Antifouling fire-resistant glass decorative panel and preparation method thereof

Abstract

The invention relates to the field of decorative materials and discloses an anti-fouling fire-resistant glass decorative panel and a preparation method thereof. The anti-fouling fire-resistant glass decorative panel comprises the following steps: providing a glass substrate; immersing the glass substrate in an AG etching solution to obtain an AG glass substrate; spraying a primer solution on the surface of the AG glass substrate to form a primer coating; spraying a modifier solution on the surface of the primer coating to obtain the anti-fouling fire-resistant glass decorative panel; the modifier solution is prepared by mixing an anti-fouling solution and a composite filler; the anti-fouling solution is prepared by reacting pentaerythritol triacrylate with modified sodium lignin sulfonate amine and amino silica colloidal body; the modified sodium lignin sulfonate amine is prepared by introducing dodecyldimethylbenzyl ammonium chloride on the side chain of the sodium lignin sulfonate amine by an electrostatic self-assembly method; the composite filler is prepared by using mesoporous silica and graphene oxide as raw materials, modifying with an aminosilane coupling agent and thermally reducing the composite filler, and imparting super-hydrophobic self-cleaning function, scratch resistance, wear resistance and corrosion resistance to the material.

Description

Technical Field

[0001] The present invention belongs to the technical field of decorative materials, and in particular relates to an anti-fouling fire-resistant glass decorative panel and a preparation method thereof. Background Art

[0002] As consumers demand higher quality homes and environmental safety, the decorative materials market is undergoing rapid changes. Traditional decorative materials such as wallpaper, paint, and ceramic tiles currently dominate the market. However, these materials suffer from drawbacks such as fragility, difficulty in cleaning, and a short lifespan, making them unable to meet modern consumers' demands for high performance, aesthetics, and low maintenance costs. While newer decorative materials (such as artificial stone and quartz stone) offer superior performance, they are relatively expensive and unsuitable for the mass market. AG glass decorative panels, with their excellent scratch and heat resistance, offer significant price and performance advantages, meeting the needs of mass consumers for cost-effective, durable decorative materials.

[0003] AG glass, short for anti-glare glass, is a type of glass that uses special optical processing to reduce reflected light and increase light transmittance. This glass uses the principle of diffuse reflection to transform the reflective surface of the original glass into a matte diffuse reflective surface, significantly reducing the reflectance, making the image clearer and more realistic, and providing viewers with a better visual experience. Existing AG glass production methods mainly include spraying, coating, sandblasting, photoresist, and chemical etching. Chemical etching has become the mainstream AG glass production method due to its ease of operation and high product reliability.

[0004] AG glass not only enhances the appearance of decorative items but is also widely used in video wall displays, televisions, LCD monitors, touch screens, and industrial instrumentation. However, after etching, the surface of AG glass exhibits an uneven surface. This surface easily harbors dirt and is difficult to clean in applications such as kitchen appliances, impacting user experience. Furthermore, the limited functionality of existing AG glass significantly limits its application. Summary of the Invention

[0005] In order to solve the deficiencies mentioned in the above-mentioned background technology, the purpose of the present invention is to provide an anti-fouling and fire-resistant glass decorative panel and a preparation method thereof, wherein an AG glass substrate is prepared by etching a glass substrate with AG etching solution, and then the epoxy linseed oil is cured with citric acid to prepare an adhesive primer coating on the surface of the AG glass substrate, and finally a modifier solution is sprayed on the surface of the primer coating to give the material super-hydrophobic self-cleaning function, scratch resistance, wear resistance and corrosion resistance.

[0006] The purpose of the present invention can be achieved through the following technical solutions:

[0007] A method for preparing an anti-fouling fire-resistant glass decorative panel comprises the following steps:

[0008] S1. Provide a glass substrate;

[0009] S2, immersing the cleaned and dried glass substrate in an AG etching solution to obtain an AG glass substrate;

[0010] S3. Evenly spray the primer solution on the surface of the AG glass substrate, bake and pre-curing, to form a primer coating;

[0011] S4. After pre-curing is completed, the modifier solution is evenly sprayed on the surface of the primer coating, and the mixture is baked and cured to prepare an anti-fouling and fire-resistant glass decorative panel;

[0012] The modifier solution is prepared by mixing an antifouling solution and a composite filler; the antifouling solution is prepared by Michael addition reaction of pentaerythritol triacrylate with modified sodium lignin sulfonate amine and amino-coated silica colloidal body;

[0013] The modified sodium lignin sulfonate amine is prepared by reacting sodium lignin sulfonate with formaldehyde and diethylenetriamine to generate sodium lignin sulfonate amine, and then introducing dodecyldimethylbenzyl ammonium chloride into the side chain of its molecular structure by electrostatic self-assembly; the amination silica colloidal body is prepared by a sol-gel method and modified by amination with 3-aminopropyltriethoxysilane;

[0014] The composite filler is prepared by using mesoporous silica and graphene oxide as raw materials and undergoing 3-aminopropyltriethoxysilane modification and thermal reduction reaction.

