A coating material for anti-fouling etching AG glass and a preparation method thereof

Abstract

The invention discloses a coating material for anti-fouling etched AG glass and a preparation method thereof, and relates to the technical field of anti-fouling coating materials; the coating material for anti-fouling etched AG glass consists of a composite modified silica sol and a high-performance polyurethane coating raw material; the composite modified silica sol consists of graphene oxide modified particles, dispersible silica sol and a low surface energy solution; the dispersible silica sol is synergistically modified by the graphene oxide modified particles and the low surface energy solution to obtain the composite modified silica sol, and then under the action of the high-performance polyurethane coating raw material, the wear resistance and hydrophobic anti-fouling property of the coating material are further enhanced, and at the same time, the coating material has good light transmittance, thereby achieving an excellent treatment effect of spraying on the AG glass.

Description

Technical Field

[0001] The invention belongs to the technical field of antifouling coating materials, and specifically refers to a coating material for antifouling etching AG glass and a preparation method thereof. Background Art

[0002] The increasingly serious light pollution makes us often experience glare in our daily life. In order to solve this problem, AG glass came into being. It can not only reduce the interference of ambient light, but also improve the viewing angle of the electronic product display screen, reduce screen reflection, and make the image clearer. At the same time, due to its beautiful appearance and the fact that it does not shield communication signals, it has been widely used in the cover of daily electronic products and equipment, and is recognized by consumers; AG glass is also used in display products in places such as conference rooms, classrooms, halls, and in the automotive field, bringing convenience to consumers' lives; AG glass, also known as anti-glare glass, is a kind of glass that is etched on the surface of the glass, thereby changing the roughness of the glass surface, making the surface matte, eliminating mirror reflection, and achieving the effect of diffuse reflection. This treatment method not only reduces the interference of ambient light and improves the viewing angle of the display screen, but also enhances the anti-slip and scratch resistance of the glass, while retaining the original exquisite touch of the glass.

[0003] There are three main processing technologies for AG glass: chemical etching, spraying and coating. Chemically etched AG glass has the best durability. Special processing is performed on the glass surface through chemical etching. Spraying AG uses a spray gun or a disc atomizer to evenly coat the particles on the glass surface. After heating and curing, a layer of particles is formed, which diffusely reflects the light to achieve an anti-glare effect. Coating AR uses vacuum coating to coat silicon dioxide on the glass surface to form irregular particles on the surface. Among them, the spraying AG processing technology is convenient and fast, does not require complex equipment and high-precision operations, has high production efficiency and low cost, and more and more manufacturers choose and use this process for the processing and production of AG glass.

[0004] The existing technology currently has the following problems:

[0005] The particle layer formed after AG spraying is easy to fall off and wear, resulting in poor wear resistance. It also limits the stability and durability of the anti-fouling performance and is not conducive to achieving a self-cleaning effect. Summary of the invention

[0006] In view of the above situation, in order to overcome the defects of the prior art, the present invention proposes a coating material for anti-fouling and etching AG glass, comprising the following components in parts by weight: 10-20 parts of composite modified silica sol and 40-50 parts of high-performance polyurethane coating raw materials.

[0007] The composite modified silica sol comprises the following components in parts by weight: 10-15 parts of graphene oxide modified particles, 10-20 parts of dispersed silica sol, and 20-40 parts of low surface energy solution.

[0008] The preparation method of the composite modified silica sol specifically comprises the following steps:

[0009] (1) 0.3-0.5 g of graphene oxide powder was dispersed in a mixed solution of 82 mL of anhydrous ethanol and 4 mL of distilled water, and ultrasonicated for 20-30 min. 6 mL of a 25% ammonia solution was added to the suspension and stirred evenly. Then 3 mL of TEOS tetraethyl orthosilicate was quickly added and stirred at room temperature for 24 h. The reaction product was vacuum filtered and washed with anhydrous ethanol for 5 times, filtered and dried. Nano-silicon dioxide was grafted on the surface of graphene oxide by TEOS in-situ hydrolysis method, which reduced the overlapping accumulation of graphene oxide. The inclusion of graphene oxide and nano-silicon dioxide at the same time was beneficial to construct a uniform micro-nano rough structure, and was also beneficial to improve the hardness and strength, thereby improving the wear resistance, and obtaining graphene oxide modified particles;

[0010] (2) 30 mL of anhydrous ethanol, TEOS tetraethyl orthosilicate and 30-50 μL of KH560γ-(2,3-epoxypropoxy)propyltrimethoxysilane liquid were added to a 50 mL beaker in sequence, the beaker was sealed, and stirred at room temperature for 30 min. Then, 1.2 mL of a 36% hydrochloric acid solution was immediately added to the above solution. Immediate addition of the hydrochloric acid solution helps to make the silica particles more evenly distributed and does not form large agglomerated molecules, which is beneficial to the uniform roughness of the glass substrate surface, thereby being more conducive to forming a hydrophobic surface and improving antifouling and wear resistance. The mixture was sealed and stirred at room temperature for 10-20 h to obtain a dispersed silica sol;

[0011] (3) Add 0.5-1.0g of perfluorinated reagent to 125mL of anhydrous ethanol, seal, and stir at room temperature for 10-30min. By modifying the polymer, fluorine atoms are introduced to make it have a lower surface energy, which can form a super-hydrophobic interface with excellent anti-fouling properties, reduce light reflection and refraction, improve light transmittance, enhance adhesion to the glass substrate, reduce shedding, improve adhesion and wear resistance, and obtain a low surface energy solution;

[0012] (4) The dispersed silica sol described in step (2) and the low surface energy solution described in step (3) are mixed evenly, and then the graphene oxide modified particles described in step (1) are added, and ultrasonic homogenization is performed. During the homogenization process, the ultrasonic temperature is 25-30°C, the ultrasonic power is 600-800W, and the ultrasonic time is 20-30min. The graphene oxide modified particles are doped into the silica sol to form a uniform supporting skeleton, enhance the strength and dispersibility of the sol, make the silica particles more evenly distributed, and form a hard and smooth protective film base. The bottom of the glass substrate is modified to improve the wear durability of the silica sol. The flaky silica formed is stacked layer by layer, which effectively squeezes the air pockets between the glass substrate and the water droplets, and is more conducive to forming a hydrophobic interface. At the same time, the Si-OH groups after hydrolysis of the low surface energy solution react with the -OH groups on the silica sol and graphene oxide to form a molecular layer with a long hydrophobic chain, which improves the hydrophobic performance and effectively constructs a micro-nano rough structure. While ensuring high transmittance, it also reduces the shedding and wear of silica particles after the coating is cured, and obtains a composite modified silica sol.

