Preparation method of open and closed hole mixed wear-resistant hydrophobic and antireflection membrane

Abstract

The application discloses a preparation method of a mixed open-closed pore wear-resistant hydrophobic and antireflection film, which comprises the following steps: preparation of a core-shell structure nanoparticle solution, preparation of a wear-resistant adhesive, preparation of a mixed open-closed pore wear-resistant antireflection film solution, preparation of an antireflection film layer, and plating of a hydrophobic film. The film layer prepared by the method combines the advantages of the open-pore antireflection film and the closed-pore antireflection film, guarantees good wear resistance and hydrophobicity of the film layer on the basis of good light transmission performance, and has good stain resistance compared with the antireflection film in the prior art, so that the system cleaning frequency can be effectively reduced, the service life can be significantly prolonged, and the long-term and efficient operation of a solar power generation system is facilitated, thereby achieving obvious economic and social benefits.

Description

Technical Field

[0001] This invention relates to the field of membrane preparation technology, and specifically to a method for preparing a hybrid open-pore and closed-pore wear-resistant hydrophobic antireflective membrane. Background Technology

[0002] Antireflective coatings have wide applications in the field of solar power generation. Specifically, coating photovoltaic (PV) power generation system panels or solar thermal power generation system glass collector tubes with antireflective coatings can effectively reduce light reflection, allowing more light to enter the PV or solar thermal conversion system, thereby improving the solar capture efficiency. Based on actual production and operation experience, both PV and solar thermal power generation systems require regular cleaning to ensure the cleanliness of the light-receiving surface and prevent dust and impurities from blocking sunlight and affecting the system's power generation efficiency. Currently, the commonly used cleaning method is water spraying and brushing. However, repeated rinsing and cleaning over a long period of time requires antireflective coatings to have good wear resistance and stain resistance. However, the antireflective coatings currently on the market are somewhat lacking in both of these properties. Therefore, a method for preparing an antireflective coating with good wear resistance and stain resistance is proposed. This method can be used to prepare antireflective coatings with good wear resistance and stain resistance. Summary of the Invention

[0003] In view of the problems existing in the background art, the purpose of this invention is to provide a method for preparing a hybrid open-pore and closed-pore wear-resistant hydrophobic antireflective membrane, which effectively solves the problems existing in the background art.

[0004] To achieve the above objectives, the present invention adopts the following technical solution:

[0005] A method for preparing a hybrid open-pore and closed-pore wear-resistant hydrophobic antireflective membrane includes the following steps:

[0006] Step one, the preparation of the core-shell structured nanoparticle solution, includes the following steps:

[0007] Step a: Mix the reaction precursor, template agent and acid catalyst in proportion, stir and react to obtain solution A and let it stand;

[0008] Step b: Stir solution A and add crosslinking agent in proportion to react and obtain solution B, then age it;

[0009] Step c: After the aging of solution B is completed, immediately stir solution B and add anhydrous ethanol in proportion to obtain a core-shell structured nanoparticle solution;

[0010] Step two, the preparation of the wear-resistant adhesive, includes the following steps:

[0011] Step d involves mixing and stirring the reaction precursor, anhydrous ethanol, crosslinking agent, template agent, acid catalyst, curing agent, and film-forming aid in a specific ratio to obtain sol solution C.

[0012] Step e involves aging the sol solution C to obtain a wear-resistant adhesive;

[0013] Step 3, preparation of the open-pore and closed-pore hybrid wear-resistant antireflective film solution, includes the following steps:

[0014] In step f, the core-shell structured nanoparticle solution obtained in step c is added dropwise to the wear-resistant adhesive obtained in step e.

[0015] Step g: After the addition is completed, continue stirring for the specified time and allow to age to obtain the anti-reflection membrane solution;

[0016] Step four, preparation of the antireflective coating layer, includes the following steps:

[0017] In step h, the antireflection coating solution obtained in step g is applied to a glass substrate using a dip coating machine;

[0018] Step i involves heating and baking the coated glass substrate using a heating device to obtain a glass substrate coated with a hybrid open-pore and closed-pore wear-resistant antireflective film.

