CN111362589B - Weather-proof double-layer high-anti-reflection coated glass and preparation method thereof - Google Patents
Weather-proof double-layer high-anti-reflection coated glass and preparation method thereof Download PDFInfo
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- CN111362589B CN111362589B CN202010356629.5A CN202010356629A CN111362589B CN 111362589 B CN111362589 B CN 111362589B CN 202010356629 A CN202010356629 A CN 202010356629A CN 111362589 B CN111362589 B CN 111362589B
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
- C03C17/008—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character comprising a mixture of materials covered by two or more of the groups C03C17/02, C03C17/06, C03C17/22 and C03C17/28
- C03C17/009—Mixtures of organic and inorganic materials, e.g. ormosils and ormocers
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/11—Deposition methods from solutions or suspensions
Abstract
The invention relates to the technical field of glass, in particular to weather-resistant double-layer high anti-reflection coated glass and a preparation method thereof. The glass substrate comprises a glass substrate, and a bottom anti-reflection coating layer and a top anti-reflection coating layer which are sequentially arranged on the upper surface of the glass substrate, wherein the top anti-reflection coating layer is made of a top anti-reflection coating liquid, the bottom anti-reflection coating layer is made of a bottom anti-reflection coating liquid, and the bottom anti-reflection coating liquid comprises the following raw materials in parts by weight: 25-35 parts of silicon dioxide prepolymer, 15-25 parts of silane coupling agent, 15-20 parts of isopropanol, 20-30 parts of cationic silica sol, 1-2 parts of surfactant, 4-8 parts of propylene glycol butyl ether and 1-10 parts of epoxy silane oligomer. According to the invention, two anti-reflection film coating liquids with different refractive indexes are sequentially coated on the solar photovoltaic glass, so that the photovoltaic anti-reflection glass has a broadband anti-reflection effect in a 380-plus-1100 nm spectral range and has higher weather resistance and light transmittance.
Description
Technical Field
The invention relates to the technical field of glass, in particular to weather-resistant double-layer high anti-reflection coated glass and a preparation method thereof.
Background
Solar photovoltaic is one of the most potential clean energy sources, and related practitioners in various countries are developing various advanced technologies and new products, hopefully improving photoelectric conversion efficiency. Among the factors determining the conversion efficiency of the crystalline silicon solar cell, the most important factor is the crystalline silicon technology in the photoelectric component, and the photovoltaic glass protecting the photoelectric component is used; in contrast, the cost is slightly lower than the cost of improving the conversion efficiency of a crystalline silicon cell by improving the optical characteristics of the photovoltaic glass.
However, in order to improve the light transmittance of photovoltaic glass in the market at present, a single-layer film is generally coated on the surface of the glass to increase the light transmittance, but the anti-reflection of the glass coated with the single-layer antireflection film layer is generally about 2.3%, and the light transmittance curve of the photovoltaic glass added with the single-layer antireflection film is in an inverted V shape, so that the reflectivity of the photovoltaic glass can only be reduced near a certain wavelength, the photovoltaic glass begins to be reduced after the peak value is reached, and the photovoltaic glass still has high reflection to visible light. The latest technology at present is to plate a double-layer antireflection film on photovoltaic glass, wherein the double-layer antireflection film can enable a certain wave band to have very low reflectivity, broaden a bandwidth area and greatly improve average light transmittance in a full spectrum range, thereby improving the output power of a solar photovoltaic module.
However, compared with a single-layer film, the double-layer antireflection film increases an interface between the film layers, and thus increases a risk point of falling off of one film layer. In practical application, the solar photovoltaic module is exposed in an atmospheric environment and needs to withstand severe environments such as sun, rain, high humidity and heat, if the coating quality is not high, the top film layer falls off, and because the refractive index of the bottom layer is generally higher, the residual antireflection effect is far inferior to that of a conventional single-layer antireflection film, so that the long-term power increase is inferior to that of a single-layer antireflection photovoltaic module.
Patent 200610025928.0 entitled "method for plating composite antireflection film on surface of silicon dioxide Crystal" adopts sol-gel method to prepare acid/alkali type coating solution with tetraethoxysilane as precursor and hydrochloric acid and ammonia water as catalysts, and then uses acid type coating solutionPlating a layer of high refractive index layer on the base material, and plating a layer of low refractive index layer on the base material by using alkali type coating liquid, thereby preparing the double-layer antireflection film with higher optical transmittance within the range of 450-1100 nm. However, it is known that alkali-catalyzed hydrolysis of tetraethoxysilane followed by coating forms SiO2The particles are randomly accumulated on the surface of the substrate, and the formed film layer has high porosity and high light transmittance, but SiO is used2The contact surface between the particles is small, and the particles are easy to fall off due to van der waals interaction, so that the method is not suitable for outdoor practical application.
To improve this problem, patent 201810513506.0 "a double-layer composite SiO2The preparation method of the antireflection film adopts a certain amount of acid-catalyzed silica sol doped in the alkali-catalyzed coating solution as the top layer coating solution, wherein the acid-catalyzed silica sol is of a chain structure and can fill SiO2The voids between the particles, thereby connecting SiO2The effect of the particles enhances the adhesive force and the hardness of the film layer to a certain extent, and is beneficial to improving the weather resistance. However, the pores of the antireflection film are open to the atmosphere, and SiO is present2The surface of the particle is provided with a large amount of silicon hydroxyl, so that the particle can easily absorb moisture in the air, the refractive index of the film layer is increased in a short term, the light transmittance is rapidly reduced, and the film layer falls off in a long term due to the fact that water molecules enter the film layer to corrode a silicon-oxygen framework of the film layer in a high-temperature high-humidity environment.
Disclosure of Invention
In order to overcome the defects and shortcomings in the prior art, the invention aims to provide weather-proof double-layer high anti-reflection coated glass, which adopts a double-layer anti-reflection film technology, and two anti-reflection film coating liquids with different refractive indexes are sequentially coated on solar photovoltaic glass, so that the photovoltaic anti-reflection glass has a broadband anti-reflection effect in a spectrum range of 380 plus 1100nm, and the power generation efficiency of a photovoltaic module can be effectively improved.
The invention also aims to provide a preparation method of the weather-resistant double-layer high anti-reflection coated glass, which has the advantages of simple operation and high production efficiency, can improve the bonding strength between the bottom anti-reflection coated layer and the glass substrate and between the bottom anti-reflection coated layer and the top anti-reflection coated layer, improves the weather resistance of the weather-resistant double-layer high anti-reflection coated glass, and is suitable for large-scale production.