[0013] Preferably, in step (1), the oxidation degree of graphene oxide is 5-10%, thereby ensuring the light transmittance of graphene oxide;

[0014] Preferably, in step (2), the amount of TEOS tetraethyl orthosilicate added is 2-3 mL, which is conducive to forming a micro-nano rough structure in a granular state with a higher density.

[0015] The present invention also provides a method for preparing a coating material for anti-fouling etching AG glass, which specifically comprises the following steps:

[0016] S1. Add 21.0g IPDI isophorone diisocyanate into a three-necked flask with nitrogen protection, gradually add 22.5g polyoxypropylene glycol at 70-80°C, continue to react for 1-2h after the addition is complete, then take 3.5g DBTDL dibutyltin dilaurate and mix with 10mL DMFN, N-dimethylformamide solvent, slowly drip into the reaction system where the temperature has dropped to 60°C, continue stirring for 0.5h to fully mix, then slowly add 2.9g BDO1,4-butanediol, continue to react for 3h, during which time add 5-10 mL DMFN, N-dimethylformamide solvent. After the reaction is completed, the viscous reaction solution is vacuum dried and aged for 12 hours. Polyoxypropylene glycol is used as the soft segment, and IPDI and BDO with an asymmetric ring structure are used as the hard segment. While increasing the hard segment content, the tight stacking degree of the hard segment can be reduced. The urethane groups in the hard segment form hydrogen bonds with the ethanol molecules, which increases the solubility of the hard segment phase in ethanol. The formed polyurethane is alcohol-soluble and also exhibits good light transmittance and hydrophobicity, thereby obtaining a high-performance polyurethane coating raw material;

[0017] S2, the high-performance polyurethane coating raw material described in step S1 is placed in a three-necked flask with a reflux device, 45 mL of anhydrous ethanol is added, and stirring is continued at 50-60° C. until it is completely dissolved, and then taken out and cooled to room temperature, and 1.0-2.0 g of composite modified silica sol is added to the high-performance polyurethane coating solution, and stirred evenly. The high-performance polyurethane coating solution further enhances the mixing uniformity of the composite modified silica sol, significantly enhances the durability and hydrophobic antifouling property of the coating material, and also exhibits good light transmittance, and has excellent use effect when used for spraying AG glass, thereby obtaining a coating material for antifouling and etching AG glass;

[0018] Preferably, in step S2, the amount of high-performance polyurethane coating raw material added is 4.0-5.0 g. The high adhesion of the high-performance polyurethane coating raw material increases the adhesion of the silica particles after the coating is cured, reduces shedding and wear, and improves wear resistance.

[0019] The beneficial effects achieved by the present invention are as follows:

[0020] The present invention obtains a composite modified silica sol by synergistically modifying the dispersed silica sol with graphene oxide modified particles and a low surface energy solution, and then further enhances the wear resistance and hydrophobic antifouling property of the coating material under the action of a high-performance polyurethane coating raw material, and also has good light transmittance, thereby achieving an excellent treatment effect of AG glass spraying; in the composite modified silica sol, the graphene oxide modified particles dope the dispersed silica sol to form a uniform supporting skeleton, which can also be used as a protective film substrate, thereby enhancing the strength and high dispersibility of the sol, making the distribution of silica particles more uniform, and improving the wear durability of the silica sol; at the same time, the special flaky silica is stacked layer by layer, effectively squeezing the air pockets between the glass substrate and the water droplets, which is more conducive to the formation of a hydrophobic interface and improves the antifouling performance; furthermore, the Si- The OH group undergoes a polycondensation reaction with the silica sol and the -OH group on the graphene oxide, further forming a molecular layer with a long hydrophobic chain, thereby improving the hydrophobic property and effectively constructing a stable and uniformly dispersed micro-nano rough structure. While ensuring high transmittance, the shedding and wear of the silica particles after the coating is cured are reduced. In the high-performance polyurethane coating raw material, an alcohol-soluble polyurethane-based transparent coating is obtained by introducing a ring structure into the hard segment, thereby having high adhesion performance and excellent hydrophobic performance, effectively enhancing the adhesion of the composite modified silica sol, reducing its shedding and wear after curing, and improving wear resistance and anti-fouling properties. The present invention uses the composite modified silica sol and the high-performance polyurethane coating raw material to prepare a coating material for anti-fouling etching AG glass, which significantly enhances the wear resistance and anti-fouling properties of the coating material after curing, and also ensures the light transmittance of the glass substrate, with excellent use effect. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 This is a scanning electron microscope image of the composite modified silica sol prepared in Example 1 of the present invention;

[0022] Figure 2 This is a scanning electron microscope image of the coating material of the anti-fouling etched AG glass prepared in Example 1 of the present invention;

[0023] Figure 3 The results of the wear resistance times of Examples 1-4 and Comparative Examples 1-3 of the present invention are shown in FIG.

[0024] Figure 4 The contact angle results of Examples 1-4 and Comparative Examples 1-3 of the present invention are shown in FIG.

[0025] Figure 5 It is a graph showing the light transmittance results of Examples 1-4 of the present invention and Comparative Examples 1-3. DETAILED DESCRIPTION

[0026] The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all the embodiments; based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0027] Unless otherwise defined, all professional and scientific terms used herein have the same meanings as those familiar to those skilled in the art. In addition, any methods and materials similar or equivalent to those described herein may be applied to the present invention. The preferred implementation methods and materials described herein are for demonstration purposes only and are not intended to limit the content of this application.

[0028] The experimental methods in the following examples are conventional methods unless otherwise specified; the experimental materials used in the following examples are purchased from commercial channels unless otherwise specified.