[0019] Step five, the deposition of the hydrophobic film, includes the following processes:

[0020] Step j: Dissolve the hydrogen-containing silicone oil in an organic solvent in a certain proportion, stir evenly, and then add the platinum catalyst dropwise in a certain proportion. After mixing evenly, the hydrophobic coating solution can be obtained.

[0021] In step k, the glass substrate coated with the hybrid open-cell and closed-cell wear-resistant and anti-reflective film obtained in step i is immersed in the hydrophobic coating solution obtained in step j for a specified time. Then, the hydrophobic coating solution is pulled out at a specified speed. Finally, the glass substrate coated with the hybrid open-cell and closed-cell wear-resistant and hydrophobic anti-reflective film is obtained by heating and baking with a heating device.

[0022] Furthermore, the reaction precursor is a silicate ester, the crosslinking agent is methyltrimethoxysilane and / or methyltriethoxysilane, the template agent in step a is styrene-acrylic emulsion, the template agent in step d is hexadecyltrimethylammonium bromide, the acid catalyst is one of dilute hydrochloric acid, dilute acetic acid, dilute citric acid, or dilute nitric acid, the curing agent is guanidine hydrochloride and / or aluminum acetylacetonate, and the film-forming aid is ethylene glycol and / or polyethylene glycol.

[0023] Furthermore, in step one, process a, the silicate ester, styrene-acrylic emulsion, and acidic catalyst contain H... + The molar ratio is 1:0.5-2.5:0.01-0.05. In step a, the reaction time of silicate ester, styrene-acrylic emulsion and acid catalyst is 1h-5h, and the standing time of solution A is 1h-3h.

[0024] Furthermore, in step one, step b, the mass ratio of crosslinking agent to solution A is 1:8-20. After adding the crosslinking agent, the reaction is stirred for 1-5 hours to obtain solution B. The aging time of solution B is 1-3 days. In step one, step c, the mass ratio of solution B to anhydrous ethanol is 1:1-3.5. Anhydrous ethanol is added drop by drop at a rate of 1-3 drops per second.

[0025] Furthermore, in step two, process d, the silicate ester, anhydrous ethanol, crosslinking agent, template agent, and acidic catalyst contain H... + The molar ratio is 1:0.5-3:20-50:5-20:0.01-0.05, and the amount of curing agent and film-forming aid added is 0.5%-5% of the total mass of sol solution C. The mixing and stirring reaction time of step d in step two is 1h-5h.

[0026] Furthermore, the aging time of the sol solution in step e of step two is 1-3 days.

[0027] Furthermore, in step three, process f, the mass ratio of the core-shell structured nanoparticle solution to the wear-resistant adhesive is 1:5-10, the dropping rate of the core-shell structured nanoparticle solution is 1 drop per second to 3 drops per second, and in step three, process g, after the dropping is completed, the stirring time is 1-5 hours and the aging time is 1-3 days.

[0028] Furthermore, in step four, process h, the speed of the coating machine is 1000μm / s-5000μm / s, and in step four, process i, the heating equipment is a muffle furnace with a heating and baking temperature of 300℃-500℃ and a heating and baking time of 0.5h-3h.

[0029] Furthermore, in step five, the mass ratio of hydrogen-containing silicone oil to organic solvent is 1:15-25, and the mass ratio of platinum catalyst to organic solvent is 1:150-200.

[0030] Furthermore, in step five, process k, the immersion time of the glass substrate in the hydrophobic coating solution is 3-10 minutes, the speed at which the glass substrate is pulled out of the hydrophobic coating solution is 1000 μm / s-3000 μm / s, and the heating equipment in step five, process k is also a muffle furnace, with a heating and baking temperature of 300℃-500℃ and a heating and baking time of 0.5h-3h.