[0015] Preferably, the AG etching solution is prepared by mixing ammonium fluoride, ammonium bifluoride, calcium fluoride, barium sulfate, potassium sulfate, oxalic acid and water.

[0016] Preferably, the primer solution is prepared by mixing epoxy linseed oil, citric acid and ethanol; the molar ratio of the epoxy linseed oil to the citric acid is 1:1.2-1.6.

[0017] Preferably, the mass ratio of the antifouling solution to the composite filler is 100:2-7.

[0018] Preferably, the method for preparing the antifouling solution comprises the following steps:

[0019] (1) Ethyl orthosilicate, tetrahydrofuran, and deionized water are placed in a reactor, concentrated hydrochloric acid is added dropwise to adjust the pH value to 4-5, and the mixture is stirred and reacted at 25-35° C. for 12-15 hours. 3-aminopropyltriethoxysilane is then added and stirred and reacted for 3-5 hours. After the reaction is completed, the mixture is allowed to stand for 20-24 hours to prepare an amino-containing silica colloidal body;

[0020] (2) Sodium lignin sulfonate is dissolved in deionized water, the pH value is adjusted to 10-12 with sodium hydroxide solution, diethylenetriamine is added and stirred, and then formaldehyde solution is added dropwise, and the mixture is refluxed at 70-85° C. for 4-6 hours. After the reaction is completed, the mixture is cooled to room temperature, and the reaction product is poured into ethanol for precipitation. The precipitated product is centrifuged, washed, and dried to prepare sodium lignin sulfonate amine;

[0021] (3) dissolving dodecyldimethylbenzyl ammonium chloride in deionized water and adding the solution to the reactor, then adding a mixed solution of sodium lignin sulfonate amine and deionized water, stirring and reacting for 0.5 to 1 hour, standing for 42 to 48 hours after the reaction is completed, decanting and removing the supernatant, filtering, washing, and drying to prepare modified sodium lignin sulfonate amine;

[0022] (4) Pentaerythritol triacrylate, ethanol and propylene glycol methyl ether acetate were stirred and mixed to obtain a mixed solution, modified sodium lignin sulfonate amine and amino silica colloidal body were added to the mixed solution, and stirred to react for 20 to 24 hours to prepare an antifouling solution.

[0023] Preferably, in step (3), the mass ratio of dodecyldimethylbenzyl ammonium chloride to sodium ammonium ligninsulfonate is 0.8 to 1:1.

[0024] Preferably, in step (4), the mass ratio of pentaerythritol triacrylate, modified sodium lignin sulfonate amine and amino-treated silica colloidal body is 1:0.03-0.1:0.7-1.2.

[0025] Preferably, the preparation method of the composite filler comprises the following steps:

[0026] A. Dissolve hexadecyltrimethylammonium bromide and sodium hydroxide in deionized water, add mesitylene, stir and heat to 75-85°C, add ethyl orthosilicate and stir for 2-2.5 hours, filter after the reaction, wash and dry, place the obtained reaction product in a mixed solution of ammonium nitrate and ethanol, and then stir at 55-70°C for 4-5 hours, filter after the reaction, wash and dry to prepare mesoporous silica;

[0027] B. Place mesoporous nano-silica and sodium hydroxide solution in a reactor, stir and react at 65-75° C. for 0.5-1 hour, and wash, filter and dry after the reaction to obtain pretreated mesoporous silica.

[0028] C. Mix 3-aminopropyltriethoxysilane, ethanol, and deionized water to obtain a silane hydrolyzate, add pretreated mesoporous silica to the silane hydrolyzate, and stir the mixture at 65-80° C. for 1-2 hours. After the reaction is completed, filter, wash, and dry to obtain modified mesoporous silica.

[0029] D. Ultrasonic dispersion of graphene oxide in deionized water, then addition of modified mesoporous silica, and reaction at 75-85°C with stirring for 1-2 hours. After the reaction is completed, the solid product is filtered, washed, and dried. The solid product is then placed in a crucible, and the temperature is raised to 300-350°C in a tube furnace at a heating rate of 5-10°C / min and maintained in a nitrogen atmosphere for 20-30 minutes to prepare a composite filler.

[0030] Preferably, in step D, the mass ratio of graphene oxide to modified mesoporous silica is 0.2-0.5:1.

[0031] A stain-resistant fire-resistant glass decorative panel is made by the above-mentioned preparation method.