[0029] Example 1

[0030] This embodiment provides a coating material for anti-fouling and etching AG glass, comprising the following components in parts by weight: 20 parts of composite modified silica sol and 50 parts of high-performance polyurethane coating raw materials.

[0031] The composite modified silica sol comprises the following components in parts by weight: 15 parts of graphene oxide modified particles, 10 parts of dispersed silica sol, and 40 parts of low surface energy solution.

[0032] The preparation method of the composite modified silica sol specifically comprises the following steps:

[0033] (1) 0.5 g of graphene oxide powder was dispersed in a mixed solution of 82 mL of anhydrous ethanol and 4 mL of distilled water, and ultrasonicated for 30 min. The oxidation degree of graphene oxide was 10%, ensuring the light transmittance of graphene oxide. 6 mL of 25% ammonia solution was added to the suspension and stirred evenly. Then 3 mL of LTEOS was quickly added and stirred at room temperature for 24 h. The reaction product was vacuum filtered and washed with anhydrous ethanol for 5 times, filtered and dried. Nano-silicon dioxide was grafted on the surface of graphene oxide by TEOS in-situ hydrolysis method, which reduced the overlapping accumulation of graphene oxide. The inclusion of graphene oxide and nano-silicon dioxide at the same time was beneficial to construct a uniform micro-nano rough structure, and was also beneficial to improve the hardness and strength, thereby improving the wear resistance, and obtaining graphene oxide modified particles;

[0034] (2) 30 mL of anhydrous ethanol, TEOS and 50 μL of KH560 liquid were added to a 50 mL beaker in sequence. The amount of TEOS added was 3 mL, which was conducive to the formation of a micro-nano rough structure in a granular state with a higher density. The beaker was sealed and stirred at room temperature for 30 min. Then 1.2 mL of a 36% hydrochloric acid solution was immediately added to the above solution. The immediate addition of the hydrochloric acid solution helped the silica particles to be more evenly distributed and would not form large agglomerated molecules, which was conducive to the uniform roughness of the glass substrate surface, thereby being more conducive to the formation of a hydrophobic surface and improving antifouling and wear resistance. The beaker was sealed and stirred at room temperature for 20 h to obtain a dispersed silica sol.

[0035] (3) Add 1.0 g of perfluorinated reagent to 125 mL of anhydrous ethanol, seal, and stir at room temperature for 30 min. By modifying the polymer, fluorine atoms are introduced to make it have a lower surface energy, which can form a super-hydrophobic interface with excellent anti-fouling properties. It can reduce the reflection and refraction of light, improve the transmittance, and enhance the adhesion to the glass substrate, reduce shedding, and improve adhesion and wear resistance to obtain a low surface energy solution.

[0036] (4) The dispersed silica sol described in step (2) and the low surface energy solution described in step (3) are mixed evenly, and then the graphene oxide modified particles described in step (1) are added, and ultrasonic homogenization is performed. During the homogenization process, the ultrasonic temperature is 30°C, the ultrasonic power is 800W, and the ultrasonic time is 30min. The graphene oxide modified particles are doped into the silica sol to form a uniform supporting skeleton, enhance the strength and dispersibility of the sol, make the silica particles more evenly distributed, and form a hard and smooth protective film substrate, thereby improving the The wear durability of silica sol and the stacking of flaky silica layers effectively squeeze the air pockets between the glass substrate and the water droplets, which is more conducive to forming a hydrophobic interface. At the same time, the Si-OH groups after hydrolysis of the low surface energy solution react with the -OH groups on the silica sol and graphene oxide to form a molecular layer with a long hydrophobic chain, which improves the hydrophobic performance and effectively constructs a micro-nano rough structure. While ensuring high transmittance, it also reduces the shedding and wear of silica particles after the coating is cured, thereby obtaining a composite modified silica sol.

[0037] This embodiment provides a method for preparing a coating material for anti-fouling and etching AG glass, which specifically includes the following steps:

[0038] S1. Add 21.0g IPDI to a three-necked flask with nitrogen protection, gradually add 22.5g polyoxypropylene glycol at 80°C, continue to react for 2h after the addition is complete, then take 3.5g DBTDL and mix with 10mL DMF solvent, slowly drip into the reaction system whose temperature has dropped to 60°C, continue to stir for 0.5h to fully mix, then slowly add 2.9g BDO, continue to react for 3h, during which 10mL DMF solvent is added, after the reaction is completed, vacuum dry the viscous reaction solution and mature it for 12h, using polyoxypropylene glycol as the soft segment and IPDI and BDO with asymmetric ring structure as the hard segment, while increasing the hard segment content, the close stacking degree of the hard segment can be reduced, the urethane group in the hard segment forms a hydrogen bond with the ethanol molecule, and the solubility of the hard segment phase in ethanol is increased, so that the formed polyurethane has alcohol solubility, and also shows good light transmittance and hydrophobicity, and a high-performance polyurethane coating raw material is obtained;

[0039] S2. The high-performance polyurethane coating raw material described in step S1 is placed in a three-necked flask with a reflux device, and 45 mL of anhydrous ethanol is added. The amount of the high-performance polyurethane coating raw material added is 5.0 g. The high adhesion of the high-performance polyurethane coating raw material increases the adhesion of the silica particles after the coating is cured, reduces shedding and wear, and improves wear resistance. Stirring is continued at 50-60° C. until it is completely dissolved, taken out and cooled to room temperature, and 2.0 g of the composite modified silica sol is added to the high-performance polyurethane coating solution, and stirred evenly. The high-performance polyurethane coating solution further enhances the mixing uniformity of the composite modified silica sol, significantly enhances the durability and hydrophobic antifouling properties of the coating material, and can also exhibit good light transmittance. It has excellent use effect when used for spraying AG glass, and a coating material for anti-fouling and etching AG glass is obtained.

[0040] In this embodiment, the prepared composite modified silica sol and anti-fouling etched AG glass coating material were subjected to scanning electron microscopy to observe their microscopic morphology. Figure 1 This is a SEM image of the composite modified silica sol prepared in Example 1 magnified 1000 times. Figure 2 The SEM image of the coating material of the anti-fouling etched AG glass prepared in Example 1 is magnified 1000 times, as shown in FIG. Figure 1 The composite modified silica sol prepared in this embodiment is a stable and uniformly dispersed micro-nano rough structure, such as Figure 2 The anti-fouling etched AG glass coating material prepared in this embodiment has high adhesion and good light transmission effect.