[0031] The present invention has the following beneficial technical effects:

[0032] This invention proposes a method for preparing a hybrid open-cell and closed-cell wear-resistant hydrophobic antireflective membrane. This method combines the advantages of both open-cell and closed-cell antireflective membranes, ensuring good wear resistance and hydrophobicity while maintaining good light transmittance. Compared with existing antireflective membranes, the membrane prepared by this invention has better dirt resistance, which can effectively reduce the frequency of system cleaning. It does not break even with frequent washing, significantly extending its service life and facilitating the long-term and efficient operation of solar power generation systems, resulting in significant economic and social benefits. Attached Figure Description

[0033] Figure 1 This is a comparison of the transmittance curves of the antireflective coating obtained in the embodiments of the present invention and the original glass without coating;

[0034] Figure 2 This is a comparison of the transmittance curves of the antireflective coating obtained in the embodiments of the present invention after being rubbed by an abrasion tester for different numbers of times.

[0035] Figure 3 This is a cross-sectional scanning electron microscope image of the antireflection coating obtained in an embodiment of the present invention;

[0036] Figure 4 This is a scanning electron microscope image of the surface of the antireflection film obtained in an embodiment of the present invention. Detailed Implementation

[0037] The embodiments of the present invention will be described in further detail below with reference to the accompanying drawings and examples. The following examples are for illustrative purposes only and should not be construed as limiting the scope of the invention.

[0038] In the description of this invention, unless otherwise stated, "a plurality of" means two or more; the terms "upper," "lower," "left," "right," "inner," "outer," "front end," "rear end," "head," and "tail," etc., indicate the orientation or positional relationship based on the orientation or positional relationship shown in the accompanying drawings, and are only for the convenience of describing this invention and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, be constructed or operated in a specific orientation, and therefore should not be construed as a limitation of this invention. In the description of this invention, it should be noted that, unless otherwise explicitly specified and limited, the terms "connected" and "linked" should be interpreted broadly. For example, it can be a fixed connection, a detachable connection, or an integral connection; it can be a mechanical connection or an electrical connection; it can be a direct connection or an indirect connection through an intermediate medium. Those skilled in the art can understand the specific meaning of the above terms in this invention based on the specific circumstances.

[0039] Example 1

[0040] A method for preparing a hybrid open-pore and closed-pore wear-resistant hydrophobic antireflective membrane includes the following steps:

[0041] Step one, the preparation of the core-shell structured nanoparticle solution, includes the following steps:

[0042] Step a: Disperse the styrene-acrylic emulsion in an appropriate amount of deionized water, add dilute hydrochloric acid with a molar concentration of 0.1 mol / L, stir evenly, slowly add silicate ester and continue stirring to react. After reacting for 3 hours, stop stirring to obtain solution A and let it stand for 2 hours; the molar ratio of H+ in silicate ester, styrene-acrylic emulsion and dilute hydrochloric acid is 1:1.5:0.03.

[0043] Step b: Add methyltriethoxysilane to solution A, with a mass ratio of methyltriethoxysilane to solution A of 1:10, and continue stirring for 2 hours to obtain solution B. Let solution B stand and age for 2 days.

[0044] Step c: After the aging of solution B is completed, immediately stir solution B and add anhydrous ethanol in proportion and at a constant rate. Specifically, the mass ratio of solution B to anhydrous ethanol is 1:2. The anhydrous ethanol should be added drop by drop at a rate of 2 drops per second. After the addition is completed, continue stirring for 30 minutes to obtain a core-shell structured nanoparticle solution for later use.

[0045] Step two, the preparation of the wear-resistant adhesive, includes the following steps:

[0046] In step d, silicate ester is added to anhydrous ethanol in a certain proportion and mixed evenly. Then, hexadecyltrimethylammonium bromide is added to the mixture and stirred evenly. 0.1 mol / L dilute hydrochloric acid is added, and after the mixture becomes clear, the reaction is continued for 3 hours. After standing for 2 days, methyltrimethoxysilane is added, and the reaction is continued for 3 hours. Then, aluminum acetylacetonate and ethylene glycol are added, and the mixture is stirred for 20 minutes before stopping, yielding sol solution C. In step d, silicate ester, anhydrous ethanol, crosslinking agent, template agent, and acidic catalyst contain H... + The molar ratio is 1:2:35:10:0.03, and the amount of aluminum acetylacetonate and ethylene glycol added is 1% of the total mass of sol solution C.

[0047] Step e involves aging the sol solution C for 2 days to obtain a wear-resistant adhesive.