The purpose of the invention is realized by the following technical scheme: a weather-proof double-layer high anti-reflection coated glass comprises a glass substrate, a bottom anti-reflection coating layer arranged on the upper surface of the glass substrate and a top anti-reflection coating layer arranged on the upper surface of the bottom anti-reflection coating layer, wherein the top anti-reflection coating layer is made of top anti-reflection coating liquid, the bottom anti-reflection coating layer is made of bottom anti-reflection coating liquid, and the bottom anti-reflection coating liquid comprises the following raw materials in parts by weight:
the bottom layer antireflection coating liquid adopts the cationic silica sol and the epoxy silane oligomer, so that the bonding effect between the bottom layer antireflection coating layer and the glass substrate and between the bottom layer antireflection coating layer and the top layer antireflection coating layer is enhanced, the film layers are not easy to fall off, and the double-layer film antireflection coating has stronger weather resistance which is more than 10 times of the national standard compared with the conventional double-layer film technology. The bottom anti-reflection coating liquid adopts the combined action of cationic silica sol and epoxy silane oligomer, so that the adhesion and combination of the bottom anti-reflection coating layer and the glass substrate are obviously improved, and the top anti-reflection coating layer is bonded, preferably, the top layer is of a core-shell hollow porous structure, the surface of the film layer is sealed, water vapor is effectively prevented from entering the film layer, and the weather resistance of the weather-resistant double-layer high-anti-reflection coating glass is further improved.
Preferably, the silane coupling agent is at least one of methyltrimethoxysilane, 3-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane and 3-mercaptopropyltriethoxysilane.
The silane coupling agent can promote the coaction of the cationic silica sol and the epoxy silane oligomer, improve the combination of the bottom anti-reflection coating liquid and the surface of the glass substrate, form a stable cross-linked network, form a bottom anti-reflection coating layer with moderate porosity and good adhesive force, improve the bonding effect between the bottom anti-reflection coating layer and the glass substrate and ensure that the coating layer is not easy to fall off.
Preferably, the surfactant is a cationic surfactant, and the cationic surfactant is at least one of cetyl trimethyl ammonium bromide, dodecyl benzyl dimethyl ammonium chloride and didodecyl dimethyl ammonium chloride.
The cationic surfactant adopted by the invention delays the hydrolysis condensation reaction speed of silane, can improve the stability of the bottom antireflection film coating liquid and plays a role in pore forming.
Preferably, the cationic silica sol is an acidic silica sol in which the surfaces of silica sol particles are treated with an aluminum compound, and has a pH of 2 to 4, a particle diameter of 10 to 30nm, and a solid content of 20 to 40%. Further preferably, the cationic silica sol is at least one of Levasil CT16PCL type cationic silica sol of NOURYON company, Levasil CT18PCL type cationic silica sol of NOURYON company and ST-AK type cationic silica sol of Nissan chemical, and the cationic silica sol of the type is prepared by surface modification treatment of an aluminum compound.
Preferably, the epoxy silane oligomer is an organosilicon oligomer containing epoxy functional groups. Further preferably, the epoxy silane oligomer is at least one of Maifang CoatOSil MP200, model LD-3168 epoxy silane oligomer of Yangzhou Liudon resin Co., Ltd, and PU118 of Guangzhou Yangsong trade Co., Ltd.
The epoxy silane oligomer can obviously improve the adhesive force between the film layer and the glass substrate, can be permanently combined with the glass substrate under the damp and hot condition, improves the adhesive stability between the bottom anti-reflection coating layer and the glass substrate, ensures that the film layer is not easy to fall off, and further improves the weather resistance of the weather-resistant double-layer high anti-reflection coated glass.
When the epoxy silane oligomer and the cationic silica sol are compounded for use, the cationic silica sol adopts an aluminum compound to carry out surface treatment on silica sol particles, so that the existence of metal aluminum ions in the cationic silica sol can catalyze the ring-opening reaction between epoxy groups and silicon hydroxyl groups more easily, and the dehydration condensation reaction between the silicon hydroxyl groups is more easily carried out, thereby enhancing the crosslinking density of a film layer, simultaneously forming Si-O-Al bonds with larger bond energy than the Si-O-Si bonds at high temperature, further increasing the weather resistance of a bottom anti-reflection coating layer, and obviously improving the performances of salt mist resistance and anti-freezing tests. Wherein the aluminum compound is an aluminum salt selected from at least one of aluminum nitrate, aluminum chloride, aluminum phosphate, aluminum formate, aluminum acetate, aluminum propionate, dialkylaluminum chloride, monoalkylaluminum dichloride, trialkyltrialuminum trichloride, aluminum isopropoxide and aluminum acetylacetonate.
Preferably, the silica prepolymer is prepared by the following steps:
according to the weight portion, 50-55 portions of ethyl silicate 40, 55-65 portions of isopropanol, 0.5-2 portions of glacial acetic acid and 15-20 portions of water are uniformly mixed, hydrolyzed for 40-50h at normal temperature, heated to 75-85 ℃ for reaction for 1.5-2.5h, and cooled to room temperature to prepare the silicon dioxide prepolymer.
According to the invention, the silicon dioxide prepolymer is prepared through the steps, so that the prepared silicon dioxide prepolymer has high stability, and the bottom anti-reflection coating layer can reduce light reflection, thereby improving light transmittance; specifically, ethyl silicate 40 is dissolved in isopropanol, and undergoes hydrolysis reaction in water to produce silicic acid sol and release heat, while glacial acetic acid catalyzes the production of silica prepolymer.
Preferably, the preparation of the bottom layer antireflection coating liquid comprises the following steps:
uniformly mixing the silicon dioxide prepolymer, the silane coupling agent, the isopropanol, the cationic silica sol, the surfactant and the propylene glycol butyl ether according to the parts by weight, releasing heat in the reaction process, heating a reaction system to 45-55 ℃, and then standing for 1-2 hours to naturally cool to the normal temperature; then adding epoxy silane oligomer, mixing uniformly to obtain a mixture, and finally diluting with isopropanol until the solid content of the mixture is 3-10% to prepare the bottom layer anti-reflection coating liquid.
Preferably, the top layer anti-reflection coating liquid contains nano core-shell SiO2The microspheres and the hydroxyl-containing silicon-aluminum sol raw material are compounded in a volume ratio of 1:1-10 to obtain the composite materialTo, wherein, the nano core-shell SiO2The microsphere is prepared by the following steps:
step S1: preparing a polystyrene core by a soap-free emulsion polymerization method: putting a comonomer and water into a reaction container, adding styrene, heating to 50-85 ℃ under the protection of nitrogen, and dropwise adding an initiator aqueous solution to react to obtain a cationic polystyrene emulsion;
step S2: preparing a core-shell structure microsphere emulsion of silicon dioxide coated polystyrene: and (4) taking the cationic polystyrene emulsion prepared in the step (S1) as a hard template, mixing the hard template with a solvent, adding a silicon source substance into the mixture at the temperature of between 15 and 35 ℃ for reaction, and obtaining the polystyrene nano core-shell structure microsphere emulsion coated with silicon dioxide.