[0041] Example 2

[0042] This embodiment provides a coating material for anti-fouling and etching AG glass, comprising the following components in parts by weight: 10 parts of composite modified silica sol and 40 parts of high-performance polyurethane coating raw materials.

[0043] The composite modified silica sol comprises the following components in parts by weight: 10 parts of graphene oxide modified particles, 10 parts of dispersed silica sol, and 20 parts of low surface energy solution.

[0044] The preparation method of the composite modified silica sol specifically comprises the following steps:

[0045] (1) 0.3 g of graphene oxide powder was dispersed in a mixed solution of 82 mL of anhydrous ethanol and 4 mL of distilled water, and ultrasonicated for 20 min. The oxidation degree of graphene oxide was 5%, ensuring the light transmittance of graphene oxide. 6 mL of 25% ammonia solution was added to the suspension and stirred evenly. Then 3 mL of LTEOS was quickly added and stirred at room temperature for 24 h. The reaction product was vacuum filtered and washed with anhydrous ethanol for 5 times, filtered and dried. Nano-silicon dioxide was grafted on the surface of graphene oxide by TEOS in-situ hydrolysis method, which reduced the overlapping accumulation of graphene oxide. The inclusion of graphene oxide and nano-silicon dioxide at the same time was beneficial to the construction of a uniform micro-nano rough structure, and was also beneficial to improving the hardness and strength, thereby improving the wear resistance, and obtaining graphene oxide modified particles;

[0046] (2) 30 mL of anhydrous ethanol, TEOS and 30 μL of KH560 liquid were added to a 50 mL beaker in sequence. The amount of TEOS added was 2 mL, which was conducive to the formation of a micro-nano rough structure in a granular state with a higher density. The beaker was sealed and stirred at room temperature for 30 min. Then 1.2 mL of a 36% hydrochloric acid solution was immediately added to the above solution. The immediate addition of the hydrochloric acid solution helped to make the silica particles more evenly distributed and would not form large agglomerated molecules, which was conducive to the uniform roughness of the glass substrate surface, thereby being more conducive to forming a hydrophobic surface and improving antifouling and wear resistance. The beaker was sealed and stirred at room temperature for 10 h to obtain a dispersed silica sol.

[0047] (3) Add 0.5 g of perfluorinated reagent to 125 mL of anhydrous ethanol, seal, and stir at room temperature for 10 min. By modifying the polymer, fluorine atoms are introduced to make it have a lower surface energy, which can form a super-hydrophobic interface with excellent anti-fouling properties. It can reduce the reflection and refraction of light, improve the transmittance, and enhance the adhesion to the glass substrate, reduce shedding, and improve adhesion and wear resistance to obtain a low surface energy solution.

[0048] (4) The dispersed silica sol described in step (2) and the low surface energy solution described in step (3) are mixed evenly, and then the graphene oxide modified particles described in step (1) are added, and ultrasonic homogenization is performed. During the homogenization process, the ultrasonic temperature is 25°C, the ultrasonic power is 600W, and the ultrasonic time is 20min. The graphene oxide modified particles are doped into the silica sol to form a uniform supporting skeleton, enhance the strength and dispersibility of the sol, make the silica particles more evenly distributed, and also form a hard and smooth protective film substrate, thereby improving the The wear durability of silica sol and the stacking of flaky silica layers effectively squeeze the air pockets between the glass substrate and the water droplets, which is more conducive to forming a hydrophobic interface. At the same time, the Si-OH groups after hydrolysis of the low surface energy solution react with the -OH groups on the silica sol and graphene oxide to form a molecular layer with a long hydrophobic chain, which improves the hydrophobic performance and effectively constructs a micro-nano rough structure. While ensuring high transmittance, it also reduces the shedding and wear of silica particles after the coating is cured, thereby obtaining a composite modified silica sol.

[0049] This embodiment provides a method for preparing a coating material for anti-fouling and etching AG glass, which specifically includes the following steps:

[0050] S1. Add 21.0g IPDI to a three-necked flask with nitrogen protection, gradually add 22.5g polyoxypropylene glycol at 70°C, continue to react for 1h after the addition is complete, then take 3.5g DBTDL and mix with 10mL DMF solvent, slowly drip into the reaction system whose temperature has dropped to 60°C, continue to stir for 0.5h to fully mix, then slowly add 2.9g BDO, continue to react for 3h, during which 5mL DMF solvent is added, after the reaction is completed, vacuum dry the viscous reaction solution and mature it for 12h, using polyoxypropylene glycol as the soft segment and IPDI and BDO with asymmetric ring structure as the hard segment, while increasing the hard segment content, the close stacking degree of the hard segment can be reduced, the urethane group in the hard segment forms a hydrogen bond with the ethanol molecule, and the solubility of the hard segment phase in ethanol is increased, so that the formed polyurethane has alcohol solubility, and also shows good light transmittance and hydrophobicity, and a high-performance polyurethane coating raw material is obtained;

[0051] S2. The high-performance polyurethane coating raw material described in step S1 is placed in a three-necked flask with a reflux device, and 45 mL of anhydrous ethanol is added. The amount of the high-performance polyurethane coating raw material added is 4.0 g. The high adhesion of the high-performance polyurethane coating raw material increases the adhesion of the silica particles after the coating is cured, reduces shedding and wear, and improves wear resistance. Stirring is continued at 50° C. until it is completely dissolved, taken out and cooled to room temperature, and 1.0 g of the composite modified silica sol is added to the high-performance polyurethane coating solution, and stirred evenly. The high-performance polyurethane coating solution further enhances the mixing uniformity of the composite modified silica sol, significantly enhances the durability and hydrophobic antifouling properties of the coating material, and can also exhibit good light transmittance. It has excellent use effect when used for spraying AG glass, and a coating material for anti-fouling and etching AG glass is obtained.

[0052] Example 3

[0053] This embodiment provides a coating material for anti-fouling and etching AG glass, comprising the following components in parts by weight: 15 parts of composite modified silica sol and 45 parts of high-performance polyurethane coating raw materials.