[0048] Step 3, preparation of the open-pore and closed-pore hybrid wear-resistant antireflective film solution, includes the following steps:

[0049] Step f: Weigh 200g of core-shell structured nanoparticle solution and add it dropwise to 1200g of continuously stirred wear-resistant binder sol solution at a dropping rate of 3 drops / second;

[0050] Step g: After the droplet is added, continue stirring for 2 hours and let it age for 3 days to obtain the anti-reflection membrane solution;

[0051] Step four, preparation of the antireflective coating layer, includes the following steps:

[0052] In step h, the antireflection coating solution obtained in step g is applied to a glass substrate using a dip coating machine at a dip coating speed of 1500 μm / s.

[0053] Step i: Place the coated glass substrate in a muffle furnace and bake at 400°C for 1 hour to obtain a glass substrate coated with a hybrid open-pore and closed-pore anti-reflective coating.

[0054] Step five, the deposition of the hydrophobic film, includes the following processes:

[0055] Step j: Dissolve 10g of hydrogen-containing silicone oil in 200g of n-hexane, then add 2g of platinum catalyst dropwise, and mix well to obtain a hydrophobic coating solution.

[0056] In step k, the glass substrate coated with the hybrid open-cell and closed-cell wear-resistant antireflective film obtained in step i is immersed in the hydrophobic coating solution obtained in step j for 5 minutes. Then, the substrate is pulled up at a speed of 2000 μm / s to perform the coating. The coated substrate is then placed in a muffle furnace and baked at 400℃ for 0.5 hours to obtain the glass substrate coated with the hybrid open-cell and closed-cell wear-resistant hydrophobic antireflective film.

[0057] The precursor for the above reaction is a silicate ester such as tetraethyl orthosilicate, the crosslinking agent is methyltriethoxysilane, the template agent in step a is styrene-acrylic emulsion, the template agent in step d is hexadecyltrimethylammonium bromide, the acid catalyst is one of dilute hydrochloric acid, dilute acetic acid, dilute citric acid or dilute nitric acid, the curing agent is guanidine hydrochloride and / or aluminum acetylacetonate, and the film-forming aid is ethylene glycol and / or polyethylene glycol.

[0058] Those skilled in the art will know that there are two main solutions to improve the stain resistance of antireflective films: one is to use hollow nanoparticles to make the film layer have a closed-pore structure, and the other is to make the film layer have self-cleaning properties such as hydrophobicity. However, there is a contradiction between the two. Generally, the surface roughness of the closed-pore structure film layer is small, while hydrophobicity requires the formation of a certain micro-nano structure on the surface, that is, a relatively large surface roughness is required. Therefore, hydrophobicity is not easy to achieve in pure closed-pore antireflective films. In order to obtain a high antireflection effect, the open-pore structure antireflective film will form a large surface roughness. However, with a large roughness, the wear resistance is relatively poor. This embodiment combines the advantages of both open-pore and closed-pore structure antireflective films. While maintaining a high transmittance, the film layer surface also has a certain roughness, which provides a certain foundation for achieving better hydrophobicity after the hydrophobic film is deposited. In addition, this embodiment also prepares relatively wear-resistant hollow particles and binders through the hydrolytic hinge of silicate ester and silane, which further improves the wear resistance of the antireflective film.

[0059] In summary, this embodiment combines the advantages of both open-cell and closed-cell antireflective membranes, ensuring good wear resistance and hydrophobicity while maintaining excellent light transmittance. Compared with existing antireflective membranes, the membrane prepared in this embodiment exhibits better dirt resistance, effectively reducing the frequency of system cleaning. It remains undamaged even with frequent washing, significantly extending its service life and facilitating the long-term, efficient operation of the solar power generation system, thus demonstrating significant economic and social benefits.