Preferably, in the step S1, the comonomer is a quaternized vinyl monomer and/or an amino group-containing vinyl monomer; the quaternized vinyl monomer is one or more of acryloyloxyethyl trimethoxy ammonium chloride, methacryloyloxyethyl trimethyl ammonium chloride, (methyl) acrylamidopropyl trimethyl ammonium chloride and diallyl dimethyl ammonium chloride; the amino-containing vinyl monomer is one or more of dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate and diisopropylaminoethyl (meth) acrylate.
When the comonomer is an amino group-containing vinyl monomer, the amino group-containing vinyl monomer is protonated with an acid selected from an inorganic acid or an organic acid before step S1 is performed.
Preferably, the inorganic acid is hydrochloric acid, sulfuric acid, nitric acid or phosphoric acid, and the organic acid is acetic acid, citric acid or oxalic acid.
The amount of the inorganic acid required is 50 to 100% by mole of the monobasic acid based on the amino group contained in the acid and the amino group-containing vinyl monomer.
Preferably, in the step S1, the mass ratios of the comonomer, the styrene, the initiator and the water in the whole system are respectively as follows: 0.5-4% of comonomer, 10-20% of styrene, 0.1-1% of initiator and 75-89.4% of water.
Preferably, in the step S1, after the styrene is added, stirring is performed at a stirring speed of 150-500 rpm.
Preferably, in step S1, the initiator is potassium persulfate or azobisisobutylamidine hydrochloride; the dropping speed of the initiator added dropwise is 0.1-2 mL/min.
Preferably, in the step S2, the silicon source material is at least one selected from tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, gamma-mercaptopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, and gamma- (methacryloyloxy) propyltrimethoxysilane.
Preferably, in step S2, the solvent is used in an amount to dilute the cationic polystyrene emulsion to a solid content of 1-20%.
Preferably, in step S2, the mass ratio of the solid mass of the polystyrene emulsion to the added amount of the silicon source material is 10 to 30%.
Preferably, in step S2, the solvent is at least one of water, methanol, ethanol, ethylene glycol, n-propanol, isopropanol, propylene glycol, glycerol, n-butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol methyl ether, propylene glycol butyl ether, tripropylene glycol monomethyl ether, or tripropylene glycol monoethyl ether.
Preferably, the hydroxyl group-containing silica-alumina sol raw material is obtained by reacting a raw material containing water, an acidic catalyst, a solvent, an aluminum salt and a silicon source material, wherein the aluminum salt has a mass of 0.025 to 0.1g, the solvent has a content of 1 to 20mL, the water has a content of 0.1 to 1mL, and the catalyst has a content of 0.01 to 0.1mL, relative to 1mL of the volume of the silicon source material.
Preferably, the catalyst is at least one of hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, acetic acid, citric acid and oxalic acid.
Preferably, the silicon source material is at least one of tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, gamma-mercaptopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane or gamma- (methacryloyloxy) propyltrimethoxysilane.
The invention prepares the SiO with the nanometer core-shell structure through the steps2Carrying out composite doping on microspheres and silicon-aluminum sol to prepare top layer anti-reflection coating liquid, coating the surface of the bottom layer anti-reflection coating liquid with the top layer anti-reflection coating liquid, and curing and toughening to obtain the nano core-shell SiO in the coating2The organic core in the microsphere is burnt to form nano SiO2The hollow microspheres are formed into a core-shell hollow porous structure by placing the holes inside the particles instead of in a silicon dioxide network, so that the film layer is ensured to have higher light transmittance and higher porosity, the film layer has higher mechanical strength and a compact surface, water vapor is effectively prevented from entering the film layer, and the weather resistance of the weather-resistant double-layer high anti-reflection coated glass is further improved.
Preferably, the thickness of the top anti-reflection coating layer is 80-200nm, and the thickness of the bottom anti-reflection coating layer is 50-200 nm; the refractive index of the top anti-reflection coating layer is 1.10-1.30, and the refractive index of the bottom anti-reflection coating layer is 1.25-1.45.
According to the invention, the thickness of the top anti-reflection coating layer and the thickness of the bottom anti-reflection coating layer are strictly controlled and are matched with the top anti-reflection coating liquid and the bottom anti-reflection coating liquid, so that the bottom coating layer and the top coating layer with gradient refractive indexes are prepared on the surface of the glass substrate, the photovoltaic anti-reflection glass has a broadband anti-reflection effect in a spectrum range of 380 plus 1100nm, and the power generation efficiency of the photovoltaic module is improved.
The other purpose of the invention is realized by the following technical scheme: the preparation method of the weather-resistant double-layer high anti-reflection coated glass comprises the following steps:
step A: coating the bottom layer anti-reflection coating liquid on the upper surface of the glass substrate, and then carrying out primary curing through a curing furnace to obtain the glass substrate coated with the bottom layer anti-reflection coating;
and B: and C, coating the top anti-reflection coating liquid on the upper surface of the bottom anti-reflection coating prepared in the step A, then performing secondary curing, further baking and curing, and then performing toughening treatment through a toughening furnace to prepare the weather-proof double-layer high anti-reflection coated glass.
Preferably, in the step A, the curing temperature of the first curing is 60-250 ℃, and the curing time is 1-5 min; in the step B, the curing temperature of the second curing is 80-250 ℃, and the tempering temperature is 500-700 ℃.
According to the optical principle of the film, the invention adopts a double-layer antireflection film technology to coat two antireflection film coating liquids with different refractive indexes on the solar photovoltaic glass in sequence to form the high antireflection coated glass with the gradient refractive index, wherein the refractive index meets n0<n1<n2<nsWherein n is0、n1、n2、nsRespectively, the refractive indices of air, the top film, the bottom film, and glass. By adjusting the refractive index matching of the bottom layer film and the top layer film, the photovoltaic anti-reflection glass has a broadband anti-reflection effect in a spectrum range of 380-1100nm, and the power generation efficiency of the photovoltaic module is greatly improved.
Meanwhile, after the bottom anti-reflection coating liquid is cured at a specific temperature and for a specific time, a formed film layer is compact, the cationic silica sol and the epoxy silane oligomer act together, the combination with the glass substrate is greatly improved, and the effect of bonding the top layer can be achieved; the top layer is of a core-shell hollow porous structure, the surface of the film layer is sealed, water vapor is greatly prevented from entering the film layer, and the weather resistance is further improved.