[0054] The composite modified silica sol comprises the following components in parts by weight: 12.5 parts of graphene oxide modified particles, 15 parts of dispersed silica sol, and 30 parts of low surface energy solution.

[0055] The preparation method of the composite modified silica sol specifically comprises the following steps:

[0056] (1) 0.4 g of graphene oxide powder was dispersed in a mixed solution of 82 mL of anhydrous ethanol and 4 mL of distilled water, and ultrasonicated for 25 min. The oxidation degree of graphene oxide was 7.5%, which ensured the light transmittance of graphene oxide. 6 mL of 25% ammonia solution was added to the suspension and stirred evenly. Then 3 mL of LTEOS was quickly added and stirred at room temperature for 24 h. The reaction product was vacuum filtered and washed with anhydrous ethanol for 5 times, filtered and dried. Nano-silicon dioxide was grafted on the surface of graphene oxide by TEOS in-situ hydrolysis method, which reduced the overlapping accumulation of graphene oxide. The inclusion of graphene oxide and nano-silicon dioxide at the same time was beneficial to the construction of a uniform micro-nano rough structure, and was also beneficial to improving the hardness and strength, thereby improving the wear resistance, and obtaining graphene oxide modified particles;

[0057] (2) 30 mL of anhydrous ethanol, TEOS and 40 μL of KH560 liquid were added to a 50 mL beaker in sequence. The amount of TEOS added was 2.5 mL, which was conducive to the formation of a micro-nano rough structure in a granular state with a higher density. The beaker was sealed and stirred at room temperature for 30 min. Then 1.2 mL of a 36% hydrochloric acid solution was immediately added to the above solution. The immediate addition of the hydrochloric acid solution helped the silica particles to be more evenly distributed and would not form large agglomerated molecules, which was conducive to the uniform roughness of the glass substrate surface, thereby being more conducive to the formation of a hydrophobic surface and improving antifouling and wear resistance. The beaker was sealed and stirred at room temperature for 15 h to obtain a dispersed silica sol.

[0058] (3) Add 0.75 g of perfluorinated reagent to 125 mL of anhydrous ethanol, seal, and stir at room temperature for 20 min. By modifying the polymer, fluorine atoms are introduced to make it have a lower surface energy, which can form a super-hydrophobic interface with excellent anti-fouling properties. It can reduce the reflection and refraction of light, improve the transmittance, and enhance the adhesion to the glass substrate, reduce shedding, and improve adhesion and wear resistance to obtain a low surface energy solution.

[0059] (4) The dispersed silica sol described in step (2) and the low surface energy solution described in step (3) are mixed evenly, and then the graphene oxide modified particles described in step (1) are added, and ultrasonic homogenization is performed. During the homogenization process, the ultrasonic temperature is 27.5°C, the ultrasonic power is 700W, and the ultrasonic time is 25min. The graphene oxide modified particles are doped into the silica sol to form a uniform supporting skeleton, enhance the strength and dispersibility of the sol, make the silica particles more evenly distributed, and form a hard and smooth protective film substrate, thereby improving The wear durability of silica sol and the stacking of flaky silica layers effectively squeeze the air pockets between the glass substrate and the water droplets, which is more conducive to forming a hydrophobic interface. At the same time, the Si-OH groups after hydrolysis of the low surface energy solution undergo condensation reaction with the -OH groups on the silica sol and graphene oxide to form a molecular layer with a long hydrophobic chain, which improves the hydrophobic performance and effectively constructs a micro-nano rough structure. While ensuring high transmittance, it also reduces the shedding and wear of silica particles after the coating is cured, thereby obtaining a composite modified silica sol.

[0060] This embodiment provides a method for preparing a coating material for anti-fouling and etching AG glass, which specifically includes the following steps:

[0061] S1. Add 21.0g IPDI to a three-necked flask with nitrogen protection, gradually add 22.5g polyoxypropylene glycol at 75°C, continue to react for 1.5h after the addition is complete, then take 3.5g DBTDL and mix with 10mL DMF solvent, slowly drip into the reaction system whose temperature has dropped to 60°C, continue to stir for 0.5h to fully mix, then slowly add 2.9g BDO, continue to react for 3h, during which 7.5mL DMF solvent is added, after the reaction is completed, vacuum dry the viscous reaction solution and mature it for 12h, using polyoxypropylene glycol as the soft segment and IPDI and BDO with asymmetric ring structure as the hard segment, while increasing the hard segment content, the close stacking degree of the hard segment can be reduced, the urethane group in the hard segment forms a hydrogen bond with the ethanol molecule, and the solubility of the hard segment phase in ethanol is increased, so that the formed polyurethane has alcohol solubility, and also shows good light transmittance and hydrophobicity, and a high-performance polyurethane coating raw material is obtained;

[0062] S2. The high-performance polyurethane coating raw material described in step S1 is placed in a three-necked flask with a reflux device, and 45 mL of anhydrous ethanol is added. The amount of the high-performance polyurethane coating raw material added is 4.5 g. The high adhesion of the high-performance polyurethane coating raw material increases the adhesion of the silica particles after the coating is cured, reduces shedding and wear, and improves wear resistance. Stirring is continued at 55° C. until it is completely dissolved, taken out and cooled to room temperature, and 1.5 g of the composite modified silica sol is added to the high-performance polyurethane coating solution, and stirred evenly. The high-performance polyurethane coating solution further enhances the mixing uniformity of the composite modified silica sol, significantly enhances the durability and hydrophobic antifouling properties of the coating material, and can also exhibit good light transmittance. It has excellent use effect when used for spraying AG glass, and a coating material for anti-fouling and etching AG glass is obtained.

[0063] Example 4

[0064] This embodiment provides a coating material for anti-fouling and etching AG glass, comprising the following components in parts by weight: 10 parts of composite modified silica sol and 50 parts of high-performance polyurethane coating raw materials.

[0065] The composite modified silica sol comprises the following components in parts by weight: 15 parts of graphene oxide modified particles, 20 parts of dispersed silica sol, and 20 parts of low surface energy solution.