[0032] Beneficial effects of the present invention:

[0033] The present invention utilizes AG etching solution to etch a glass substrate to prepare an AG glass substrate, wherein oxalic acid provides hydrogen ions for the corrosion reaction, and can convert the silicon-oxygen skeleton structure on the glass surface into [SiOH2] and silanol (Si-OH). The [SiOH2] and Si-OH present on the substrate surface react in a fluorine-containing mixed salt solution to generate SiF4, achieving the same effect as hydrofluoric acid. Then, citric acid is used to cure the epoxy linseed oil, and an adhesive primer coating is prepared on the surface of the AG glass substrate. Finally, a modifier solution is sprayed on the surface of the primer coating to give the material a super-hydrophobic self-cleaning function, thereby protecting the glass decorative panel from water and oily pollutants, and at the same time giving the material excellent scratch resistance, wear resistance and corrosion resistance.

[0034] The invention uses tetraethyl orthosilicate as a raw material to prepare 3-aminopropyltriethoxysilane aminated silica colloidal body through a sol-gel method. At the same time, the invention uses sodium lignin sulfonate, formaldehyde and diethylenetriamine through a Mannich reaction to prepare sodium lignin sulfonate amine. Then, dodecyldimethylbenzyl ammonium chloride is introduced into the side chain of the sodium lignin sulfonate amine molecular structure through an electrostatic self-assembly method, thereby introducing a hydrophobic long chain to prepare modified sodium lignin sulfonate amine. Then, the modified sodium lignin sulfonate amine and the amino groups in the aminated silica colloidal body structure react with double bonds in the pentaerythritol triacrylate structure through a Michael addition reaction to prepare an antifouling solution that is transparent and easy to handle. The remaining ungrafted double bonds of the pentaerythritol triacrylate help to establish a highly cross-linked reaction. Under subsequent heating conditions, the double bonds are tightly linked through thermal curing to form a high-hardness antifouling coating with a high degree of cross-linking. In addition, the present invention uses mesoporous silica and graphene oxide as raw materials, and prepares a functionalized composite filler of reduced graphene oxide-coated mesoporous silica through 3-aminopropyltriethoxysilane modification and thermal reduction. The composite filler is applied to an antifouling solution. The resulting modifier solution has high transparency and effectively prevents water, moisture and salt from corroding the surface of the glass decorative panel, thereby extending the service life of the glass decorative panel. DETAILED DESCRIPTION

[0035] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts shall fall within the scope of protection of the present invention.

[0036] Example 1 A method for preparing an antifouling solution comprises the following steps:

[0037] (1) 20.8 g of ethyl orthosilicate, 43.3 g of tetrahydrofuran, and 10.8 g of deionized water were placed in a reactor, concentrated hydrochloric acid was added dropwise to adjust the pH value to 4, and the mixture was stirred at 30° C. for 15 h. Then, 4.5 g of 3-aminopropyltriethoxysilane was added and stirred for 3 h. After the reaction was completed, the mixture was allowed to stand for 24 h to prepare an amino-containing silica colloidal body;

[0038] (2) 20 g of sodium lignin sulfonate was dissolved in 100 mL of deionized water, the pH value was adjusted to 10 using a 10 wt % sodium hydroxide solution, 12.2 g of diethylenetriamine was added and stirred, and then 4.8 g of a 10 wt % formaldehyde aqueous solution was added dropwise, and the mixture was refluxed at 80° C. for 4 h. After the reaction was completed, the mixture was cooled to room temperature, and the reaction product was poured into ethanol for precipitation. The precipitated product was centrifuged, washed, and dried to prepare sodium lignin sulfonate amine;

[0039] (3) 0.8 g of dodecyldimethylbenzyl ammonium chloride was dissolved in 20 mL of deionized water and added to the reactor, and then a mixed solution of 1 g of sodium lignin sulfonate amine and 20 mL of deionized water was added, and the mixture was stirred for 0.5 h. After the reaction was completed, the mixture was allowed to stand for 42 h, and the supernatant was removed by decanting. The modified sodium lignin sulfonate amine was prepared by suction filtration, washing, and drying.

[0040] (4) 6 g of pentaerythritol triacrylate, 3 mL of ethanol, and 2 mL of propylene glycol methyl ether acetate were stirred and mixed to obtain a mixed solution. 0.5 g of modified sodium lignin sulfonate amine and 4.2 g of amino-containing silica gel were added to the mixed solution, and the mixture was stirred and reacted for 24 h to prepare an antifouling solution.

