, 0.4g of BYK-333, and 0.2g of BYK-180; stir the above components in a 40℃ water bath for 60min to obtain coating B6.

[0136] This embodiment also provides a coated glass, as shown in FIG1. ​​The coated glass includes a glass substrate 100 and a coating 101. The coating 101 is located on at least one surface of the glass substrate 100 and is formed by curing paint B6. In this embodiment, the glass substrate 100 is curved glass.

[0137] The preparation method of the above-mentioned coated glass is as follows:

[0138] In a Class 10,000 cleanroom environment with a temperature of 22℃±3℃ and a humidity of 65%RH±5%RH, coating B6 was applied to the surface of a cleaned curved glass substrate using a manual spray gun. After standing for 10 minutes and allowing the coating to level on the surface of the curved glass substrate, the coating was pre-dried with an infrared lamp to form a high UV-blocking coating with a thickness of 5μm-6μm. The coated curved glass substrate was then placed in 120℃ for curing for 60 minutes. After the curved glass substrate cooled naturally to room temperature, it was removed to obtain coated glass C6, which can be used as a high UV-blocking coating for automotive glass.

[0139] Example 7

[0140] This embodiment provides a coating, the preparation method of which includes:

[0141] Weigh out 50g of propylene glycol methyl ether, 10g of tetraethyl orthosilicate, 23g of chelate A1, 0.02g of nitric acid, 16g of deionized water, 0.5g of BYK-333, and 0.2g of BYK-180; stir the above components in a 40℃ water bath for 60min to obtain coating B7.

[0142] This embodiment also provides a coated glass, as shown in FIG1. ​​The coated glass includes a glass substrate 100 and a coating 101. The coating 101 is located on at least one surface of the glass substrate 100 and is formed by curing paint B7. In this embodiment, the glass substrate 100 is curved glass.

[0143] The preparation method of the above-mentioned coated glass is as follows:

[0144] In a Class 10,000 cleanroom environment with a temperature of 22℃±3℃ and a humidity of 65%RH±5%RH, coating B7 was applied to the surface of a cleaned curved glass substrate using a manual spray gun. After standing for 10 minutes and allowing the coating to level on the surface of the curved glass substrate, the coating was pre-dried with an infrared lamp to form a high UV-blocking coating with a thickness of 5μm-6μm. The coated curved glass substrate was then placed in 120℃ for curing for 60 minutes. After the curved glass substrate cooled naturally to room temperature, it was removed to obtain coated glass C7, which can be used as a high UV-blocking coating for automotive glass.

[0145] Comparative Example 1

[0146] This comparative example provides a coating solution, the preparation method of which includes:

[0147] Weigh out 60g of propylene glycol methyl ether, 15g of tetraethyl orthosilicate, 9g of chelate A1, 0.3g of acetic acid, 15g of deionized water, 0.5g of BYK-333, and 0.2g of BYK-180; stir the above components in a 40℃ water bath for 60 minutes to obtain coating B8.

[0148] This comparative example also provides a coated glass, as shown in FIG1. ​​The coated glass includes a glass substrate 100 and a coating 101. The coating 101 is located on at least one surface of the glass substrate 100 and is formed by curing paint B8. In this embodiment, the glass substrate 100 is curved glass.

[0149] The preparation method of the above-mentioned coated glass is as follows:

[0150] In a Class 10,000 cleanroom environment with a temperature of 22℃±3℃ and a humidity of 65%RH±5%RH, coating B8 is applied to the surface of a cleaned curved glass substrate using a manual spray gun. After standing for 10 minutes and allowing the coating to level on the surface of the curved glass substrate, the coating is pre-dried with an infrared lamp to form a high UV-blocking coating with a thickness of 5μm-6μm. Then, the curved glass substrate with the high UV-blocking coating is placed in 120℃ for curing for 60 minutes. After the curved glass substrate is allowed to cool naturally to room temperature, it is removed to obtain coated glass C8, which can be used as a high UV-blocking coating for automotive glass.