[0060] Example 2

[0061] A method for preparing a hybrid open-pore and closed-pore wear-resistant hydrophobic antireflective membrane includes the following steps:

[0062] Step one, the preparation of the core-shell structured nanoparticle solution, includes the following steps:

[0063] Step a: Disperse the styrene-acrylic emulsion in an appropriate amount of deionized water, add dilute acetic acid with a molar concentration of 0.1 mol / L, stir evenly, slowly add silicate ester and continue stirring to react. After reacting for 3 hours, stop stirring to obtain solution A and let it stand for 1 hour; the molar ratio of H+ in silicate ester, styrene-acrylic emulsion and dilute acetic acid is 1:0.5:0.01.

[0064] Step b: Add methyltriethoxysilane to solution A, with a mass ratio of methyltriethoxysilane to solution A of 1:15, and continue stirring for 1 hour to obtain solution B. Let solution B stand and age for 1 day.

[0065] Step c: After the aging of solution B is completed, immediately stir solution B and add anhydrous ethanol in proportion and at a constant rate. Specifically, the mass ratio of solution B to anhydrous ethanol is 1:1. The anhydrous ethanol should be added drop by drop at a rate of 1 drop per second. After the addition is completed, continue stirring for 30 minutes to obtain a core-shell structured nanoparticle solution for later use.

[0066] Step two, the preparation of the wear-resistant adhesive, includes the following steps:

[0067] In step d, silicate ester is added to anhydrous ethanol in a certain proportion and mixed evenly. Then, hexadecyltrimethylammonium bromide is added to the mixture and stirred evenly. 0.1 mol / L dilute acetic acid is added, and after the mixture becomes clear, the reaction is continued for 3 hours. After standing for 2 days, methyltriethoxysilane is added, and the reaction is continued for 3 hours. Then, aluminum acetylacetonate and ethylene glycol are added, and the mixture is stirred for 20 minutes before stopping, yielding sol solution C. In step d, silicate ester, anhydrous ethanol, methyltriethoxysilane, template agent, and acidic catalyst contain H... + The molar ratio is 1:0.5:20:5:0.01, and the addition amounts of aluminum acetylacetonate and ethylene glycol are both 0.5% of the total mass of sol solution C;

[0068] Step e involves aging the sol solution C for 1 day to obtain a wear-resistant adhesive.

[0069] Step 3, preparation of the open-pore and closed-pore hybrid wear-resistant antireflective film solution, includes the following steps:

[0070] Step f: Weigh 200g of core-shell structured nanoparticle solution and add it dropwise to 1000g of continuously stirred wear-resistant binder sol solution at a dropping rate of 1 drop / second;

[0071] Step g: After the droplet is added, continue stirring for 1 hour and let it age for 1 day to obtain the anti-reflection membrane solution.

[0072] Step four, preparation of the antireflective coating layer, includes the following steps:

[0073] In step h, the antireflection coating solution obtained in step g is applied to a glass substrate using a dip coating machine at a dip coating speed of 1000 μm / s.

[0074] Step i: Place the coated glass substrate in a muffle furnace and bake at 300°C for 0.5 hours to obtain a glass substrate coated with a hybrid open-pore and closed-pore wear-resistant antireflective film.

[0075] Step five, the deposition of the hydrophobic film, includes the following processes:

[0076] Step j: Dissolve 10g of hydrogen-containing silicone oil in 150g of n-hexane, then add 1g of platinum catalyst dropwise, and mix well to obtain a hydrophobic coating solution.

[0077] In step k, the glass substrate coated with the hybrid open-cell and closed-cell wear-resistant and anti-reflective film obtained in step i is immersed in the hydrophobic coating solution obtained in step j for 3 minutes. Then, the coating is applied by pulling at a speed of 1000 μm / s. The coated substrate is then placed in a muffle furnace and baked at a high temperature of 300℃ for 0.5 hours to obtain the glass substrate coated with the hybrid open-cell and closed-cell wear-resistant and hydrophobic anti-reflective film.

[0078] The precursor for the above reaction is a silicate ester such as tetraethyl orthosilicate, the crosslinking agent is methyltriethoxysilane, the template agent in step a is styrene-acrylic emulsion, the template agent in step d is hexadecyltrimethylammonium bromide, the acid catalyst is one of dilute hydrochloric acid, dilute acetic acid, dilute citric acid or dilute nitric acid, the curing agent is guanidine hydrochloride and / or aluminum acetylacetonate, and the film-forming aid is ethylene glycol and / or polyethylene glycol.