The invention has the beneficial effects that: the weather-proof double-layer high anti-reflection coated glass adopts a double-layer anti-reflection film technology, and two anti-reflection film coating liquids with different refractive indexes are sequentially coated on the solar photovoltaic glass to form the high anti-reflection coated glass with the gradient refractive index, wherein the refractive index meets n0<n1<n2<nsWherein n is0、n1、n2、nsThe refractive indexes of air, the top layer film, the bottom layer film and the glass respectively can ensure that the photovoltaic anti-reflection glass has a broadband anti-reflection effect in a spectrum range of 380 plus 1100nm, thereby greatly improving the power generation efficiency of the photovoltaic module。
The bottom anti-reflection coating liquid adopts cationic silica sol and epoxy silane oligomer to enhance the bonding effect between the bottom anti-reflection coating layer and the glass substrate and between the bottom anti-reflection coating layer and the top anti-reflection coating layer, so that the film layers are not easy to fall off, and compared with the existing double-layer film technology, the double-layer film anti-reflection film provided by the invention has stronger weather resistance, and the weather resistance exceeds the national standard by more than 10 times. The bottom anti-reflection coating liquid adopts the combined action of cationic silica sol and epoxy silane oligomer, so that the adhesion and combination of the bottom anti-reflection coating layer and the glass substrate are obviously improved, and the top anti-reflection coating layer is bonded, preferably, the top layer is of a core-shell hollow porous structure, the surface of the film layer is sealed, water vapor is effectively prevented from entering the film layer, and the weather resistance of the weather-resistant double-layer high-anti-reflection coating glass is further improved.
The preparation method of the weather-resistant double-layer high anti-reflection coated glass is simple and convenient to operate and high in production efficiency, a film layer formed on the surface of a glass substrate is compact after a bottom anti-reflection coating liquid is cured at a specific temperature for a specific time, and the cationic silica sol and the epoxy silane oligomer act together, so that the combination with the glass substrate is greatly improved, the top layer can be bonded, and the bonding strength between the bottom anti-reflection coating layer and the glass substrate and between the bottom anti-reflection coating layer and the top anti-reflection coating layer is improved; the top layer is of a core-shell hollow porous structure, the surface of the film layer is sealed, water vapor is greatly prevented from entering the film layer, and the weather resistance of the weather-resistant double-layer high anti-reflection coated glass is further improved, so that the anti-reflection of the prepared anti-reflection coated glass can reach more than 2.6%, the salt mist resistance can reach more than 1440h, and the wet freezing performance can reach more than 2400 h.
Drawings
FIG. 1 is a schematic cross-sectional view of a weatherable double-layer high anti-reflection coated glass of the present invention.
The reference signs are: 1-glass substrate, 2-bottom anti-reflection coating layer and 3-top anti-reflection coating layer.
Detailed Description
For the understanding of those skilled in the art, the present invention will be further described with reference to the following examples and the accompanying fig. 1, and the description of the embodiments is not intended to limit the present invention.
Example 1
Referring to the attached drawing 1, the weather-resistant double-layer high anti-reflection coated glass comprises a glass substrate 1, a bottom anti-reflection coated layer 2 arranged on the upper surface of the glass substrate 1 and a top anti-reflection coated layer 3 arranged on the upper surface of the bottom anti-reflection coated layer 2, wherein the top anti-reflection coated layer 3 is made of top anti-reflection coated liquid, the bottom anti-reflection coated layer 2 is made of bottom anti-reflection coated liquid, and the bottom anti-reflection coated liquid comprises the following raw materials in parts by weight:
the silane coupling agent is 3-aminopropyl triethoxysilane.
The surfactant is a cationic surfactant which is dodecyl benzyl dimethyl ammonium chloride.
The cation silica sol is Levasil CT16PCL type cation silica sol of NOURYON company.
The epoxy silane oligomer is an organic silicon oligomer containing epoxy functional groups.
The epoxy silane oligomer is selected from mayform CoatOSil MP 200.
The silica prepolymer is prepared by the following steps:
according to the weight portion, 50 portions of ethyl silicate 40, 55 portions of isopropanol, 0.5 portion of glacial acetic acid and 15 portions of water are uniformly mixed, hydrolyzed for 40 hours at normal temperature, heated to 75 ℃ for reaction for 2.5 hours, and cooled to room temperature to prepare the silicon dioxide prepolymer.
The preparation method of the bottom layer antireflection coating liquid comprises the following steps:
uniformly mixing the silicon dioxide prepolymer, the silane coupling agent, the isopropanol, the cationic silica sol, the surfactant and the propylene glycol butyl ether according to the parts by weight, releasing heat in the reaction process, heating the reaction system to 45 ℃, and then standing for 1.8h and naturally cooling to the normal temperature; and adding epoxy silane oligomer, uniformly mixing to obtain a mixture, and finally diluting with isopropanol until the solid content of the mixture is 3% to prepare the bottom layer anti-reflection coating liquid.
The top layer anti-reflection coating liquid passes through SiO containing nano core shell2The microspheres and the hydroxyl-containing silicon-aluminum sol raw material are compounded in a volume ratio of 1:1, wherein the nano core-shell SiO is2The microsphere is prepared by the following steps:
step S1: preparing a polystyrene core by a soap-free emulsion polymerization method: putting a comonomer and water into a reaction container, adding styrene, heating to 50 ℃ under the protection of nitrogen, and dropwise adding an initiator aqueous solution to react to obtain a cationic polystyrene emulsion;
step S2: preparing a core-shell structure microsphere emulsion of silicon dioxide coated polystyrene: and (4) taking the cationic polystyrene emulsion prepared in the step S1 as a hard template, mixing the hard template with a solvent, and adding a silicon source substance to react under stirring at 15 ℃ to obtain the polystyrene nano core-shell structure microsphere emulsion coated with silicon dioxide.
In the step S1, the comonomer is a quaternized vinyl monomer; the quaternized vinyl monomer is acryloyloxyethyl trimethoxy ammonium chloride.
In the step S1, the mass ratios of the comonomer, the styrene, the initiator and the water in the whole system are respectively as follows: 0.5 percent of comonomer, 10 percent of styrene, 0.1 percent of initiator and 75 percent of water.
In the step S1, after styrene was added, stirring was carried out at a stirring speed of 150 rpm.
In the step S1, the initiator is potassium persulfate; the dropping speed of the initiator added dropwise was 0.1 mL/min.
In step S2, the silicon source material is tetramethoxysilane.