[0066] The preparation method of the composite modified silica sol specifically comprises the following steps:

[0067] (1) 0.5 g of graphene oxide powder was dispersed in a mixed solution of 82 mL of anhydrous ethanol and 4 mL of distilled water, and ultrasonicated for 20 min. The oxidation degree of graphene oxide was 10%, ensuring the light transmittance of graphene oxide. 6 mL of 25% ammonia solution was added to the suspension and stirred evenly. Then 3 mL of LTEOS was quickly added and stirred at room temperature for 24 h. The reaction product was vacuum filtered and washed with anhydrous ethanol for 5 times, filtered and dried. Nano-silicon dioxide was grafted on the surface of graphene oxide by TEOS in-situ hydrolysis method, which reduced the overlapping accumulation of graphene oxide. The inclusion of graphene oxide and nano-silicon dioxide at the same time was beneficial to the construction of a uniform micro-nano rough structure, and was also beneficial to improving the hardness and strength, thereby improving the wear resistance, and obtaining graphene oxide modified particles;

[0068] (2) 30 mL of anhydrous ethanol, TEOS and 30 μL of KH560 liquid were added to a 50 mL beaker in sequence. The amount of TEOS added was 3 mL, which was conducive to the formation of a micro-nano rough structure in a granular state with a higher density. The beaker was sealed and stirred at room temperature for 30 min. Then 1.2 mL of a 36% hydrochloric acid solution was immediately added to the above solution. The immediate addition of the hydrochloric acid solution helped the silica particles to be more evenly distributed and would not form large agglomerated molecules, which was conducive to the uniform roughness of the glass substrate surface, thereby being more conducive to the formation of a hydrophobic surface and improving antifouling and wear resistance. The mixture was sealed and stirred at room temperature for 10 h to obtain a dispersed silica sol.

[0069] (3) Add 1.0 g of perfluorinated reagent to 125 mL of anhydrous ethanol, seal, and stir at room temperature for 10 min. By modifying the polymer, fluorine atoms are introduced to make it have a lower surface energy, which can form a super-hydrophobic interface with excellent anti-fouling properties. It can reduce the reflection and refraction of light, improve the transmittance, and enhance the adhesion to the glass substrate, reduce shedding, and improve adhesion and wear resistance to obtain a low surface energy solution.

[0070] (4) The dispersed silica sol described in step (2) and the low surface energy solution described in step (3) are mixed evenly, and then the graphene oxide modified particles described in step (1) are added, and ultrasonic homogenization is performed. During the homogenization process, the ultrasonic temperature is 30°C, the ultrasonic power is 800W, and the ultrasonic time is 20min. The graphene oxide modified particles are doped into the silica sol to form a uniform supporting skeleton, enhance the strength and dispersibility of the sol, make the silica particles more evenly distributed, and also form a hard and smooth protective film substrate, thereby improving the The wear durability of silica sol and the stacking of flaky silica layers effectively squeeze the air pockets between the glass substrate and the water droplets, which is more conducive to forming a hydrophobic interface. At the same time, the Si-OH groups after hydrolysis of the low surface energy solution react with the -OH groups on the silica sol and graphene oxide to form a molecular layer with a long hydrophobic chain, which improves the hydrophobic performance and effectively constructs a micro-nano rough structure. While ensuring high transmittance, it also reduces the shedding and wear of silica particles after the coating is cured, thereby obtaining a composite modified silica sol.

[0071] This embodiment provides a method for preparing a coating material for anti-fouling and etching AG glass, which specifically includes the following steps:

[0072] S1. Add 21.0g IPDI to a three-necked flask with nitrogen protection, gradually add 22.5g polyoxypropylene glycol at 80°C, continue to react for 1h after the addition is completed, then take 3.5g DBTDL and mix with 10mL DMF solvent, slowly drip into the reaction system whose temperature has dropped to 60°C, continue to stir for 0.5h to fully mix, then slowly add 2.9g BDO, continue to react for 3h, during which 10mL DMF solvent is added, after the reaction is completed, vacuum dry the viscous reaction solution and mature it for 12h, using polyoxypropylene glycol as the soft segment and IPDI and BDO with asymmetric ring structure as the hard segment, while increasing the hard segment content, the close stacking degree of the hard segment can be reduced, the urethane group in the hard segment forms a hydrogen bond with the ethanol molecule, and the solubility of the hard segment phase in ethanol is increased, so that the formed polyurethane has alcohol solubility, and also shows good light transmittance and hydrophobicity, and a high-performance polyurethane coating raw material is obtained;

[0073] S2. The high-performance polyurethane coating raw material described in step S1 is placed in a three-necked flask with a reflux device, and 45 mL of anhydrous ethanol is added. The amount of the high-performance polyurethane coating raw material added is 5.0 g. The high adhesion of the high-performance polyurethane coating raw material increases the adhesion of the silica particles after the coating is cured, reduces shedding and wear, and improves wear resistance. Stirring is continued at 60° C. until it is completely dissolved, taken out and cooled to room temperature, and 1.0 g of the composite modified silica sol is added to the high-performance polyurethane coating solution, and stirred evenly. The high-performance polyurethane coating solution further enhances the mixing uniformity of the composite modified silica sol, significantly enhances the durability and hydrophobic antifouling properties of the coating material, and can also exhibit good light transmittance. It has excellent use effect when used for spraying AG glass, and a coating material for anti-fouling and etching AG glass is obtained.

[0074] Comparative Example 1

[0075] This comparative example provides a coating material for anti-fouling and etching AG glass, which differs from Example 1 in that the composite modified silica sol does not contain graphene oxide modified particles; the preparation method of the composite modified silica sol does not include step (1); the preparation method of the coating material for anti-fouling and etching AG glass is the same as that of Example 1.

[0076] Comparative Example 2

[0077] This comparative example provides a coating material for anti-fouling and etching AG glass, which differs from Example 1 in that the composite modified silica sol does not contain a low surface energy solution; the preparation method of the composite modified silica sol does not include step (3); and the preparation method of the coating material for anti-fouling and etching AG glass is the same as that of Example 1.

[0078] Comparative Example 3

[0079] This comparative example provides a coating material for anti-fouling and etching AG glass, which is different from Example 1 in that the coating material for anti-fouling and etching AG glass does not contain high-performance polyurethane coating raw materials; the preparation method of the composite modified silica sol is the same as that of Example 1; the preparation method of the coating material for anti-fouling and etching AG glass does not include step S1.