[0041] Example 2 A method for preparing a composite filler comprises the following steps:

[0042] A. Take 1.3 g of hexadecyltrimethylammonium bromide and 0.6 g of sodium hydroxide and dissolve them in 550 mL of deionized water, add 8 mL of mesitylene, stir and heat to 80 ° C, add 6 mL of ethyl orthosilicate and stir to react for 2 hours. After the reaction is completed, filter, wash and dry. The obtained reaction product is placed in a mixed solution of 0.5 g of ammonium nitrate and 180 mL of 95% ethanol, and then placed at 60 ° C and stirred for 5 hours. After the reaction is completed, filter, wash and dry to prepare mesoporous silica;

[0043] B. Take 10g of mesoporous nano-silica and 200mL of 0.5mol / L sodium hydroxide solution in a reactor, place it at 70°C and stir for 1h. After the reaction is completed, wash, filter and dry to prepare pretreated mesoporous silica;

[0044] C. Take 20 mL of 3-aminopropyltriethoxysilane, 120 mL of ethanol and 60 mL of deionized water to mix to obtain a silane hydrolyzate, add 8 g of pretreated mesoporous silica to the silane hydrolyzate, place it at 70 ° C and stir for 2 hours, and after the reaction is completed, filter, wash and dry to prepare modified mesoporous silica;

[0045] D. Take 0.2 g of graphene oxide and ultrasonically disperse it in 150 mL of deionized water, then add 1 g of modified mesoporous silica, place it at 80 ° C and stir to react for 2 h. After the reaction is completed, filter, wash, and dry it. Then, place the solid product in a crucible, raise the temperature to 320 ° C in a tube furnace at a heating rate of 10 ° C / min and maintain it in a nitrogen atmosphere for 30 min to prepare a composite filler.

[0046] Example 3 A modifier solution is prepared by mixing the antifouling solution prepared in Example 1 and the composite filler prepared in Example 2, wherein the mass ratio of the antifouling solution to the composite filler is 100:2.

[0047] Example 4 A modifier solution is prepared by mixing the antifouling solution prepared in Example 1 and the composite filler prepared in Example 2, wherein the mass ratio of the antifouling solution to the composite filler is 100:5.

[0048] Example 5 A modifier solution is prepared by mixing the antifouling solution prepared in Example 1 and the composite filler prepared in Example 2, wherein the mass ratio of the antifouling solution to the composite filler is 100:7.

[0049] Example 6 A method for preparing an antifouling fire-resistant glass decorative panel comprises the following steps:

[0050] S1. Provide high-aluminum glass, ultrasonically clean it with a glass cleaner at an ultrasonic frequency of 25 kHz, then rinse it with water, and dry it in a drying oven until the weight is constant;

[0051] S2. Ammonium fluoride, ammonium bifluoride, calcium fluoride, barium sulfate, potassium sulfate, oxalic acid, and water are mixed in a mass ratio of 30:2:3:1:1:1:62, and then stirred at 100 r / min for 2 hours, allowed to mature for 8 hours, and an AG etching solution is prepared. A polyethylene plastic protective film is attached to one side of the cleaned high-aluminum glass, and the glass is immersed in the AG etching solution and etched for 12 minutes. After the etching is completed, the glass is removed, cleaned, and dried to obtain an AG glass substrate;

[0052] S3. Prepare a primer solution by mixing 1.8 g of epoxy linseed oil (molar mass 880 g / mol), 0.6 g of citric acid, and 50 mL of ethanol. Evenly spray the primer solution on the surface of the AG glass substrate and pre-cure in an oven at 130° C. for 10 min to form a primer coating.

[0053] S4. After the pre-curing is completed, the modifier solution prepared in Example 3 is evenly sprayed on the surface of the primer coating, and cured in an oven at 180° C. for 2 h to prepare an anti-fouling and fire-resistant glass decorative panel.

[0054] Example 7 A method for preparing an antifouling fire-resistant glass decorative panel comprises the following steps:

[0055] S1. Provide high-aluminum glass, ultrasonically clean it with a glass cleaner at an ultrasonic frequency of 25 kHz, then rinse it with water, and dry it in a drying oven until the weight is constant;

[0056] S2. Ammonium fluoride, ammonium bifluoride, calcium fluoride, barium sulfate, potassium sulfate, oxalic acid, and water are mixed in a mass ratio of 30:2:3:1:1:1:62, and then stirred at 100 r / min for 2 hours, allowed to mature for 8 hours, and an AG etching solution is prepared. A polyethylene plastic protective film is attached to one side of the cleaned high-aluminum glass, and the glass is immersed in the AG etching solution and etched for 12 minutes. After the etching is completed, the glass is removed, cleaned, and dried to obtain an AG glass substrate;

[0057] S3. Prepare a primer solution by mixing 1.8 g of epoxy linseed oil (molar mass 880 g / mol), 0.6 g of citric acid, and 50 mL of ethanol. Evenly spray the primer solution on the surface of the AG glass substrate and pre-cure in an oven at 130° C. for 10 min to form a primer coating.