[0151] Comparative Example 2

[0152] This comparative example provides a coating solution, the preparation method of which includes:

[0153] Weigh out 40g of propylene glycol methyl ether, 15g of tetraethyl orthosilicate, 30g of chelate A1, 0.3g of acetic acid, 15g of deionized water, 0.5g of BYK-333, and 0.2g of BYK-180; stir the above components in a 40℃ water bath for 60 minutes to obtain coating B9.

[0154] This comparative example also provides a coated glass, as shown in FIG1. ​​The coated glass includes a glass substrate 100 and a coating 101. The coating 101 is located on at least one surface of the glass substrate 100 and is formed by curing paint B9. In this embodiment, the glass substrate 100 is curved glass.

[0155] The preparation method of the above-mentioned coated glass is as follows:

[0156] In a Class 10,000 cleanroom environment with a temperature of 22℃±3℃ and a humidity of 65%RH±5%RH, coating B9 is applied to the surface of a cleaned curved glass substrate using a manual spray gun. After standing for 10 minutes and allowing the coating to level on the surface of the curved glass substrate, the coating is pre-dried with an infrared lamp to form a high UV-blocking coating with a thickness of 5μm-6μm. Then, the curved glass substrate with the high UV-blocking coating is placed in 120℃ for curing for 60 minutes. After the curved glass substrate is allowed to cool naturally to room temperature, it is removed to obtain coated glass C9, which can be used as a high UV-blocking coating for automotive glass.

[0157] Comparative Example 3

[0158] This comparative example provides a coating solution, the preparation method of which includes:

[0159] Weigh out 54g of propylene glycol methyl ether, 15g of tetraethyl orthosilicate, 15g of chelate A2, 0.3g of acetic acid, 15g of deionized water, 0.5g of BYK-333, and 0.2g of BYK-180; stir the above components in a 40℃ water bath for 60 minutes to obtain coating B10.

[0160] This comparative example also provides a coated glass, as shown in FIG1. ​​The coated glass includes a glass substrate 100 and a coating 101. The coating 101 is located on at least one surface of the glass substrate 100 and is formed by curing paint B10. In this embodiment, the glass substrate 100 is curved glass.

[0161] The preparation method of the above-mentioned coated glass is as follows:

[0162] In a Class 10,000 cleanroom environment with a temperature of 22℃±3℃ and a humidity of 65%RH±5%RH, coating B10 was applied to the surface of a cleaned curved glass substrate using a manual spray gun. After standing for 10 minutes and allowing the coating to level on the surface of the curved glass substrate, the coating was pre-dried with an infrared lamp to form a high UV-blocking coating with a thickness of 5μm-6μm. The coated curved glass substrate was then placed in 120℃ for curing for 60 minutes. After the curved glass substrate cooled naturally to room temperature, it was removed to obtain coated glass C10, which can be used as a high UV-blocking coating for automotive glass.

[0163] Comparative Example 4

[0164] This comparative example provides a coating solution, the preparation method of which includes:

[0165] Weigh out 54g of propylene glycol methyl ether, 15g of tetraethyl orthosilicate, 15g of chelate A3, 0.3g of acetic acid, 15g of deionized water, 0.5g of BYK-333, and 0.2g of BYK-180; stir the above components in a 40℃ water bath for 60 minutes to obtain coating B11.

[0166] This comparative example also provides a coated glass, as shown in FIG1. ​​The coated glass includes a glass substrate 100 and a coating 101. The coating 101 is located on at least one surface of the glass substrate 100 and is formed by curing paint B11. In this embodiment, the glass substrate 100 is curved glass.