[0079] Example 3

[0080] A method for preparing a hybrid open-pore and closed-pore wear-resistant hydrophobic antireflective membrane includes the following steps:

[0081] Step one, the preparation of the core-shell structured nanoparticle solution, includes the following steps:

[0082] Step a: Disperse the styrene-acrylic emulsion in an appropriate amount of deionized water, add dilute nitric acid with a molar concentration of 0.1 mol / L, stir evenly, slowly add silicate ester and continue stirring to react. After reacting for 5 hours, stop stirring to obtain solution A and let it stand for 3 hours; the molar ratio of H+ in silicate ester, styrene-acrylic emulsion and dilute nitric acid is 1:2.5:0.05.

[0083] Step b: Add methyltrimethoxysilane to solution A, with a mass ratio of methyltrimethoxysilane to solution A of 1:18, and continue stirring for 5 hours to obtain solution B. Let solution B stand and age for 3 days.

[0084] Step c: After the aging of solution B is completed, immediately stir solution B and add anhydrous ethanol in proportion and at a constant rate. Specifically, the mass ratio of solution B to anhydrous ethanol is 1:3.5. The anhydrous ethanol should be added drop by drop at a rate of 3 drops per second. After completion, continue stirring for 30 minutes to obtain a core-shell structured nanoparticle solution for later use.

[0085] Step two, the preparation of the wear-resistant adhesive, includes the following steps:

[0086] In step d, silicate ester is added to anhydrous ethanol in a certain proportion and mixed evenly. Then, hexadecyltrimethylammonium bromide is added to the mixture and stirred evenly. 0.1 mol / L dilute nitric acid is added, and after the mixture is stirred until clear, the reaction is continued for 5 hours. After standing for 2 days, methyltrimethoxysilane is added, and the reaction is continued for 3 hours. Then, guanidine hydrochloride and ethylene glycol are added, and the mixture is stirred for 20 minutes before stopping, yielding sol solution C. In step d, silicate ester, anhydrous ethanol, methyltrimethoxysilane, template agent, and acidic catalyst contain H... + The molar ratio is 1:3:50:20:0.05, and the amount of guanidine hydrochloride and ethylene glycol added is 5% of the total mass of sol solution C;

[0087] Step e involves aging the sol solution C for 3 days to obtain a wear-resistant adhesive.

[0088] Step 3, preparation of the open-pore and closed-pore hybrid wear-resistant antireflective film solution, includes the following steps:

[0089] Step f: Weigh 200g of core-shell structured nanoparticle solution and add it dropwise to 2000g of continuously stirred wear-resistant binder sol solution at a dropping rate of 3 drops / second;

[0090] Step g: After the droplet is added, continue stirring for 5 hours and let it age for 3 days to obtain the anti-reflection membrane solution;

[0091] Step four, preparation of the antireflective coating layer, includes the following steps:

[0092] In step h, the antireflection coating solution obtained in step g is applied to a glass substrate using a dip coating machine at a dip coating speed of 5000 μm / s.

[0093] Step i: Place the coated glass substrate in a muffle furnace and bake at 500°C for 3 hours to obtain a glass substrate coated with a hybrid open-pore and closed-pore wear-resistant anti-reflective film.

[0094] Step five, the deposition of the hydrophobic film, includes the following processes:

[0095] Step j: Dissolve 10g of hydrogen-containing silicone oil in 250g of n-hexane, then add 2g of platinum catalyst dropwise, and mix well to obtain a hydrophobic coating solution.

[0096] In step k, the glass substrate coated with the hybrid open-cell and closed-cell wear-resistant antireflective film obtained in step i is immersed in the hydrophobic coating solution obtained in step j for 10 minutes. Then, the coating is applied by pulling at a speed of 3000 μm / s. The coated substrate is then placed in a muffle furnace and baked at a high temperature of 500℃ for 3 hours to obtain the glass substrate coated with the hybrid open-cell and closed-cell wear-resistant hydrophobic antireflective film.