[0058] S4. After the pre-curing is completed, the modifier solution prepared in Example 4 is evenly sprayed on the surface of the primer coating, and cured in an oven at 180° C. for 2 h to prepare an anti-fouling and fire-resistant glass decorative panel.

[0059] Example 8 A method for preparing an antifouling fire-resistant glass decorative panel comprises the following steps:

[0060] S1. Provide high-aluminum glass, ultrasonically clean it with a glass cleaner at an ultrasonic frequency of 25 kHz, then rinse it with water, and dry it in a drying oven until the weight is constant;

[0061] S2. Ammonium fluoride, ammonium bifluoride, calcium fluoride, barium sulfate, potassium sulfate, oxalic acid, and water are mixed in a mass ratio of 30:2:3:1:1:1:62, and then stirred at 100 r / min for 2 hours, allowed to mature for 8 hours, and an AG etching solution is prepared. A polyethylene plastic protective film is attached to one side of the cleaned high-aluminum glass, and the glass is immersed in the AG etching solution and etched for 12 minutes. After the etching is completed, the glass is removed, cleaned, and dried to obtain an AG glass substrate;

[0062] S3. Prepare a primer solution by mixing 1.8 g of epoxy linseed oil (molar mass 880 g / mol), 0.6 g of citric acid, and 50 mL of ethanol. Evenly spray the primer solution on the surface of the AG glass substrate and pre-cure in an oven at 130° C. for 10 min to form a primer coating.

[0063] S4. After the pre-curing is completed, the modifier solution prepared in Example 5 is evenly sprayed on the surface of the primer coating, and cured in an oven at 180° C. for 2 h to prepare an anti-fouling and fire-resistant glass decorative panel.

[0064] Comparative Example 1 A method for preparing an antifouling solution comprises the following steps:

[0065] (1) 20.8 g of ethyl orthosilicate, 43.3 g of tetrahydrofuran, and 10.8 g of deionized water were placed in a reactor, concentrated hydrochloric acid was added dropwise to adjust the pH value to 4, and the mixture was stirred at 30° C. for 15 h. Then, 4.5 g of 3-aminopropyltriethoxysilane was added and stirred for 3 h. After the reaction was completed, the mixture was allowed to stand for 24 h to prepare an amino-containing silica colloidal body;

[0066] (2) 20 g of sodium lignin sulfonate was dissolved in 100 mL of deionized water, the pH value was adjusted to 10 using a 10 wt % sodium hydroxide solution, 12.2 g of diethylenetriamine was added and stirred, and then 4.8 g of a 10 wt % formaldehyde aqueous solution was added dropwise, and the mixture was refluxed at 80° C. for 4 h. After the reaction was completed, the mixture was cooled to room temperature, and the reaction product was poured into ethanol for precipitation. The precipitated product was centrifuged, washed, and dried to prepare sodium lignin sulfonate amine;

[0067] (3) 6 g of pentaerythritol triacrylate, 3 mL of ethanol, and 2 mL of propylene glycol methyl ether acetate were stirred and mixed to obtain a mixed solution. 0.5 g of sodium lignin sulfonate amine and 4.2 g of amino-containing silica gel were added to the mixed solution, and the mixture was stirred and reacted for 24 h to prepare an antifouling solution.

[0068] Comparative Example 2 A method for preparing an antifouling solution comprises the following steps:

[0069] (1) 20.8 g of ethyl orthosilicate, 43.3 g of tetrahydrofuran, and 10.8 g of deionized water were placed in a reactor, concentrated hydrochloric acid was added dropwise to adjust the pH value to 4, and the mixture was stirred at 30° C. for 15 h. Then, 4.5 g of 3-aminopropyltriethoxysilane was added and stirred for 3 h. After the reaction was completed, the mixture was allowed to stand for 24 h to prepare an amino-containing silica colloidal body;

[0070] (2) 20 g of sodium lignin sulfonate was dissolved in 100 mL of deionized water, the pH value was adjusted to 10 using a 10 wt % sodium hydroxide solution, 12.2 g of diethylenetriamine was added and stirred, and then 4.8 g of a 10 wt % formaldehyde aqueous solution was added dropwise, and the mixture was refluxed at 80° C. for 4 h. After the reaction was completed, the mixture was cooled to room temperature, and the reaction product was poured into ethanol for precipitation. The precipitated product was centrifuged, washed, and dried to prepare sodium lignin sulfonate amine;

[0071] (3) 0.8 g of dodecyldimethylbenzyl ammonium chloride was dissolved in 20 mL of deionized water and added to the reactor, and then a mixed solution of 1 g of sodium lignin sulfonate amine and 20 mL of deionized water was added, and the mixture was stirred for 0.5 h. After the reaction was completed, the mixture was allowed to stand for 42 h, and the supernatant was removed by decanting. The modified sodium lignin sulfonate amine was prepared by suction filtration, washing, and drying.