In the step S2, the solvent is used in an amount to dilute the cationic polystyrene emulsion to a solid content of 1%.
In step S2, the mass ratio of the solid mass of the polystyrene emulsion to the amount of the silicon source material added is 10%.
In step S2, the solvent is methanol.
The hydroxyl-containing silicon-aluminum sol raw material is obtained by reacting raw materials containing water, an acidic catalyst, a solvent, an aluminum salt and a silicon source material, wherein the mass of the aluminum salt is 0.025g, the content of the solvent is 1mL, the content of the water is 0.1mL, and the content of the catalyst is 0.01mL relative to 1mL of the volume of the silicon source material.
The catalyst is hydrochloric acid; the silicon source substance is tetramethoxysilane; the aluminum salt is aluminum phosphate; the solvent is ethylene glycol.
The thickness of the top anti-reflection coating layer 3 is 80nm, and the thickness of the bottom anti-reflection coating layer 2 is 50 nm; the refractive index of the top anti-reflection coating layer 3 is 1.30, and the refractive index of the bottom anti-reflection coating layer 2 is 1.45.
The preparation method of the weather-resistant double-layer high anti-reflection coated glass comprises the following steps:
step A: coating the bottom layer antireflection coating liquid on the upper surface of the glass substrate 1, and then carrying out primary curing to obtain the glass substrate 1 coated with the bottom layer antireflection coating;
and B: and C, coating the top anti-reflection coating liquid on the upper surface of the bottom anti-reflection coating prepared in the step A, curing for the second time, and tempering to prepare the weather-proof double-layer high anti-reflection coated glass.
In the step A, the curing temperature of the first curing is 60 ℃, and the curing time is 5 min; in the step B, the curing temperature of the second curing is 80 ℃, and the tempering temperature is 500 ℃.
Example 2
Referring to the attached drawing 1, the weather-resistant double-layer high anti-reflection coated glass comprises a glass substrate 1, a bottom anti-reflection coated layer 2 arranged on the upper surface of the glass substrate 1 and a top anti-reflection coated layer 3 arranged on the upper surface of the bottom anti-reflection coated layer 2, wherein the top anti-reflection coated layer 3 is made of top anti-reflection coated liquid, the bottom anti-reflection coated layer 2 is made of bottom anti-reflection coated liquid, and the bottom anti-reflection coated liquid comprises the following raw materials in parts by weight:
the silane coupling agent is gamma-glycidol ether oxygen propyl trimethoxy silane.
The surfactant is a cationic surfactant which is didodecyldimethylammonium chloride.
The cationic silica sol is selected from ST-AK type cationic silica sols of Nissan chemical.
The epoxy silane oligomer is LD-3168 epoxy silane oligomer produced by Yangzhou Liuda resin Co.
The silica prepolymer is prepared by the following steps:
according to the weight portion, 51 portions of ethyl silicate 40, 58 portions of isopropanol, 0.8 portion of glacial acetic acid and 16 portions of water are uniformly mixed, hydrolyzed for 42 hours at normal temperature, heated to 78 ℃ for reaction for 2.3 hours, and cooled to room temperature to prepare the silicon dioxide prepolymer.
The preparation method of the bottom layer antireflection coating liquid comprises the following steps:
uniformly mixing the silicon dioxide prepolymer, the silane coupling agent, the isopropanol, the cationic silica sol, the surfactant and the propylene glycol butyl ether according to the parts by weight, releasing heat in the reaction process, heating the reaction system to 48 ℃, and then standing for 1.8h and naturally cooling to the normal temperature; and adding epoxy silane oligomer, uniformly mixing to obtain a mixture, and finally diluting with isopropanol until the solid content of the mixture is 5% to prepare the bottom layer anti-reflection coating liquid.
The top layer anti-reflection coating liquid passes through SiO containing nano core shell2The microspheres and the hydroxyl-containing silicon-aluminum sol raw material are compounded in a volume ratio of 1:3, wherein the nano core-shell SiO is2The microsphere is prepared by the following steps:
step S1: preparing a polystyrene core by a soap-free emulsion polymerization method: putting a comonomer and water into a reaction container, adding styrene, heating to 65 ℃ under the protection of nitrogen, and dropwise adding an initiator aqueous solution to react to obtain a cationic polystyrene emulsion;
step S2: preparing a core-shell structure microsphere emulsion of silicon dioxide coated polystyrene: and (4) taking the cationic polystyrene emulsion prepared in the step (S1) as a hard template, mixing the hard template with a solvent, stirring at 20 ℃, adding a silicon source substance, and reacting to obtain the polystyrene nano core-shell structure microsphere emulsion coated with silicon dioxide.
In the step S1, the comonomer is an amino group-containing vinyl monomer; the vinyl monomer containing amino is dimethylaminoethyl (meth) acrylate. And protonating the amino group-containing vinyl monomer with an acid, wherein the acid is an inorganic acid, the inorganic acid is hydrochloric acid, and the molar ratio of the acid to the amino group contained in the amino group-containing vinyl monomer is 50% in terms of monobasic acid.
In the step S1, the mass ratios of the comonomer, the styrene, the initiator and the water in the whole system are respectively as follows: 1% of comonomer, 12% of styrene, 0.3% of initiator and 78% of water.
In the step S1, after styrene was added, stirring was performed at a stirring speed of 200 rpm.
In the step S1, the initiator is azobisisobutylamidine hydrochloride; the dropping speed of the initiator added dropwise was 0.5 mL/min.
In step S2, the silicon source is methyltrimethoxysilane.
In the step S2, the solvent is used in an amount to dilute the cationic polystyrene emulsion to a solid content of 5%.
In step S2, the mass ratio of the solid mass of the polystyrene emulsion to the amount of the silicon source material added was 15%.
In step S2, the solvent is n-propanol.
The hydroxyl-containing silicon-aluminum sol raw material is obtained by reacting raw materials containing water, an acidic catalyst, a solvent, an aluminum salt and a silicon source substance, wherein the mass of the aluminum salt is 0.05g, the content of the solvent is 5mL, the content of the water is 0.3mL, and the content of the catalyst is 0.03mL relative to 1mL of the volume of the silicon source substance.
The catalyst is nitric acid; the silicon source material is methyl trimethoxy silane; the aluminum salt is aluminum acetylacetonate; the solvent is isopropanol.
The thickness of the top anti-reflection coating layer 3 is 120nm, and the thickness of the bottom anti-reflection coating layer 2 is 80 nm; the refractive index of the top anti-reflection coating layer 3 is 1.25, and the refractive index of the bottom anti-reflection coating layer 2 is 1.40.