[0167] The preparation method of the above-mentioned coated glass is as follows:

[0168] In a Class 10,000 cleanroom environment with a temperature of 22℃±3℃ and a humidity of 65%RH±5%RH, coating B11 was applied to the surface of a cleaned curved glass substrate using a manual spray gun. After standing for 10 minutes and allowing the coating to level on the surface of the curved glass substrate, the coating was pre-dried with an infrared lamp to form a high UV-blocking coating with a thickness of 5μm-6μm. The coated curved glass substrate was then placed in 120℃ for curing for 60 minutes. After the curved glass substrate cooled naturally to room temperature, it was removed to obtain coated glass C11, which can be used as a high UV-blocking coating for automotive glass.

[0169] Comparative Example 5

[0170] This comparative example provides a coating solution, the preparation method of which includes:

[0171] Weigh out 54g of propylene glycol methyl ether, 15g of tetraethyl orthosilicate, 15g of chelate A4, 0.3g of acetic acid, 15g of deionized water, 0.5g of BYK-333, and 0.2g of BYK-180; stir the above components in a 40℃ water bath for 60 minutes to obtain coating B12.

[0172] This comparative example also provides a coated glass, as shown in FIG1. ​​The coated glass includes a glass substrate 100 and a coating 101. The coating 101 is located on at least one surface of the glass substrate 100 and is formed by curing paint B12. In this embodiment, the glass substrate 100 is curved glass.

[0173] The preparation method of the above-mentioned coated glass is as follows:

[0174] In a Class 10,000 cleanroom environment with a temperature of 22℃±3℃ and a humidity of 65%RH±5%RH, coating B12 was applied to the surface of a cleaned curved glass substrate using a manual spray gun. After standing for 10 minutes and allowing the coating to level on the surface of the curved glass substrate, the coating was pre-dried with an infrared lamp to form a high UV-blocking coating with a thickness of 5μm-6μm. The coated curved glass substrate was then placed in 120℃ for curing for 60 minutes. After the curved glass substrate cooled naturally to room temperature, it was removed to obtain coated glass C12, which can be used as a high UV-blocking coating for automotive glass.

[0175] Comparative Example 6

[0176] This comparative example provides a coating, the preparation method of which includes:

[0177] Weigh out 54g of propylene glycol methyl ether, 15g of tetraethyl orthosilicate, 3g of butanol, 0.75g of UV absorber A, 1.5g of UV absorber B, 0.05g of light stabilizer, 9.7g of γ-methacryloyloxypropyltrimethoxysilane, 0.0075g of the first catalyst, 0.3g of acetic acid, 15g of deionized water, 0.5g of BYK-333, and 0.2g of BYK-180; stir the above components in a 40℃ water bath for 60 minutes to obtain coating B13.

[0178] This comparative example also provides a coated glass, as shown in FIG1. ​​The coated glass includes a glass substrate 100 and a coating 101. The coating 101 is located on at least one surface of the glass substrate 100 and is formed by curing coating B13. In this embodiment, the glass substrate 100 is curved glass.

[0179] The preparation method of the above-mentioned coated glass is as follows:

[0180] In a Class 10,000 cleanroom environment with a temperature of 22℃±3℃ and a humidity of 65%RH±5%RH, coating B13 was applied to the surface of a cleaned curved glass substrate using a manual spray gun. After standing for 10 minutes and allowing the coating to level on the surface of the curved glass substrate, the coating was pre-dried with an infrared lamp to form a high UV-blocking coating with a thickness of 5μm-6μm. The coated curved glass substrate was then placed in 120℃ for curing for 60 minutes. After the curved glass substrate cooled naturally to room temperature, it was removed to obtain coated glass C13, which can be used as a high UV-blocking coating for automotive glass.

[0181] Comparative Example 7

[0182] This comparative example provides a coating, the preparation method of which includes:

[0183] Weigh out 54g of propylene glycol methyl ether, 15g of tetraethyl orthosilicate, 25g of chelate A5, 0.3g of acetic acid, 15g of deionized water, 0.5g of BYK-333, and 0.2g of BYK-180; stir the above components in a 40℃ water bath for 60 minutes to obtain coating B14.