[0072] (4) 3 mL of ethanol and 2 mL of propylene glycol methyl ether acetate were stirred to obtain a mixed solution, 0.5 g of modified sodium lignin sulfonate amine and 4.2 g of amino silica colloidal body were added to the mixed solution, and the mixture was stirred for 24 h to prepare an antifouling solution.

[0073] Comparative Example 3 A method for preparing an antifouling fire-resistant glass decorative panel comprises the following steps:

[0074] S1. Provide high-aluminum glass, ultrasonically clean it with a glass cleaner at an ultrasonic frequency of 25 kHz, then rinse it with water, and dry it in a drying oven until the weight is constant;

[0075] S2. Ammonium fluoride, ammonium bifluoride, calcium fluoride, barium sulfate, potassium sulfate, oxalic acid, and water are mixed in a mass ratio of 30:2:3:1:1:1:62, and then stirred at 100 r / min for 2 hours, allowed to mature for 8 hours, and an AG etching solution is prepared. A polyethylene plastic protective film is attached to one side of the cleaned high-aluminum glass, and the glass is immersed in the AG etching solution and etched for 12 minutes. After the etching is completed, the glass is removed, cleaned, and dried to obtain an AG glass substrate;

[0076] S3. Prepare a primer solution by mixing 1.8 g of epoxy linseed oil (molar mass 880 g / mol), 0.6 g of citric acid, and 50 mL of ethanol. Evenly spray the primer solution on the surface of the AG glass substrate and pre-cure in an oven at 130° C. for 10 min to form a primer coating.

[0077] S4. After the pre-curing is completed, the modifier solution prepared in Comparative Example 1 is evenly sprayed on the surface of the primer coating, and cured in an oven at 180° C. for 2 hours to prepare an anti-fouling and fire-resistant glass decorative panel.

[0078] Comparative Example 4 A method for preparing an antifouling fire-resistant glass decorative panel comprises the following steps:

[0079] S1. Provide high-aluminum glass, ultrasonically clean it with a glass cleaner at an ultrasonic frequency of 25 kHz, then rinse it with water, and dry it in a drying oven until the weight is constant;

[0080] S2. Ammonium fluoride, ammonium bifluoride, calcium fluoride, barium sulfate, potassium sulfate, oxalic acid, and water are mixed in a mass ratio of 30:2:3:1:1:1:62, and then stirred at 100 r / min for 2 hours, allowed to mature for 8 hours, and an AG etching solution is prepared. A polyethylene plastic protective film is attached to one side of the cleaned high-aluminum glass, and the glass is immersed in the AG etching solution and etched for 12 minutes. After the etching is completed, the glass is removed, cleaned, and dried to obtain an AG glass substrate;

[0081] S3. Prepare a primer solution by mixing 1.8 g of epoxy linseed oil (molar mass 880 g / mol), 0.6 g of citric acid, and 50 mL of ethanol. Evenly spray the primer solution on the surface of the AG glass substrate and pre-cure in an oven at 130° C. for 10 min to form a primer coating.

[0082] S4. After pre-curing, the modifier solution prepared in Comparative Example 2 is evenly sprayed on the surface of the primer coating, and cured in an oven at 180° C. for 2 h to prepare an anti-fouling and fire-resistant glass decorative panel.

[0083] Comparative Example 5 A method for preparing an antifouling fire-resistant glass decorative panel comprises the following steps:

[0084] S1. Provide high-aluminum glass, ultrasonically clean it with a glass cleaner at an ultrasonic frequency of 25 kHz, then rinse it with water, and dry it in a drying oven until the weight is constant;

[0085] S2. Ammonium fluoride, ammonium bifluoride, calcium fluoride, barium sulfate, potassium sulfate, oxalic acid, and water are mixed in a mass ratio of 30:2:3:1:1:1:62, and then stirred at 100 r / min for 2 hours, allowed to mature for 8 hours, and an AG etching solution is prepared. A polyethylene plastic protective film is attached to one side of the cleaned high-aluminum glass, and the glass is immersed in the AG etching solution and etched for 12 minutes. After the etching is completed, the glass is removed, cleaned, and dried to obtain an AG glass substrate;

[0086] S3. Prepare a primer solution by mixing 1.8 g of epoxy linseed oil (molar mass 880 g / mol), 0.6 g of citric acid, and 50 mL of ethanol. Evenly spray the primer solution on the surface of the AG glass substrate and pre-cure in an oven at 130° C. for 10 min to form a primer coating.