[0080] Experimental Example 1

[0081] Wear resistance test

[0082] Test sample: the anti-fouling and etched AG glass coating material prepared in Examples 1-4 and Comparative Examples 1-3.

[0083] Test method: Spray the test sample on AG glass, and after curing, place it on the workbench of the reciprocating linear wear tester. Set the instrument friction speed to 60 cycles / min and the load to 120g / cm 2, rub the surface of the AG glass, and then test the CA value of the AG glass after the friction. When the CA value is greater than 90°, continue to rub until the CA value is less than 90°, and record the number of frictions at this time.

[0084] Figure 3 It is a result graph of the wear resistance times of Examples 1-4 and Comparative Examples 1-3; as shown in the figure, the wear resistance times of Examples 1-4 are 12980-15000 times, indicating good wear resistance; the wear resistance times of Comparative Examples 1-3 are 6000-9600 times, indicating poor wear resistance; the composite modified silica sol of Comparative Example 1 does not contain graphene oxide modified particles, and the dispersed silica sol cannot be doped and modified, resulting in poor wear resistance; the composite modified silica sol of Comparative Example 2 does not contain a low surface energy solution, and cannot further undergo a condensation reaction, resulting in poor wear resistance; the coating material of the anti-fouling etched AG glass of Comparative Example 3 does not contain a high-performance polyurethane coating raw material, and cannot enhance the adhesion of the composite modified silica sol, resulting in poor wear resistance.

[0085] Experimental Example 2

[0086] Contact angle test

[0087] Test sample: the anti-fouling and etched AG glass coating material prepared in Examples 1-4 and Comparative Examples 1-3.

[0088] Test method: Spray the test sample on AG glass. After curing, drop 5 μL of pure water vertically on the coating to be tested according to GB / T30693-2014. Take horizontal photos of the droplets from 4 directions. Measure the surface water contact angle in parallel 3 times and take the arithmetic average.

[0089] Figure 4 The contact angle result diagram of Examples 1-4 and Comparative Examples 1-3; as shown in the figure, the contact angle of Examples 1-4 is 129.5-135.2°, indicating that the hydrophobic antifouling property is strong; the contact angle of Comparative Examples 1-3 is 97.9-118.7°, indicating that the hydrophobic antifouling property is weak; the composite modified silica sol of Comparative Example 1 does not contain graphene oxide modified particles, and cannot form special flaky silica layers, which is not conducive to the formation of a hydrophobic interface, resulting in weak hydrophobic antifouling property; the composite modified silica sol of Comparative Example 2 does not contain a low surface energy solution, and cannot form a molecular layer with a long hydrophobic chain through a condensation reaction, resulting in weak hydrophobic antifouling property; the coating material of the anti-fouling etched AG glass of Comparative Example 3 does not contain a high-performance polyurethane coating raw material, which can neither exert its own hydrophobicity nor be conducive to the stability of the composite modified silica sol, resulting in weak hydrophobic antifouling property.

[0090] Experimental Example 3

[0091] Light transmittance experiment

[0092] Test sample: the anti-fouling and etched AG glass coating material prepared in Examples 1-4 and Comparative Examples 1-3.

[0093] Test method: Spray the test sample on AG glass. After curing, use UV-visible spectrophotometer to characterize the transmittance of the glass substrate surface. Use clean and transparent bare glass as blank background. The test wavelength range is 380-780nm.

[0094] Figure 5 It is a graph of the transmittance results of Examples 1-4 and Comparative Examples 1-3; as shown in the figure, the transmittance of Examples 1-4 is 93.4-95.6%, indicating that the transmittance is better; the transmittance of Comparative Examples 1-3 is 85.3-90.6%, indicating that the transmittance is general; the composite modified silica sol of Comparative Example 1 does not contain graphene oxide modified particles, and cannot form a uniform supporting skeleton, which is not conducive to the uniformity of the distribution of silica particles, resulting in general transmittance; the composite modified silica sol of Comparative Example 2 does not contain a low surface energy solution, which is not conducive to the construction of a stable and uniformly dispersed micro-nano rough structure, resulting in general transmittance; the coating material of the anti-fouling etched AG glass of Comparative Example 3 does not contain a high-performance polyurethane coating raw material, which is not conducive to the adhesion of the composite modified silica sol, thereby adversely affecting the stability of the micro-nano rough structure, resulting in general transmittance.

[0095] The above experimental results show that the wear resistance, hydrophobicity and antifouling properties and light transmittance of Examples 1-4 of the present invention are significantly better than those of Comparative Examples 1-3. Among them, Example 1 using the composite modified silica sol and high-performance polyurethane coating raw materials has better wear resistance, stronger hydrophobicity and antifouling properties, and better light transmittance. In the composite modified silica sol, the graphene oxide modified particles are doped and modified to modify the dispersed silica sol to form a uniform supporting skeleton, which can also be used as a protective film substrate, which not only enhances the strength and dispersibility of the sol, makes the silica particles more evenly distributed, but also improves the wear durability of the silica sol. The special flaky silica is stacked layer by layer, effectively squeezing the glass substrate. The air pockets between the water droplets are more conducive to the formation of a hydrophobic interface. Furthermore, the Si-OH groups of the low surface energy solution react with the -OH groups on the silica sol and graphene oxide to form a molecular layer with a long hydrophobic chain, which improves the hydrophobic property and effectively constructs a stable and uniformly dispersed micro-nano rough structure. While ensuring high transmittance, it also reduces the shedding and wear of silica particles after the coating is cured. The high-performance polyurethane coating raw material has high adhesion and excellent hydrophobic properties by introducing annular structures into the hard segment, which effectively enhances the adhesion of the composite modified silica sol, reduces its shedding and wear after curing, and improves wear resistance and anti-fouling properties.

[0096] While the embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that many changes, modifications, substitutions and variations can be made to the embodiments without departing from the principles and spirit of the invention.

[0097] The present invention and its implementation methods are described above, which is not restrictive. The drawings are only one of the implementation methods of the present invention, and the actual application is not limited thereto. In short, if ordinary technicians in the field are inspired by it and design methods and embodiments similar to the technical solution without creativity without departing from the purpose of the invention, they should all fall within the protection scope of the present invention.