[0184] This comparative example also provides a coated glass, as shown in FIG1. ​​The coated glass includes a glass substrate 100 and a coating 101. The coating 101 is located on at least one surface of the glass substrate 100 and is formed by curing coating B14. In this embodiment, the glass substrate 100 is a curved glass.

[0185] The preparation method of the above-mentioned coated glass is as follows:

[0186] In a Class 10,000 cleanroom environment with a temperature of 22℃±3℃ and a humidity of 65%RH±5%RH, coating B14 was applied to the surface of a cleaned curved glass substrate using a manual spray gun. After standing for 10 minutes and allowing the coating to level on the surface of the curved glass substrate, the coating was pre-dried with an infrared lamp to form a high UV-blocking coating with a thickness of 5μm-6μm. The coated curved glass substrate was then placed in 120℃ for curing for 60 minutes. After the curved glass substrate cooled naturally to room temperature, it was removed to obtain coated glass C14, which can be used as a high UV-blocking coating for automotive glass.

[0187] The testing methods used in the following test cases are as follows:

[0188] Visible light transmittance: The transmittance spectrum in the wavelength range of 250nm-2550nm was measured using a spectrophotometer (instrument model: Perkin Elmer, Lambda 950) at angles of 5°, 45° and 90°.

[0189] Visible light transmittance was calculated according to ISO 9050 standard; the optical transmittance in this test was the average value obtained by measuring five different points on the same film.

[0190] Ultraviolet transmittance: The ultraviolet portion is measured at 10nm intervals from 280nm to 400nm. The average value is obtained by measuring the ultraviolet transmittance at five different points on the same film.

[0191] Coating thickness: The thickness of the coating was measured using a step profile meter (instrument model: KLA-TENCOR P16+ USA).

[0192] Abrasion resistance: Surface abrasion tester (instrument model: Taber5135 USA), cut a 10cm×10cm sample, place the sample on the instrument with the coating facing up, and perform surface abrasion for 1000 revolutions at a pressure of 4.9N.

[0193] Haze Test: Place the abrasion test sample in the haze meter (instrument model: HZ-V3 Japan). The haze level of the un-polished area is measured as Haze1. Move the sample to the polished area and measure the haze level as Haze2. The difference in haze level before and after is equal to |Haze2 - Haze1|.

[0194] Weather resistance test of coating: The weather resistance test refers to GB / T31849-2015 "Automotive window tinting glass". Cut a 10cm×30cm sample, place the coated side of the sample facing the light source (wavelength range 300-400nm), and irradiate continuously for 100h. Use a spectrophotometer to test the Tuv (ultraviolet transmittance) (the calculation standard of Tuv is according to ISO13837). Calculate the difference before and after the experiment and record it as ΔTuv.

[0195] Coating Adhesion Test: Adhesion testing was conducted according to ISO 2409 standard. Table 1 lists the adhesion rating criteria. A cross-cut adhesion tester (model 5123) manufactured by BYK GmbH, Germany, was used. First, the coated glass was fixed face up on the test platform. A 1mm cross-cut adhesion tester (11 blades) was selected. The pressure was controlled so that when the blade scratched the glass, the cross-cut adhesion tester was used to cut approximately 10cm across the coated surface. Then, the cross-cut adhesion tester was used to cut 100 square grids at an angle perpendicular to the first cut. Approximately 10cm of designated adhesive tape was cut and pressed onto the grid, ensuring complete coverage. The tape was then quickly pulled up within 0.5-1 second, with the angle between the pulled-up tape and the coated surface at 60°. Finally, the cut area was brushed clean to remove any remaining impurities. The 100 square grids cut by the cross-cut adhesion tester were observed using a magnifying glass. The adhesion rating of the coating was determined by referring to Table 1.

[0196] Table 1 Adhesion Grade Evaluation

[0197] Test Example 1

[0198] The chelates from the preparation examples were structurally characterized.

[0199] The unreacted raw material in Preparation Example 1 was characterized by infrared spectroscopy and absorbance testing. The results are shown in the "before chelation" curves in Figures 2 and 3. The chelate obtained after the reaction was then characterized as described above, and the results are shown in the "after chelation" curves in Figures 2 and 3.