[0087] S4. After the pre-curing is completed, the antifouling solution prepared in Example 1 is evenly sprayed on the surface of the primer coating, and cured in an oven at 180° C. for 2 h to prepare an antifouling fire-resistant glass decorative panel.

[0088] Performance testing

[0089] The glass decorative panels prepared in Examples 6-8 and Comparative Examples 3-5 were subjected to performance tests:

[0090] (1) According to GB / T 6739-1996, the pencil hardness of the coating was measured by a pencil hardness tester; the coating was measured by a transmittance tester, and the transmittance test was performed at three different positions. The average value was taken and the data results were shown in Table 1.

[0091] (2) The hydrophobicity of the material was tested using a water contact angle meter with a water drop size of 5 μL. The sample was immersed in a 5% sodium chloride solution for 3 h to evaluate the corrosion resistance of the material. The glass decorative panel was placed flat on 800-mesh (15 μm) sandpaper (270 mm × 220 mm, Yan brand sandpaper) with the coating facing the rough surface of the sandpaper. A 100 g weight load was then applied and the substrate was moved horizontally to overcome the friction resistance of the sandpaper. Each movement of 1 sandpaper length (270 mm) was recorded as 1 friction cycle. The sandpaper was replaced after each friction. The wear resistance and durability of the material were evaluated after 5 friction cycles. The data results are shown in Table 1.

[0092] Table 1 Test results of sample performance

[0093]

[0094] As can be seen from the data in Table 1, the glass decorative panels prepared in Examples 6-8 of the present invention have high hardness and good light transmittance, and their water contact angles are all greater than 150°, exhibiting superhydrophobic surfaces. After three friction cycles and immersion in a 5% sodium chloride solution, the water contact angle remains greater than 150°, and the wear resistance and corrosion resistance are excellent. After five friction cycles, the water contact angle shows a slight decrease, falling below 150°, but still exhibits good hydrophobic properties. In Comparative Example 3, the antifouling solution does not incorporate dodecyldimethylbenzylammonium chloride into the sodium ligninsulfonate amine molecular chain, resulting in a decrease in the water contact angle compared to Examples 6-8. In Comparative Example 4, the antifouling solution does not incorporate the pentaerythritol triacrylate component, resulting in decreases in the water contact angle, hardness, and wear resistance compared to Examples 6-8. This is due to the lack of grafting of amino groups and the introduction of double bond groups to establish a highly cross-linked reaction. In Comparative Example 5, no composite filler component is added, resulting in decreases in the corrosion resistance, wear resistance, and hardness compared to Examples 6-8, indicating that the addition of the composite filler improves the mechanical properties and corrosion resistance of the material to a certain extent.

[0095] Throughout this specification, references to terms such as "one embodiment," "example," or "specific example" indicate that the specific features, structures, materials, or characteristics described in conjunction with that embodiment or example are included in at least one embodiment or example of the present invention. In this specification, schematic representations of these terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.

[0096] The basic principles, main features, and advantages of the present invention are shown and described above. Those skilled in the art should understand that the present invention is not limited to the above embodiments. The above embodiments and descriptions are merely illustrative of the principles of the present invention. Various changes and modifications may be made to the present invention without departing from the spirit and scope of the present invention, and such changes and modifications fall within the scope of the invention as claimed.

Claims

1. A method for preparing an antifouling fire-resistant glass decorative panel, characterized in that: The following steps are involved: S1. Provide a glass substrate; S2, immersing the cleaned and dried glass substrate in an AG etching solution to obtain an AG glass substrate; S3. Evenly spray the primer solution on the surface of the AG glass substrate, bake and pre-curing, to form a primer coating; S4. After pre-curing is completed, the modifier solution is evenly sprayed on the surface of the primer coating, and the mixture is baked and cured to prepare an anti-fouling and fire-resistant glass decorative panel; The modifier solution is prepared by mixing an antifouling solution and a composite filler; the antifouling solution is prepared by simultaneously reacting pentaerythritol triacrylate with modified sodium lignin sulfonate amine and amino-coated silica colloidal body to undergo Michael addition reaction; The modified sodium lignin sulfonate amine is prepared by reacting sodium lignin sulfonate with formaldehyde and diethylenetriamine to generate sodium lignin sulfonate amine, and then introducing dodecyldimethylbenzyl ammonium chloride into the side chain of its molecular structure by electrostatic self-assembly; the amination silica colloidal body is prepared by a sol-gel method and modified by amination with 3-aminopropyltriethoxysilane; The composite filler is made of mesoporous silica and graphene oxide as raw materials, modified with 3-aminopropyltriethoxysilane and subjected to thermal reduction reaction; The AG etching solution is prepared by mixing ammonium fluoride, ammonium bifluoride, calcium fluoride, barium sulfate, potassium sulfate, oxalic acid and water; the primer solution is prepared by mixing epoxy linseed oil, citric acid and ethanol; the molar ratio of the epoxy linseed oil to the citric acid is 1:1.2-1.6; and the mass ratio of the antifouling solution to the composite filler is 100:2-7.