The preparation method of the weather-resistant double-layer high anti-reflection coated glass comprises the following steps:
step A: coating the bottom layer antireflection coating liquid on the upper surface of the glass substrate 1, and then carrying out primary curing to obtain the glass substrate 1 coated with the bottom layer antireflection coating;
and B, step B: and (D) coating the top anti-reflection coating liquid on the upper surface of the bottom anti-reflection coating prepared in the step (A), then carrying out secondary curing, and then carrying out toughening treatment to prepare the weather-proof double-layer high anti-reflection coated glass.
In the step A, the curing temperature of the first curing is 100 ℃, and the curing time is 4 min; in the step B, the curing temperature of the second curing is 120 ℃, and the temperature of the toughening treatment is 550 ℃.
Example 3
Referring to the attached drawing 1, the weather-resistant double-layer high anti-reflection coated glass comprises a glass substrate 1, a bottom anti-reflection coated layer 2 arranged on the upper surface of the glass substrate 1 and a top anti-reflection coated layer 3 arranged on the upper surface of the bottom anti-reflection coated layer 2, wherein the top anti-reflection coated layer 3 is made of top anti-reflection coated liquid, the bottom anti-reflection coated layer 2 is made of bottom anti-reflection coated liquid, and the bottom anti-reflection coated liquid comprises the following raw materials in parts by weight:
the silane coupling agent is methyl trimethoxy silane.
The surfactant is a cationic surfactant, and the cationic surfactant is cetyl trimethyl ammonium bromide.
The cationic silica sol is selected from the Levasil CT16PCL type cationic silica sol from NOURYON company.
The epoxy silane oligomer is Michael CoatOSil MP 200.
The silica prepolymer is prepared by the following steps:
according to the weight portion, 52 portions of ethyl silicate 40, 60 portions of isopropanol, 1 portion of glacial acetic acid and 18 portions of water are uniformly mixed, hydrolyzed for 48 hours at normal temperature, heated to 80 ℃ for reaction for 2 hours, and cooled to room temperature to prepare the silicon dioxide prepolymer.
The preparation method of the bottom layer antireflection coating liquid comprises the following steps:
uniformly mixing silicon dioxide prepolymer, silane coupling agent, isopropanol, cationic silica sol, surfactant and propylene glycol butyl ether according to parts by weight, releasing heat in the reaction process, heating the reaction system to 50 ℃, and then standing for 2 hours and naturally cooling to normal temperature; and adding epoxy silane oligomer, uniformly mixing to obtain a mixture, and finally diluting with isopropanol until the solid content of the mixture is 6% to prepare the bottom layer anti-reflection coating liquid.
The top layer anti-reflection coating liquid passes through SiO containing nano core shell2The microspheres and the hydroxyl-containing silicon-aluminum sol raw material are compounded in a volume ratio of 1:5 to obtain the nano core-shell SiO2The microsphere is prepared by the following steps:
step S1: preparing a polystyrene core by a soap-free emulsion polymerization method: placing a comonomer and water in a reaction vessel, adding styrene, heating to 75 ℃ under the protection of nitrogen, and dropwise adding an initiator aqueous solution to react to obtain a cationic polystyrene emulsion;
step S2: preparing a core-shell structure microsphere emulsion of silicon dioxide coated polystyrene: and (4) taking the cationic polystyrene emulsion prepared in the step (S1) as a hard template, mixing the hard template with a solvent, stirring at 25 ℃, adding a silicon source substance, and reacting to obtain the polystyrene nano core-shell structure microsphere emulsion coated with silicon dioxide.
In the step S1, the comonomer is a quaternized vinyl monomer; the quaternized vinyl monomer is methacryloyloxyethyl trimethyl ammonium chloride.
In the step S1, the mass ratios of the comonomer, the styrene, the initiator and the water in the whole system are respectively as follows: 2% of comonomer, 15% of styrene, 0.5% of initiator and 82% of water.
In the step S1, after styrene was added, stirring was performed at a stirring speed of 300 rpm.
In the step S1, the initiator is potassium persulfate; the dropping speed of the initiator added dropwise was 1 mL/min.
In step S2, the silicon source is vinyltrimethoxysilane.
In the step S2, the solvent is used in an amount to dilute the cationic polystyrene emulsion to a solid content of 10%.
In step S2, the mass ratio of the solid mass of the polystyrene emulsion to the amount of the silicon source material added is 20%.
In the step S2, the solvent is ethylene glycol monomethyl ether.
The hydroxyl-containing silicon-aluminum sol raw material is obtained by reacting raw materials containing water, an acidic catalyst, a solvent, an aluminum salt and a silicon source substance, wherein the mass of the aluminum salt is 0.06g, the content of the solvent is 10mL, the content of the water is 0.5mL, and the content of the catalyst is 0.05mL relative to 1mL of the volume of the silicon source substance.
The catalyst is sulfuric acid; the silicon source material is vinyl trimethoxy silane; the aluminum salt is aluminum nitrate; the solvent is ethylene glycol monomethyl ether.
The thickness of the top anti-reflection coating layer 3 is 150nm, and the thickness of the bottom anti-reflection coating layer 2 is 120 nm; the refractive index of the top anti-reflection coating layer 3 is 1.20, and the refractive index of the bottom anti-reflection coating layer 2 is 1.35.
The preparation method of the weather-resistant double-layer high anti-reflection coated glass comprises the following steps:
step A: coating the bottom layer antireflection coating liquid on the upper surface of the glass substrate 1, and then carrying out primary curing to obtain the glass substrate 1 coated with the bottom layer antireflection coating;
and B: and (D) coating the top anti-reflection coating liquid on the upper surface of the bottom anti-reflection coating prepared in the step (A), then carrying out secondary curing, and then carrying out toughening treatment to prepare the weather-proof double-layer high anti-reflection coated glass.
In the step A, the curing temperature of the first curing is 150 ℃, and the curing time is 3 min; in the step B, the curing temperature of the second curing is 180 ℃, and the temperature of the toughening treatment is 600 ℃.
Example 4
Referring to the attached drawing 1, the weather-resistant double-layer high anti-reflection coated glass comprises a glass substrate 1, a bottom anti-reflection coated layer 2 arranged on the upper surface of the glass substrate 1 and a top anti-reflection coated layer 3 arranged on the upper surface of the bottom anti-reflection coated layer 2, wherein the top anti-reflection coated layer 3 is made of top anti-reflection coated liquid, the bottom anti-reflection coated layer 2 is made of bottom anti-reflection coated liquid, and the bottom anti-reflection coated liquid comprises the following raw materials in parts by weight:
the silane coupling agent is 3-mercaptopropyltriethoxysilane.