[0200] As shown in Figure 2, compared to the raw materials before the reaction, the sample after the reaction has a larger diameter at 1002 cm⁻¹. -1 The appearance of a new peak at 3500 cm⁻¹ indicates that an aromatic ether ketone ester ether may have formed after the reaction, with oxygen linked to a side-chain carbon. -1 The peak at this location is more pronounced, indicating that there may be more free hydroxyl groups at this point. These factors combined may explain the appearance of a new absorption peak near 360 nm in the ultraviolet light after the reaction.

[0201] As shown in Figure 3, the raw materials before the reaction exhibit two absorption peaks in the 280-350 nm wavelength range, which originate from the two UV absorbers in the raw materials. The chelate after the reaction retains the two absorption peaks present before the reaction and also generates a new absorption peak in the 360-400 nm position. This result indicates that the present invention, through the first reaction, generates new functional groups in the chelate and enhances its absorption capacity for light in the 380-400 nm wavelength range, significantly improving its UV absorption capability.

[0202] Test Example 2

[0203] This test example provides the performance test results of the coated glass of the above embodiments and comparative examples.

[0204] The evaluation results of visible light transmittance, ultraviolet transmittance, film thickness, coating abrasion resistance, coating weather resistance, and coating-glass adhesion of the coated glass in each embodiment are shown in Tables 2 and 3. In addition, a glass substrate (uncoated blank glass) was provided as a control sample for the above-mentioned coated glass. In Tables 2 and 3, the "Visible Light Transmittance Change Value" represents the difference in visible light transmittance between the coated glass and the uncoated blank glass of the embodiments. Tables 4 and 5 show the evaluation results of visible light transmittance, ultraviolet transmittance, film thickness, coating abrasion resistance, coating weather resistance, and coating-glass adhesion of the coated glass in each comparative example.

[0205] Table 2 Evaluation results of blank glass and coated glass of Examples 1-3

[0206] Table 3 Evaluation results of the coated glass in Examples 4-7

[0207] Table 4 Evaluation results of the coated glass in Comparative Examples 1-4

[0208] Table 5 Evaluation results of the coated glass in Comparative Examples 5-7

[0209] As can be seen from Tables 2 and 3, the coated glasses provided in the examples all exhibit excellent visible light transmittance, high UV blocking performance, abrasion resistance, and coating adhesion. Specifically, the difference in visible light transmittance between the coated glass and the uncoated blank glass plate is less than or equal to 5%; the transmittance of the coated glass for UV light (especially light with a wavelength of 380-400nm) with an incident angle of 5-90° and a wavelength of 280-400nm is less than or equal to 1%; the change in visible light transmittance is <2%; the difference in haze before and after the abrasion resistance test is less than or equal to 5%; the change in UV transmittance after radiation resistance is <1%; and the cross-cut test result of the coated glass can reach level 0.

[0210] A comparison of the test results in Tables 2 and 3 with those in Tables 4 and 5 shows that:

[0211] In Comparative Example 1, when the amount of chelate added was too low, the weather resistance of the coating decreased, the UV blocking ability decreased, and the adhesion between the coating and the glass decreased; however, the visible light transmittance of the coating increased, and the wear resistance improved.

[0212] In Comparative Example 2, when the amount of chelate added was too large, the visible light transmittance of the coating decreased and the wear resistance was reduced; however, the weather resistance of the coating improved, the UV blocking ability improved, and the adhesion between the coating and the glass improved.

[0213] In Comparative Example 3, UV absorber A was not added to the raw materials of the UV absorber chelate. Although the visible light transmittance, weather resistance, adhesion between the coating and glass, and wear resistance of the coating were not significantly different from those in Example 1, the UV absorber A content in the 280nm-320nm UV region could not meet the requirement of <1%.