2. The method for preparing the antifouling fire-resistant glass decorative panel according to claim 1, characterized in that: The preparation method of the antifouling solution comprises the following steps: (1) Put ethyl orthosilicate, tetrahydrofuran and deionized water in a reactor, add concentrated hydrochloric acid dropwise to adjust the pH value to 4-5, place at 25-35°C and stir to react for 12-15 hours, then add 3-aminopropyltriethoxysilane and stir to react for 3-5 hours. After the reaction is completed, let it stand for 20-24 hours to prepare amino-containing silica colloidal body; (2) Sodium lignin sulfonate was dissolved in deionized water, and the pH value was adjusted to 10-12 with sodium hydroxide solution. Diethylenetriamine was added and stirred, and then formaldehyde solution was added dropwise. The mixture was refluxed at 70-85°C for 4-6 hours. After the reaction was completed, the mixture was cooled to room temperature. The reaction product was poured into ethanol for precipitation. The precipitated product was centrifuged, washed, and dried to prepare sodium lignin sulfonate amine. (3) dissolving dodecyldimethylbenzyl ammonium chloride in deionized water and adding the solution to the reactor, then adding a mixed solution of sodium lignin sulfonate amine and deionized water, stirring and reacting for 0.5 to 1 hour, standing for 42 to 48 hours after the reaction is completed, decanting and removing the supernatant, filtering, washing, and drying to prepare modified sodium lignin sulfonate amine; (4) Pentaerythritol triacrylate, ethanol and propylene glycol methyl ether acetate were stirred and mixed to obtain a mixed solution, modified sodium lignin sulfonate amine and amino silica colloidal body were added to the mixed solution, and the mixture was stirred and reacted for 20 to 24 hours to prepare an antifouling solution.

3. The method for preparing the antifouling fire-resistant glass decorative panel according to claim 2, characterized in that: In the step (3), the mass ratio of dodecyldimethylbenzyl ammonium chloride to sodium ammonium ligninsulfonate is 0.8-1:

1.

4. The method for preparing the antifouling fire-resistant glass decorative panel according to claim 2, characterized in that: In the step (4), the mass ratio of pentaerythritol triacrylate, modified sodium lignin sulfonate amine and amino silica colloidal body is 1:0.03~0.1:0.7~1.

2.

5. The method for preparing the antifouling fire-resistant glass decorative panel according to claim 1, characterized in that: The preparation method of the composite filler comprises the following steps: A. Dissolve hexadecyltrimethylammonium bromide and sodium hydroxide in deionized water, add mesitylene, stir and heat to 75-85°C, add ethyl orthosilicate and stir to react for 2-2.5 hours. After the reaction is completed, filter, wash and dry. Place the obtained reaction product in a mixed solution of ammonium nitrate and ethanol, and then stir and react at 55-70°C for 4-5 hours. After the reaction is completed, filter, wash and dry to prepare mesoporous silica. B. Place mesoporous nano-silica and sodium hydroxide solution in a reactor, stir and react at 65-75° C. for 0.5-1 hour, and wash, filter and dry after the reaction to obtain pretreated mesoporous silica. C. Mix 3-aminopropyltriethoxysilane, ethanol, and deionized water to obtain a silane hydrolyzate, add pretreated mesoporous silica to the silane hydrolyzate, and stir the mixture at 65-80° C. for 1-2 hours. After the reaction is completed, filter, wash, and dry to obtain modified mesoporous silica. D. Ultrasonic dispersion of graphene oxide in deionized water, then addition of modified mesoporous silica, and reaction at 75-85°C with stirring for 1-2 hours. After the reaction is completed, the solid product is filtered, washed, and dried. The solid product is then placed in a crucible and the temperature is raised to 300-350°C in a tube furnace at a heating rate of 5-10°C / min and maintained in a nitrogen atmosphere for 20-30 minutes to prepare a composite filler.

6. The method for preparing the antifouling fire-resistant glass decorative panel according to claim 5, characterized in that: In the step D, the mass ratio of graphene oxide to modified mesoporous silica is 0.2-0.5:

1.

7. An antifouling fire-resistant glass decorative panel, made by the preparation method according to any one of claims 1 to 6.

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