The surfactant is a cationic surfactant, and the cationic surfactant is cetyl trimethyl ammonium bromide.
The cationic silica sol is selected from Levasil CT18PCL type cationic silica sol from NOURYON company.
The epoxy silane oligomer is PU118 of Guangzhou Yangsong trade company Limited.
The silica prepolymer is prepared by the following steps:
according to the weight parts, 53 parts of ethyl silicate 40, 63 parts of isopropanol, 1.5 parts of glacial acetic acid and 19 parts of water are uniformly mixed, hydrolyzed at normal temperature for 45 hours, heated to 83 ℃ for reaction for 1.8 hours, and cooled to room temperature to obtain the silicon dioxide prepolymer.
The preparation method of the bottom layer antireflection coating liquid comprises the following steps:
uniformly mixing the silicon dioxide prepolymer, the silane coupling agent, the isopropanol, the cationic silica sol, the surfactant and the propylene glycol butyl ether according to the parts by weight, releasing heat in the reaction process, heating a reaction system to 53 ℃, and then standing for 1.5 hours and naturally cooling to the normal temperature; and adding an epoxy silane oligomer, uniformly mixing to obtain a mixture, and finally diluting with isopropanol until the solid content of the mixture is 8% to prepare the bottom anti-reflection coating liquid.
The top layer anti-reflection coating liquid passes through SiO containing nano core shell2The microspheres and the hydroxyl-containing silicon-aluminum sol raw material are compounded in a volume ratio of 1:8, wherein the nano core-shell SiO is2The microsphere is prepared by the following steps:
step S1: preparing a polystyrene core by a soap-free emulsion polymerization method: putting a comonomer and water into a reaction container, adding styrene, heating to 80 ℃ under the protection of nitrogen, and dropwise adding an initiator aqueous solution to react to obtain a cationic polystyrene emulsion;
step S2: preparing a core-shell structure microsphere emulsion of silicon dioxide coated polystyrene: and (4) taking the cationic polystyrene emulsion prepared in the step (S1) as a hard template, mixing the hard template with a solvent, adding a silicon source substance under stirring at 30 ℃ for reaction, and obtaining the polystyrene nano core-shell structure microsphere emulsion coated with silicon dioxide.
In the step S1, the comonomer is an amino group-containing vinyl monomer; the vinyl monomer containing amino is diisopropylaminoethyl (meth) acrylate. And protonating the amino group-containing vinyl monomer with an acid, which is an organic acid, and the organic acid is acetic acid, before performing step S1.
In the step S1, the mass ratios of the comonomer, the styrene, the initiator and the water in the whole system are respectively as follows: 3% of comonomer, 18% of styrene, 0.8% of initiator and 85% of water.
In the step S1, after styrene was added, stirring was performed at a stirring speed of 400 rpm.
In the step S1, the initiator is potassium persulfate; the dropping speed of the initiator added dropwise was 1.5 mL/min.
In the step S2, the silicon source substance is γ -mercaptopropyl-trimethoxysilane.
In the step S2, the solvent is used in an amount to dilute the cationic polystyrene emulsion to a solid content of 15%.
In step S2, the mass ratio of the solid mass of the polystyrene emulsion to the amount of the silicon source material added is 25%.
In the step S2, the solvent is tripropylene glycol monomethyl ether.
The hydroxyl-containing silicon-aluminum sol raw material is obtained by reacting raw materials containing water, an acidic catalyst, a solvent, an aluminum salt and a silicon source substance, wherein the mass of the aluminum salt is 0.085g, the content of the solvent is 15mL, the content of the water is 0.7mL, and the content of the catalyst is 0.08mL relative to 1mL of the volume of the silicon source substance.
The catalyst is phosphoric acid; the silicon source substance is gamma-mercaptopropyl trimethoxysilane; the aluminum salt is aluminum isopropoxide; the solvent is tripropylene glycol monomethyl ether.
The thickness of the top anti-reflection coating layer 3 is 180nm, and the thickness of the bottom anti-reflection coating layer 2 is 150 nm; the refractive index of the top anti-reflection coating layer 3 is 1.15, and the refractive index of the bottom anti-reflection coating layer 2 is 1.30.
The preparation method of the weather-resistant double-layer high anti-reflection coated glass comprises the following steps:
step A: coating the bottom layer antireflection coating liquid on the upper surface of the glass substrate 1, and then carrying out primary curing to obtain the glass substrate 1 coated with the bottom layer antireflection coating;
and B: and C, coating the top anti-reflection coating liquid on the upper surface of the bottom anti-reflection coating prepared in the step A, curing for the second time, and tempering to prepare the weather-proof double-layer high anti-reflection coated glass.
In the step A, the curing temperature of the first curing is 200 ℃, and the curing time is 2 min; in the step B, the curing temperature of the second curing is 220 ℃, and the tempering temperature is 650 ℃.
Example 5
Referring to the attached drawing 1, the weather-resistant double-layer high anti-reflection coated glass comprises a glass substrate 1, a bottom anti-reflection coated layer 2 arranged on the upper surface of the glass substrate 1 and a top anti-reflection coated layer 3 arranged on the upper surface of the bottom anti-reflection coated layer 2, wherein the top anti-reflection coated layer 3 is made of top anti-reflection coated liquid, the bottom anti-reflection coated layer 2 is made of bottom anti-reflection coated liquid, and the bottom anti-reflection coated liquid comprises the following raw materials in parts by weight:
the silane coupling agent is 3-aminopropyl triethoxysilane.
The surfactant is a cationic surfactant which is didodecyldimethylammonium chloride.
The cationic silica sol is selected from ST-AK type cationic silica sols of Nissan chemical.
The epoxy silane oligomer is Michael CoatOSil MP 200.
The silica prepolymer is prepared by the following steps:
according to the weight portion, 55 portions of ethyl silicate 40, 65 portions of isopropanol, 2 portions of glacial acetic acid and 20 portions of water are uniformly mixed, hydrolyzed for 50 hours at normal temperature, heated to 85 ℃ for reaction for 1.5 hours, and cooled to room temperature to prepare the silicon dioxide prepolymer.
The preparation method of the bottom layer antireflection coating liquid comprises the following steps:
uniformly mixing a silicon dioxide prepolymer, a silane coupling agent, isopropanol, cationic silica sol, a surfactant and propylene glycol butyl ether according to parts by weight, releasing heat in the reaction process, heating the reaction system to 55 ℃, and then standing for 1 hour to naturally cool to the normal temperature; and adding epoxy silane oligomer, uniformly mixing to obtain a mixture, and finally diluting with isopropanol until the solid content of the mixture is 10% to prepare the bottom layer anti-reflection coating liquid.