Claims

1. A coating material for anti-fouling etching AG glass, characterized in that: The coating material of the anti-fouling etched AG glass comprises the following components in parts by weight: 10-20 parts of composite modified silica sol and 40-50 parts of high-performance polyurethane coating raw materials; the composite modified silica sol comprises the following components in parts by weight: 10-15 parts of graphene oxide modified particles, 10-20 parts of dispersed silica sol and 20-40 parts of low surface energy solution; The preparation method of the composite modified silica sol specifically comprises the following steps: (1) Disperse 0.3-0.5 g of graphene oxide powder in a mixed solution of 82 mL of anhydrous ethanol and 4 mL of distilled water, and ultrasonicate for 20-30 min. Add 6 mL of 25% ammonia solution to the suspension and stir evenly. Then quickly add 3 mL of LTEOS and stir at room temperature for 24 h. Vacuum filter the reaction product, wash it with anhydrous ethanol for 5 times, filter it with suction, and dry it to obtain graphene oxide modified particles. (2) 30 mL of anhydrous ethanol, TEOS and 30-50 μL of KH560 liquid were added to a 50 mL beaker in sequence, the beaker was sealed, and stirred at room temperature for 30 min. Then, 1.2 mL of 36% hydrochloric acid solution was immediately added to the above solution, and the mixture was sealed and stirred at room temperature for 10-20 h to obtain a dispersed silica sol; (3) Add 0.5-1.0 g of perfluorinated reagent into 125 mL of anhydrous ethanol, seal, and stir at room temperature for 10-30 min to obtain a low surface energy solution; (4) The dispersed silica sol described in step (2) and the low surface energy solution described in step (3) are mixed evenly, and then the graphene oxide modified particles described in step (1) are added, and ultrasonic homogenization is performed. During the homogenization process, the ultrasonic temperature is 25-30° C., the ultrasonic power is 600-800 W, and the ultrasonic time is 20-30 min to obtain a composite modified silica sol; The method for preparing the coating material of the anti-fouling etching AG glass specifically comprises the following steps: S1. Add 21.0g IPDI into a three-necked flask with nitrogen protection, gradually add 22.5g polyoxypropylene glycol at 70-80°C, continue to react for 1-2h after the addition is complete, then take 3.5g DBTDL and mix with 10mL DMF solvent, slowly drip into the reaction system where the temperature has dropped to 60°C, continue stirring for 0.5h to fully mix, then slowly add 2.9g BDO, continue to react for 3h, add 5-10mL DMF solvent during the reaction, after the reaction is completed, vacuum dry the viscous reaction solution and mature it for 12h to obtain a high-performance polyurethane coating raw material; S2, placing the high-performance polyurethane coating raw material described in step S1 into a three-necked flask with a reflux device, adding 45 mL of anhydrous ethanol, stirring continuously at 50-60° C. until completely dissolved, taking it out and cooling it to room temperature, adding 1.0-2.0 g of composite modified silica sol to the high-performance polyurethane coating solution, stirring evenly, to obtain a coating material for anti-fouling etching AG glass; In step S2, the amount of high-performance polyurethane coating raw material added is 4.0-5.0 g.

2. A method for preparing the coating material of the anti-fouling etching AG glass according to claim 1, characterized in that: The specific steps include: S1. Add 21.0g IPDI into a three-necked flask with nitrogen protection, gradually add 22.5g polyoxypropylene glycol at 70-80°C, continue to react for 1-2h after the addition is complete, then take 3.5g DBTDL and mix with 10mL DMF solvent, slowly drip into the reaction system where the temperature has dropped to 60°C, continue stirring for 0.5h to fully mix, then slowly add 2.9g BDO, continue to react for 3h, add 5-10mL DMF solvent during the reaction, after the reaction is completed, vacuum dry the viscous reaction solution and mature it for 12h to obtain a high-performance polyurethane coating raw material; S2, placing the high-performance polyurethane coating raw material described in step S1 into a three-necked flask with a reflux device, adding 45 mL of anhydrous ethanol, stirring continuously at 50-60° C. until completely dissolved, taking it out and cooling it to room temperature, adding 1.0-2.0 g of composite modified silica sol to the high-performance polyurethane coating solution, stirring evenly, to obtain a coating material for anti-fouling etching AG glass; The preparation method of the composite modified silica sol specifically comprises the following steps: (1) Disperse 0.3-0.5 g of graphene oxide powder in a mixed solution of 82 mL of anhydrous ethanol and 4 mL of distilled water, and ultrasonicate for 20-30 min. Add 6 mL of 25% ammonia solution to the suspension and stir evenly. Then quickly add 3 mL of LTEOS and stir at room temperature for 24 h. Vacuum filter the reaction product, wash it with anhydrous ethanol for 5 times, filter it with suction, and dry it to obtain graphene oxide modified particles. (2) 30 mL of anhydrous ethanol, TEOS and 30-50 μL of KH560 liquid were added to a 50 mL beaker in sequence, the beaker was sealed, and stirred at room temperature for 30 min. Then, 1.2 mL of 36% hydrochloric acid solution was immediately added to the above solution, and the mixture was sealed and stirred at room temperature for 10-20 h to obtain a dispersed silica sol; (3) Add 0.5-1.0 g of perfluorinated reagent into 125 mL of anhydrous ethanol, seal, and stir at room temperature for 10-30 min to obtain a low surface energy solution; (4) The dispersed silica sol described in step (2) and the low surface energy solution described in step (3) are mixed evenly, and then the graphene oxide modified particles described in step (1) are added, and ultrasonic homogenization is performed. During the homogenization process, the ultrasonic temperature is 25-30° C., the ultrasonic power is 600-800 W, and the ultrasonic time is 20-30 min to obtain a composite modified silica sol.

3. The method for preparing the coating material of the anti-fouling etching AG glass according to claim 2, characterized in that: In step (1), the oxidation degree of graphene oxide is 5-10%.

4. The method for preparing the coating material of anti-fouling etching AG glass according to claim 3, characterized in that: In step (2), the amount of TEOS added is 2-3 mL.

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