Antifouling fireproof glass decoration panel and preparation method thereof

Abstract

The invention relates to the field of decorative materials, and discloses an antifouling fireproof glass decorative panel and a preparation method thereof, and the preparation method comprises the following steps: providing a glass substrate; immersing the glass substrate into 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; and spraying a modifier solution on the surface of the primer coating to obtain the antifouling fireproof glass decoration panel. The modifier solution is prepared by mixing an antifouling solution and a composite filler; the antifouling solution is prepared by reacting pentaerythritol triacrylate with modified sodium lignin sulfonate amine and aminated silicon dioxide colloid; the modified sodium lignin sulfonate amine is prepared by introducing dodecyl dimethyl benzyl ammonium chloride to a sodium lignin sulfonate amine side chain by using an electrostatic self-assembly method; the composite filler is prepared by using mesoporous silica and graphene oxide as raw materials through modification and thermal reduction of an amino silane coupling agent, and the material is endowed with a super-hydrophobic self-cleaning function, scratch resistance, wear resistance and corrosion resistance.

Description

Technical Field

[0001] The 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' requirements for home quality and environmental safety increase, the decorative materials market is changing rapidly. At present, traditional decorative materials such as wallpaper, paint, and tiles dominate the market, but these materials have disadvantages such as being easily damaged, difficult to clean, and having a short lifespan, and can no longer meet the needs of modern consumers for high performance, high aesthetics, and low maintenance costs. Although new decorative materials (such as artificial stone, quartz stone, etc.) have better performance, they are more expensive and are not suitable for the mass market. AG glass decorative panels have great advantages in price and performance due to their excellent scratch resistance and high temperature resistance, and can meet the needs of mass consumers for cost-effective, durable decorative materials.

[0003] AG glass, full name Anti-glare glass, is a kind of glass that reduces reflected light and increases light transmittance through special optical treatment. This glass uses the principle of diffuse reflection to change the reflective surface of the original glass into a matte diffuse reflection surface, significantly reducing the reflectivity, making the picture clearer and more realistic, and bringing a better visual experience to the viewer. The existing AG glass production methods mainly include spraying, coating, sandblasting, photoresist, and chemical etching. Among them, chemical etching has become the mainstream of AG glass production because of its easy operation and high reliability of the products produced.

[0004] AG glass can not only beautify the appearance of decorations, but also be widely used in TV splicing walls, TVs, LCD monitors, touch screens, industrial instruments and other fields. After the etching process, the surface of AG glass presents an uneven structure, which is easy to hide dirt and is difficult to clean in applications such as kitchen appliances, affecting the customer's experience of use. In addition, the existing AG glass has a single function, and its application is greatly limited. 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 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, and an adhesive primer coating is prepared 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 antifouling fire-resistant glass decorative panel comprises the following steps:

[0008] S1. Provide a glass substrate;

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

[0010] S3, spraying the primer solution evenly on the surface of the AG glass substrate, baking and pre-curing, to form a primer coating;

[0011] S4, after the 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 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 a Michael addition reaction of pentaerythritol triacrylate with modified sodium lignin sulfonate amine and amino silica colloidal body;

[0013] The modified sodium lignin sulfonate amine is prepared by using sodium lignin sulfonate to react with formaldehyde and diethylenetriamine to generate sodium lignin sulfonate amine, and then introducing dodecyl dimethyl benzyl ammonium chloride on the side chain of its molecular structure by electrostatic self-assembly method; the aminated silica colloid is prepared by using sol-gel method and aminated with 3-aminopropyl triethoxysilane;

[0014] The composite filler is prepared by using mesoporous silicon dioxide 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) placing ethyl orthosilicate, tetrahydrofuran and deionized water in a reactor, dropping concentrated hydrochloric acid to adjust the pH value to 4-5, placing the reactor at 25-35° C. and stirring for 12-15 hours, then adding 3-aminopropyltriethoxysilane and stirring for 3-5 hours, and standing the reactor for 20-24 hours after the reaction is completed to prepare an amino silica colloidal body;

[0020] (2) dissolving sodium lignin sulfonate in deionized water, adjusting the pH value to 10-12 with sodium hydroxide solution, adding diethylenetriamine and stirring, then dropping formaldehyde solution, placing at 70-85° C. for reflux reaction for 4-6 hours, cooling to room temperature after the reaction is completed, pouring the reaction product into ethanol for precipitation, centrifuging, washing, and drying the precipitated product to prepare sodium lignin sulfonate amine;

[0021] (3) dissolving dodecyl dimethyl benzyl 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 the reaction for 0.5 to 1 hour, standing for 42 to 48 hours after the reaction is completed, removing the supernatant by decantation, filtering, washing, and drying to prepare modified sodium lignin sulfonate amine;

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

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

[0024] Preferably, in 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.