[0097] The precursor for the above reaction is tetraethyl orthosilicate, the crosslinking agent is methyltrimethoxysilane, the template agent in step a is styrene-acrylic emulsion, the template agent in step d is hexadecyltrimethylammonium bromide, the acid catalyst is one of dilute hydrochloric acid, dilute acetic acid, dilute citric acid or dilute nitric acid, the curing agent is guanidine hydrochloride and / or aluminum acetylacetonate, and the film-forming aid is ethylene glycol and / or polyethylene glycol.

[0098] Figure 1 A comparison graph of the transmittance curves of the antireflective coating obtained in one embodiment of the present invention and the original uncoated glass is shown. Figure 2 A comparison of transmittance curves of the antireflection film obtained in one embodiment of the present invention after being rubbed by an abrasion tester for different numbers of times is shown. The abrasion tester is a Taber5900 abrasion tester. Figure 3 A cross-sectional scanning electron microscope image of an antireflection film obtained according to an embodiment of the present invention is shown. The cross-sectional image shows that there are closed pores inside the film. Figure 4 The image shows a scanning electron microscope (SEM) image of the antireflection membrane obtained according to an embodiment of the present invention. The surface image shows that the membrane has external pores. The present invention combines the advantages of both open-pore and closed-pore antireflection membranes, ensuring good permeability of the membrane. The final antireflection effect is ≥5%. The membrane also has good wear resistance. After 100 abrasion tests using a Taber 5900 abrasion tester, the permeability of the membrane decreases by ≤1%. In addition, the membrane also has good hydrophobic properties.

[0099] The embodiments of the present invention are given for illustrative and descriptive purposes only, and are not intended to be exhaustive or to limit the invention to the forms disclosed. Many modifications and variations will be apparent to those skilled in the art. The embodiments were chosen and described to better illustrate the principles of the invention and its practical application, and to enable those skilled in the art to understand the invention and design various embodiments with various modifications suitable for a particular purpose.

Claims

1. A method for preparing a hybrid open-pore and closed-pore wear-resistant hydrophobic antireflective membrane, characterized in that, Includes the following steps: Step one, preparation of core-shell structured nanoparticle solution, its The process includes the following steps: Step a: Mix silicate ester, template agent and acid catalyst in proportion, stir and react to obtain solution A and let stand; Step b: Stir solution A and add crosslinking agent in proportion to react and obtain solution B, then age it; Step c: After the aging of solution B is completed, immediately stir solution B and add anhydrous ethanol in proportion to obtain a core-shell structured nanoparticle solution; Step two, preparation of the wear-resistant adhesive, its The process includes the following steps: In step d, silicate ester, anhydrous ethanol, crosslinking agent, template agent, acid catalyst, curing agent and film-forming aid are mixed and stirred in proportion to obtain sol solution C; Step e involves aging the sol solution C to obtain a wear-resistant adhesive; Step 3: Preparation of the open-pore and closed-pore hybrid wear-resistant and anti-reflection membrane solution. The process includes the following steps: In step f, the core-shell structured nanoparticle solution obtained in step c is added dropwise to the wear-resistant binder obtained in step e; Step g: After the addition is completed, continue stirring for the specified time and allow to age to obtain the anti-reflection membrane solution; Step four, preparation of the antireflection membrane layer, its The process includes the following steps: In step h, the antireflection coating solution obtained in step g is applied to a glass substrate using a dip coating machine; Step i involves heating and baking the coated glass substrate using a heating device to obtain a glass substrate coated with a hybrid open-pore and closed-pore wear-resistant antireflective film. Step five, the deposition of the hydrophobic film, includes the following processes: Step j: Dissolve the hydrogen-containing silicone oil in an organic solvent in a certain proportion, stir evenly, and then add the platinum catalyst dropwise in a certain proportion. After mixing evenly, the hydrophobic coating solution can be obtained. In step k, the glass substrate coated with the hybrid open-cell and closed-cell wear-resistant and anti-reflective film obtained in step i is immersed in the hydrophobic coating solution obtained in step j for a specified time. Then, the hydrophobic coating solution is pulled out at a specified speed. Finally, the glass substrate coated with the hybrid open-cell and closed-cell wear-resistant and hydrophobic anti-reflective film is obtained by heating and baking with a heating device.