[0214] In Comparative Example 4, no UV absorber B was added to the raw materials of the UV absorber chelate. The visible light transmittance, weather resistance, adhesion between the coating and glass, and wear resistance of the coating were not significantly different from those in Example 1. However, the requirement of <1% could not be met in the UV 320nm-400nm region.

[0215] In Comparative Example 5, no light stabilizer was added to the raw materials of the ultraviolet absorber chelate. Although the visible light transmittance, weather resistance, adhesion between the coating and glass, and wear resistance of the coating were not significantly different from those in Example 1, they could not meet the requirement of <1% in the ultraviolet 380nm-400nm region.

[0216] Comparing the test results of Comparative Examples 3 to 5 with those of Example 1, it can be seen that: when existing UV absorbers are added alone, the resulting coating can only absorb UV light corresponding to the absorption band of the raw material UV absorber. However, the UV absorber chelate generated by reacting two UV absorbers with a light stabilizer in this invention not only retains the absorption capacity (280-380nm) of the raw material UV absorber, but also expands the absorption range to 380-400nm, and maintains a light transmittance of less than 1% throughout the entire absorption range (280-400nm), thus exhibiting high UV blocking ability.

[0217] In Comparative Example 6, the chelate used to prepare the coating was not subjected to the first reaction, and the coating cracked during the weather resistance test, indicating that the weather resistance of the coating was significantly reduced; in addition, the wear resistance of the coating in Comparative Example 6 was also reduced.

[0218] In Comparative Example 7, the excessive coupling agent in the chelate resulted in a significant reduction in the coating's wear resistance and weather resistance.

[0219] As can be seen from the above test results, the coating liquid provided by the present invention can be cured to form a coating with high visible light transmittance, high ultraviolet blocking performance, high wear resistance and high adhesion. Glass containing this coating can be used as automotive glass with high ultraviolet blocking coating.

Claims

1. A chelate of ultraviolet absorbers, wherein, The raw materials for the ultraviolet absorber chelate, by weight, include: First solvent: 10-30 parts, UV absorber A: 2.5-10 parts, UV absorber B: 2.5-15 parts, light stabilizer: 0.05-1.5 parts, coupling agent: 40-65 parts, first catalyst: 0.01-0.1 parts; The absorption peak of ultraviolet absorber A is located in the range of 280nm-315nm; the absorption peak of ultraviolet absorber B is located in the range of 315nm-380nm.

2. The ultraviolet absorber chelate according to claim 1, wherein, The ultraviolet absorber A and ultraviolet absorber B each comprise one or more of the following reagents: benzophenone ultraviolet absorbers, benzimidazole ultraviolet absorbers, triazine ultraviolet absorbers, oxaloylaniline ultraviolet absorbers, Chiguard P, Chiguard 1033, and Chiguard 5540.

3. The ultraviolet absorber chelate according to claim 2, wherein, The benzimidazole ultraviolet absorbers include one or more of 2-(2'-hydroxy-5'-methylphenyl)-benzotriazole, 2-(2'-hydroxy-3',5'-bis[1,1-dimethylphenyl]phenyl)-benzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chloro-benzotriazole, Chiguard 234, and Chiguard 380; And / or, the benzophenone-based ultraviolet absorber includes 2-hydroxy-4-methoxybenzophenone and / or 2-hydroxy-4-octoxybenzophenone; And / or, the triazine UV absorber includes one or more of ethyl 2-cyano-3,3-diphenylacrylate, isooctyl 2-cyano-3,3-diphenylacrylate, Chiguard 1064, and Chiguard 5431. And / or, the oxaloylaniline-based ultraviolet absorbers include N-(ethyl 4-benzoate)-N',N'-(methyl,phenyl)formamidine and / or N,N'-bis(4-ethoxycarbonylphenyl)-N'-benzylformamidine.

4. The ultraviolet absorber chelate according to claim 1, wherein, The absorption peak of the ultraviolet absorber A is 290-305 nm; And / or, the absorption peak of the ultraviolet absorber B is 340nm-380nm.