[0025] Preferably, the method for preparing 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 to react for 2-2.5h, filter, wash and dry after the reaction is completed, place the obtained reaction product in a mixed solution of ammonium nitrate and ethanol, and then place it at 55-70°C and stir to react for 4-5h, filter, wash and dry after the reaction is completed to prepare mesoporous silica;

[0027] B. Put mesoporous nano-silica and sodium hydroxide solution into a reactor, place them at 65-75° C. and stir for 0.5-1 h. After the reaction is completed, wash, filter and dry to prepare 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, stir and react at 65-80° C. for 1-2 hours, and 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 adding modified mesoporous silica, stirring and reacting at 75-85°C for 1-2h. After the reaction is completed, the solid product is filtered, washed and dried. Then, the solid product is placed in a crucible, and the temperature is increased to 300-350°C at a heating rate of 5-10°C / min in a tubular furnace and maintained in a nitrogen atmosphere for 20-30min 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 preparation method described above.

[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), and [SiOH2] and Si-OH exist on the substrate surface to react in a fluorine-containing mixed salt solution to generate SiF4, thereby achieving the same effect as that of hydrofluoric acid, and 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, and finally a modifier solution is sprayed on the surface of the primer coating, so as to give the material a super-hydrophobic self-cleaning function, protect the glass decorative panel from water and oily pollutants, and at the same time give the material excellent scratch resistance, wear resistance and corrosion resistance.

[0034] The invention uses tetraethyl orthosilicate as a raw material to prepare 3-aminopropyl triethoxysilane aminated modified silica colloidal body through a sol-gel method, and simultaneously uses sodium lignin sulfonate, formaldehyde and diethylenetriamine through a Mannich reaction to prepare sodium lignin sulfonate amine, and then uses an electrostatic self-assembly method to introduce dodecyl dimethyl benzyl ammonium chloride on the side chain of the molecular structure of the sodium lignin sulfonate amine, thereby introducing a hydrophobic long chain to prepare modified sodium lignin sulfonate amine, and then reacts the amino groups in the modified sodium lignin sulfonate amine and the aminated silica colloidal body structure with double bonds in the pentaerythritol triacrylate structure through a Michael addition reaction to prepare a transparent and easy-to-handle antifouling solution, wherein the remaining ungrafted double bonds of the pentaerythritol triacrylate are helpful to construct a highly cross-linked reaction, and 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 functional composite filler of reduced graphene oxide-coated mesoporous silica through 3-aminopropyltriethoxysilane modification and thermal reduction, and applies it to an antifouling solution. The formed 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 described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are 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 and reacted at 30° C. for 15 h, and then 4.5 g of 3-aminopropyltriethoxysilane was added and stirred and reacted for 3 h. After the reaction was completed, the mixture was allowed to stand for 24 h to prepare an amino 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 with 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 dodecyl dimethyl benzyl 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 reaction 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, and 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 silica colloidal body were added to the mixed solution, and the mixture was stirred and reacted for 24 hours to prepare an antifouling solution.

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

[0042] A. Take 1.3g of hexadecyltrimethylammonium bromide and 0.6g of sodium hydroxide and dissolve them in 550mL of deionized water, add 8mL of mesitylene, stir and heat to 80°C, add 6mL of ethyl orthosilicate and stir to react for 2h, filter, wash and dry after the reaction is completed, place the obtained reaction product in a mixed solution of 0.5g of ammonium nitrate and 180mL of 95% ethanol, and then place it at 60°C and stir to react for 5h, filter, wash and dry after the reaction is completed 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 them 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 and mix them to obtain a silane hydrolyzate. Add 8 g of pretreated mesoporous silica to the silane hydrolyzate. Stir and react at 70 ° C for 2 h. After the reaction is completed, filter, wash and dry to obtain 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 hours. 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 tubular furnace at a heating rate of 10 ° C / min and maintain it in a nitrogen atmosphere for 30 minutes 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] Embodiment 6 A method for preparing an antifouling fire-resistant glass decorative panel comprises the following steps:

[0050] S1. Provide high-aluminum glass, clean it with a glass cleaner at an ultrasonic frequency of 25kHz, then rinse it with water, and put it in a drying oven to dry it until the mass 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 for 2 hours at 100r / min, and left to mature for 8 hours to prepare an AG etching solution, and the cleaned high-aluminum glass is affixed with a polyethylene plastic protective film on one side and then immersed in the AG etching solution for etching for 12 minutes. After the etching is completed, the glass is taken out, cleaned and dried to obtain an AG glass substrate;

[0052] S3, 1.8 g of epoxy linseed oil (molar mass 880 g / mol), 0.6 g of citric acid and 50 mL of ethanol were mixed to prepare a primer solution, the primer solution was evenly sprayed on the surface of the AG glass substrate, and pre-cured 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 hours to prepare an anti-fouling fire-resistant glass decorative panel.

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

[0055] S1. Provide high-aluminum glass, clean it with a glass cleaner at an ultrasonic frequency of 25kHz, then rinse it with water, and dry it in a drying oven until the mass 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 for 2 hours at 100r / min, and left to mature for 8 hours to prepare an AG etching solution, and the cleaned high-aluminum glass is affixed with a polyethylene plastic protective film on one side and then immersed in the AG etching solution for etching for 12 minutes. After the etching is completed, the glass is taken out, cleaned and dried to obtain an AG glass substrate;

[0057] S3, 1.8 g of epoxy linseed oil (molar mass 880 g / mol), 0.6 g of citric acid and 50 mL of ethanol were mixed to prepare a primer solution, the primer solution was evenly sprayed on the surface of the AG glass substrate, and pre-cured 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 hours to prepare an anti-fouling fire-resistant glass decorative panel.

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

[0060] S1. Provide high-aluminum glass, clean it with a glass cleaner at an ultrasonic frequency of 25kHz, then rinse it with water, and dry it in a drying oven until the mass 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 for 2 hours at 100r / min, and left to mature for 8 hours to prepare an AG etching solution, and the cleaned high-aluminum glass is affixed with a polyethylene plastic protective film on one side and then immersed in the AG etching solution for etching for 12 minutes. After the etching is completed, the glass is taken out, cleaned and dried to obtain an AG glass substrate;

[0062] S3, 1.8 g of epoxy linseed oil (molar mass 880 g / mol), 0.6 g of citric acid and 50 mL of ethanol were mixed to prepare a primer solution, the primer solution was evenly sprayed on the surface of the AG glass substrate, and pre-cured 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 hours to prepare an anti-fouling 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 and reacted at 30° C. for 15 h, and then 4.5 g of 3-aminopropyltriethoxysilane was added and stirred and reacted for 3 h. After the reaction was completed, the mixture was allowed to stand for 24 h to prepare an amino 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 with 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 silica colloidal body were added to the mixed solution, and the mixture was stirred and reacted for 24 hours 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 and reacted at 30° C. for 15 h, and then 4.5 g of 3-aminopropyltriethoxysilane was added and stirred and reacted for 3 h. After the reaction was completed, the mixture was allowed to stand for 24 h to prepare an amino 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 with 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 dodecyl dimethyl benzyl 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 reaction 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, and 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 and mixed 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 and reacted for 24 hours 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, clean it with a glass cleaner at an ultrasonic frequency of 25kHz, then rinse it with water, and dry it in a drying oven until the mass 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 for 2 hours at 100r / min, and left to mature for 8 hours to prepare an AG etching solution, and the cleaned high-aluminum glass is affixed with a polyethylene plastic protective film on one side and then immersed in the AG etching solution for etching for 12 minutes. After the etching is completed, the glass is taken out, cleaned and dried to obtain an AG glass substrate;