2. The method for preparing a hybrid open-pore and closed-pore wear-resistant hydrophobic antireflective membrane according to claim 1, characterized in that, In step one, step b, and step two, step d, the crosslinking agent is methyltrimethoxysilane and / or methyltriethoxysilane; in step one, step a, the template agent is styrene-acrylic emulsion; in step d, the template agent is hexadecyltrimethylammonium bromide; the acidic catalyst is one of dilute hydrochloric acid, dilute acetic acid, dilute citric acid, or dilute nitric acid; the curing agent is guanidine hydrochloride and / or aluminum acetylacetonate; and the film-forming aid is ethylene glycol and / or polyethylene glycol.

3. The method for preparing a hybrid open-pore and closed-pore wear-resistant hydrophobic antireflective membrane according to claim 2, characterized in that, In step one, process a, the silicate, styrene-acrylic emulsion, and acidic catalyst contain H... + The molar ratio is 1:0.5-2.5:0.01-0.

05. In step a, the reaction time of silicate ester, styrene-acrylic emulsion and acid catalyst is 1h-5h, and the standing time of solution A is 1h-3h.

4. The method for preparing a hybrid open-pore and closed-pore wear-resistant hydrophobic antireflective membrane according to claim 3, characterized in that, In step one, process b, the mass ratio of crosslinking agent to solution A is 1:8-20. After adding the crosslinking agent, the reaction is stirred for 1-5 hours to obtain solution B. The aging time of solution B is 1-3 days. In step one, process c, the mass ratio of solution B to anhydrous ethanol is 1:1-3.

5. Anhydrous ethanol is added drop by drop at a rate of 1-3 drops per second.

5. The method for preparing a hybrid open-pore and closed-pore wear-resistant hydrophobic antireflective membrane according to claim 2, characterized in that, In step two, process d, the silicate ester, anhydrous ethanol, crosslinking agent, template agent, and acidic catalyst contain H. + The molar ratio is 1:0.5-3:20-50:5-20:0.01-0.05, and the amount of curing agent and film-forming aid added is 0.5%-5% of the total mass of sol solution C. The mixing and stirring reaction time of step d in step two is 1h-5h.

6. The method for preparing a hybrid open-cell and closed-cell wear-resistant hydrophobic antireflective membrane according to claim 5, characterized in that, The aging time of the sol solution in step two, process e, is 1-3 days.

7. The method for preparing a hybrid open-pore and closed-pore wear-resistant hydrophobic antireflective membrane according to claim 1, characterized in that, In step three, process f, the mass ratio of the core-shell structured nanoparticle solution to the wear-resistant binder is 1:5-10, the dropping rate of the core-shell structured nanoparticle solution is 1 drop per second to 3 drops per second, and after the dropping is completed in step three, process g, the stirring time is 1-5 hours and the aging time is 1-3 days.

8. The method for preparing a hybrid open-cell and closed-cell wear-resistant hydrophobic antireflective membrane according to claim 1, characterized in that, In step four, process h, the speed of the coating machine is 1000μm / s-5000μm / s. In step four, process i, the heating equipment is a muffle furnace, the heating and baking temperature is 300℃-500℃, and the heating and baking time is 0.5h-3h.

9. The method for preparing a hybrid open-pore and closed-pore wear-resistant hydrophobic antireflective membrane according to claim 1, characterized in that, In step five, the mass ratio of hydrogen-containing silicone oil to organic solvent is 1:15-25, and the mass ratio of platinum catalyst to organic solvent is 1:150-200.

10. The method for preparing a hybrid open-cell and closed-cell wear-resistant hydrophobic antireflective membrane according to claim 9, characterized in that, In step five, process k, the glass substrate is immersed in the hydrophobic coating solution for 3-10 minutes, and the glass substrate is pulled out of the hydrophobic coating solution at a speed of 1000μm / s-3000μm / s. The heating equipment in step five, process k is also a muffle furnace, with a heating and baking temperature of 300℃-500℃ and a heating and baking time of 0.5h-3h.

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