5. The ultraviolet absorber chelate according to claim 1, wherein, The light stabilizers include pentamethylpiperidinol, tetramethylpiperidinol, polymers of succinic acid and (4-hydroxy-2,2,6,6-tetramethyl-1-piperidinol), polysuccinic acid (4-hydroxy-2,2,6,6-tetramethyl-1-piperidinol) ester, bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, and... HS-3310 One or more combinations of HS-508.

6. The ultraviolet absorber chelate according to claim 1, wherein, The first catalyst comprises one or a combination of two or more of benzyltriethylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium hydrogen sulfate, trioctylmethylammonium chloride, dodecyltrimethylammonium chloride, and tetradecyltrimethylammonium chloride.

7. The ultraviolet absorber chelate according to claim 1, wherein, The coupling agent includes silane coupling agents and / or titanate coupling agents.

8. The ultraviolet absorber chelate according to claim 1 or 7, wherein, The coupling agent includes one or more of the following: γ-aminoethylaminopropyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, 3-(methacryloyloxy)propyltrimethoxysilane, 3-(2-aminoethyl)-aminopropyltrimethoxysilane, 3-(methacryloyloxy)propyltriethoxysilane, polybutyl titanate, tetrapropyl titanate, and isopropyltris(dioctylphosphoyloxy)titanate.

9. A method for preparing the ultraviolet absorber chelate according to any one of claims 1-8, comprising: A light stabilizer, UV absorber A, UV absorber B, coupling agent and a first catalyst are mixed and subjected to a first reaction to obtain the UV absorber chelate. The temperature of the first reaction is 120-150℃, and the reaction time is 2h-6h.

10. A coating liquid, wherein the raw materials of the coating liquid, based on 100% of the total mass of the coating liquid, include: The composition includes 10%-30% alkoxysilane, 30%-60% second solvent, 10%-25% ultraviolet absorber chelate according to any one of claims 1-8, 0.01%-1% second catalyst, 0.5%-3% auxiliary agent, and 10%-30% water.

11. The coating liquid according to claim 10, wherein, The alkoxysilane includes one or more of methyl orthosilicate, ethyl orthosilicate, trimethoxysilane, triethoxysilane, and dimethyldimethoxysilane; And / or, the additives include one or more of leveling agents, defoamers, and wetting agents.

12. The method for preparing the coating liquid according to claim 10 or 11, the method comprising: The ultraviolet absorber chelate is mixed with alkoxysilane, a second solvent, a second catalyst, an auxiliary agent, and water to carry out a second reaction, thereby obtaining the coating solution.

13. The preparation method according to claim 12, wherein, The temperature of the second reaction is 20℃-50℃, and the reaction time is 30min-120min.

14. A coating formed by drying and curing the coating liquid according to claim 10 or 11.

15. A coated glass comprising a glass substrate and a coating, the coating being disposed on at least one surface of the glass substrate; The coating is formed by drying and curing the coating liquid according to claim 10 or 11.

16. The coated glass according to claim 15, wherein, The coating thickness is 5μm-10μm.

17. The coated glass according to claim 15, wherein the transmittance of the coated glass for light with an incident angle of 0°-90° and a wavelength of 280-315nm is less than or equal to 2%; and the transmittance of the coated glass for light with an incident angle of 0°-90° and a wavelength of 315-400nm is less than or equal to 2%. And / or, the T400nm of the coated glass is ≤1%.

18. The coated glass according to claim 15, wherein, The difference in haze of the coated glass before and after the abrasion resistance test is less than or equal to 5%. And / or, the difference in ultraviolet transmittance of the coated glass after 100 hours of irradiation is <1%.

19. A method for preparing coated glass according to any one of claims 15-18, the method comprising: The coating is applied to the surface of the glass substrate and leveled, then dried and cured to obtain the glass.

20. The preparation method according to claim 19, wherein, The curing temperature is 80℃-200℃, and the curing time is 10min-200min.

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