[0076] S3, 1.8 g of epoxy linseed oil (molar mass 880 g / mol), 0.6 g of citric acid and 50 mL of ethanol were mixed to prepare a primer solution, the primer solution was evenly sprayed on the surface of the AG glass substrate, and pre-cured 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, clean it with a glass cleaner at an ultrasonic frequency of 25kHz, then rinse it with water, and dry it in a drying oven until the mass 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 for 2 hours at 100r / min, and left to mature for 8 hours to prepare an AG etching solution, and the cleaned high-aluminum glass is affixed with a polyethylene plastic protective film on one side and then immersed in the AG etching solution for etching for 12 minutes. After the etching is completed, the glass is taken out, cleaned and dried to obtain an AG glass substrate;

[0081] S3, 1.8 g of epoxy linseed oil (molar mass 880 g / mol), 0.6 g of citric acid and 50 mL of ethanol were mixed to prepare a primer solution, the primer solution was evenly sprayed on the surface of the AG glass substrate, and pre-cured in an oven at 130° C. for 10 min to form a primer coating;

[0082] S4. After the pre-curing is completed, 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 hours to prepare an anti-fouling 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, clean it with a glass cleaner at an ultrasonic frequency of 25kHz, then rinse it with water, and dry it in a drying oven until the mass 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 for 2 hours at 100r / min, and left to mature for 8 hours to prepare an AG etching solution, and the cleaned high-aluminum glass is affixed with a polyethylene plastic protective film on one side and then immersed in the AG etching solution for etching for 12 minutes. After the etching is completed, the glass is taken out, cleaned and dried to obtain an AG glass substrate;

[0086] S3, 1.8 g of epoxy linseed oil (molar mass 880 g / mol), 0.6 g of citric acid and 50 mL of ethanol were mixed to prepare a primer solution, the primer solution was evenly sprayed on the surface of the AG glass substrate, and pre-cured in an oven at 130° C. for 10 min to form a primer coating;

[0087] S4. After the pre-curing is completed, the anti-fouling 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 hours to prepare an anti-fouling 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 testing:

[0090] (1) According to GB / T 6739-1996 standard, 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 3 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, and then a 100 g weight load was applied to move the substrate 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, good transmittance, and water contact angles greater than 150°, and have super hydrophobic surfaces. After 3 friction cycles and immersion in 5% sodium chloride solution, the water contact angle is still greater than 150°, and the wear resistance and corrosion resistance are excellent. After 5 friction cycles, the water contact angle shows a relatively low degree of decline, falling below 150°, but still presents good hydrophobic properties. Among them, the antifouling solution in Comparative Example 3 does not introduce dodecyl dimethyl benzyl ammonium chloride into the molecular chain of sodium lignin sulfonate amine, and the measured water contact angle is lower than that of Examples 6-8. In Comparative Example 4, the antifouling solution does not add pentaerythritol triacrylate component, and the measured water contact angle, hardness, and wear resistance are lower than those of Examples 6-8. The reason is that the amino group is not grafted, and the double bond group is not introduced to construct a high cross-linking reaction. In Comparative Example 5, no composite filler component is added, and the measured anticorrosion performance, wear resistance, and hardness are lower than those of Examples 6-8, indicating that the addition of composite fillers improves the mechanical properties and corrosion resistance of the material to a certain extent.

[0095] In the description of this specification, the description with reference to the terms "one embodiment", "example", "specific example", etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representation of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.

[0096] The above shows and describes the basic principles, main features and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited to the above embodiments, and the above embodiments and descriptions are only for explaining the principles of the present invention. Without departing from the spirit and scope of the present invention, the present invention may have various changes and improvements, and these changes and improvements all fall within the scope of the present invention to be protected.

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 into an AG etching solution to obtain an AG glass substrate; S3, spraying the primer solution evenly on the surface of the AG glass substrate, baking and pre-curing, to form a primer coating; S4, after the 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 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 a Michael addition reaction of pentaerythritol triacrylate with modified sodium lignin sulfonate amine and amino silica colloidal body; The modified sodium lignin sulfonate amine is prepared by using sodium lignin sulfonate to react with formaldehyde and diethylenetriamine to generate sodium lignin sulfonate amine, and then introducing dodecyl dimethyl benzyl ammonium chloride on the side chain of its molecular structure by electrostatic self-assembly method; the aminated silica colloid is prepared by using sol-gel method and aminated with 3-aminopropyl triethoxysilane; The composite filler is prepared by using mesoporous silicon dioxide and graphene oxide as raw materials and undergoing 3-aminopropyltriethoxysilane modification and thermal reduction reaction.

2. The method for preparing the antifouling fire-resistant glass decorative panel according to claim 1, characterized in that: The AG etching solution is prepared by mixing ammonium fluoride, ammonium bifluoride, calcium fluoride, barium sulfate, potassium sulfate, oxalic acid and water.

3. The method for preparing the antifouling fire-resistant glass decorative panel according to claim 1, characterized in that: 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.

4. The method for preparing the antifouling fire-resistant glass decorative panel according to claim 1, characterized in that: The mass ratio of the antifouling solution to the composite filler is 100:2-7.

5. The method for preparing the antifouling fire-resistant glass decorative panel according to claim 1, characterized in that: The method for preparing the antifouling solution comprises the following steps: (1) placing ethyl orthosilicate, tetrahydrofuran and deionized water in a reactor, dropping concentrated hydrochloric acid to adjust the pH value to 4-5, placing the reactor at 25-35° C. and stirring for 12-15 hours, then adding 3-aminopropyltriethoxysilane and stirring for 3-5 hours, and standing the reactor for 20-24 hours after the reaction is completed to prepare an amino silica colloidal body; (2) dissolving sodium lignin sulfonate in deionized water, adjusting the pH value to 10-12 with sodium hydroxide solution, adding diethylenetriamine and stirring, then dropping formaldehyde solution, placing at 70-85° C. for reflux reaction for 4-6 hours, cooling to room temperature after the reaction is completed, pouring the reaction product into ethanol for precipitation, centrifuging, washing, and drying the precipitated product to prepare sodium lignin sulfonate amine; (3) dissolving dodecyl dimethyl benzyl 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 the reaction for 0.5 to 1 hour, standing for 42 to 48 hours after the reaction is completed, removing the supernatant by decantation, filtering, washing, and drying to prepare modified sodium lignin sulfonate amine; (4) Pentaerythritol triacrylate, ethanol and propylene glycol methyl ether acetate are stirred and mixed to obtain a mixed solution, modified sodium lignin sulfonate amine and amino silica colloidal body are added to the mixed solution, and the mixture is stirred and reacted for 20 to 24 hours to prepare an antifouling solution.

6. The method for preparing the antifouling fire-resistant glass decorative panel according to claim 5, characterized in that: In the step (3), the mass ratio of dodecyl dimethyl benzyl ammonium chloride to sodium lignin sulfonate ammonium is 0.8 to 1:

1.

7. The method for preparing the antifouling fire-resistant glass decorative panel according to claim 5, 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.

8. 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 2-2.5h, filter, wash and dry after the reaction is completed, place the obtained reaction product in a mixed solution of ammonium nitrate and ethanol, and then place it at 55-70°C and stir to react for 4-5h, filter, wash and dry after the reaction is completed to prepare mesoporous silica; B. Put mesoporous nano-silica and sodium hydroxide solution into a reactor, place them at 65-75° C. and stir for 0.5-1 h. After the reaction is completed, wash, filter and dry to prepare pretreated mesoporous silica. C. Mix 3-aminopropyltriethoxysilane, ethanol and deionized water to obtain a silane hydrolyzate, add pretreated mesoporous silica to the silane hydrolyzate, stir and react at 65-80° C. for 1-2 hours, and after the reaction is completed, filter, wash and dry to obtain modified mesoporous silica; D. Ultrasonic dispersion of graphene oxide in deionized water, then adding modified mesoporous silica, stirring and reacting at 75-85°C for 1-2h. After the reaction is completed, the solid product is filtered, washed and dried. Then, the solid product is placed in a crucible, and the temperature is increased to 300-350°C at a heating rate of 5-10°C / min in a tubular furnace and maintained in a nitrogen atmosphere for 20-30min to prepare a composite filler.

9. The method for preparing the antifouling fire-resistant glass decorative panel according to claim 8, characterized in that: In the step D, the mass ratio of graphene oxide to modified mesoporous silica is 0.2-0.5:

1.

10. An antifouling fire-resistant glass decorative panel, made by the preparation method according to any one of claims 1 to 9.

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