The top layer anti-reflection coating liquid passes through SiO containing nano core shell2The microspheres and the hydroxyl-containing silicon-aluminum sol raw material are compounded in a volume ratio of 1:10 to obtain the nano core-shell SiO2The microsphere is prepared by the following steps:
step S1: preparing a polystyrene core by a soap-free emulsion polymerization method: putting a comonomer and water into a reaction container, adding styrene, heating to 85 ℃ under the protection of nitrogen, and dropwise adding an initiator aqueous solution to react to obtain a cationic polystyrene emulsion;
step S2: preparing a core-shell structure microsphere emulsion of silicon dioxide coated polystyrene: and (4) taking the cationic polystyrene emulsion prepared in the step (S1) as a hard template, mixing the hard template with a solvent, adding a silicon source substance under stirring at 35 ℃ for reaction, and obtaining the polystyrene nano core-shell structure microsphere emulsion coated with silicon dioxide.
In the step S1, the comonomer is a quaternized vinyl monomer; the quaternized vinyl monomer is diallyl dimethyl ammonium chloride.
In the step S1, the mass ratios of the comonomer, the styrene, the initiator and the water in the whole system are respectively as follows: 4% of comonomer, 20% of styrene, 1% of initiator and 89.4% of water.
In the step S1, after styrene was added, stirring was performed at a stirring speed of 500 rpm.
In the step S1, the initiator is azobisisobutylamidine hydrochloride; the dropping speed of the initiator added dropwise was 2 mL/min.
In step S2, the silicon source is γ - (methacryloyloxy) propyltrimethoxysilane.
In step S2, the solvent is used in an amount to dilute the cationic polystyrene emulsion to a solid content of 20%.
In step S2, the mass ratio of the solid mass of the polystyrene emulsion to the amount of the silicon source material added is 130%.
In the step S2, the solvent is propylene glycol butyl ether.
The hydroxyl-containing silicon-aluminum sol raw material is obtained by the reaction of raw materials containing water, an acidic catalyst, a solvent, an aluminum salt and a silicon source substance, wherein the mass of the aluminum salt is 0.1g, the content of the solvent is 20mL, the content of the water is 1mL, and the content of the catalyst is 0.1mL relative to 1mL of the volume of the silicon source substance.
The catalyst is citric acid; the silicon source substance is gamma- (methacryloyloxy) propyl trimethoxy silane; the aluminum salt is aluminum phosphate, and the solvent is propylene glycol butyl ether.
The thickness of the top anti-reflection coating layer 3 is 200nm, and the thickness of the bottom anti-reflection coating layer 2 is 200 nm; the refractive index of the top anti-reflection coating layer 3 is 1.10, and the refractive index of the bottom anti-reflection coating layer 2 is 1.25.
The preparation method of the weather-resistant double-layer high anti-reflection coated glass comprises the following steps:
step A: coating the bottom layer antireflection coating liquid on the upper surface of the glass substrate 1, and then carrying out primary curing to obtain the glass substrate 1 coated with the bottom layer antireflection coating;
and B: and C, coating the top anti-reflection coating liquid on the upper surface of the bottom anti-reflection coating prepared in the step A, curing for the second time, and tempering to prepare the weather-proof double-layer high anti-reflection coated glass.
In the step A, the curing temperature of the first curing is 250 ℃, and the curing time is 1 min; in the step B, the curing temperature of the second curing is 250 ℃, and the temperature of the toughening treatment is 700 ℃.
Comparative example 1
Double-layer composite SiO2The preparation method of the antireflection film comprises the following steps:
step 2, adding a silicon source into a mixed solution of absolute ethyl alcohol, ammonia water and water according to a certain molar ratio, stirring uniformly at room temperature, standing for several days to obtain base-catalyzed SiO2Sol B; wherein the mass percentage concentration of the SiO2 sol B is 3%;
step 3, taking the required amount of SiO prepared in the step 12Removing acid from the sol A to obtain SiO2Sol a 1; taking the required amount of SiO prepared in the step 22Removing ammonia from the sol B to obtain SiO2Sol B1;
step 4, SiO2Sol A1 and SiO2Mixing the sol B according to the mass ratio of 1: 4, and mixing SiO2Sol A and SiO2Mixing the sol B1 according to the mass ratio of 2: 3, uniformly stirring, standing for several days to respectively obtain composite sol S-20% and composite sol S-40%;
step 5, immersing the pretreated substrate into the composite sol S-40% in the step 4 in an environment with the relative humidity less than 50%, and coating a film on the substrate by adopting a dip-coating method, wherein the coating speed is 80 mm/min; standing the coated substrate for several minutes after pulling, immersing the substrate into the S-20% of the composite sol obtained in the step (4), and coating at a pulling speed of 40 mm/min;
step 6, the substrate plated with the double-layer film in the step 5 is placed in HMDS atmosphere for treatment for a period of time to obtain the required double-layer composite SiO2An antireflection film.
In the step 1 and the step 2, the silicon source is tetraethoxysilane.
In the step 1, the mixing molar ratio of the silicon source, the absolute ethyl alcohol, the hydrochloric acid and the water is 1: 40: 0.04: 4.
In the step 1, the mass percentage concentration of the hydrochloric acid is 37%.
In the step 2, the mixing molar ratio of the silicon source, the absolute ethyl alcohol, the ammonia water and the water is 1: 37.6: 0.17: 3.25.
In the step 2, the mass percentage concentration of the ammonia water is 26%.
In the step 5, the substrate is any one of a silicon wafer, a K9 glass substrate, fused quartz or common glass.
In the step 5, the pretreatment of the substrate refers to that the substrate is put into washing liquor to be fully washed, then is fully cleaned by absolute ethyl alcohol and deionized water through ultrasonic waves respectively, and then is dried by nitrogen.
The anti-reflection coated glass prepared in the example 3 and the anti-reflection coated glass prepared in the comparative example 1 are respectively subjected to a salt spray test and a wet freezing test, and the salt spray test results are as follows:
wherein Y represents the light transmittance and T represents the simulated conversion efficiency.
The results of the freeze-thaw test are shown below:
wherein Y represents the light transmittance and T represents the simulated conversion efficiency.
The data show that the weather-proof double-layer high anti-reflection coated glass prepared by the invention has high anti-reflection rate, the anti-reflection rate can reach 2.5-2.7%, and the broadband anti-reflection is realized within the range of 380-; the salt spray resistance can reach more than 1440h (96 h in national standard), is 15 times higher than the national standard, the wet freezing resistance can reach more than 2400h (240 h in national standard), is 10 times higher than the national standard, and therefore, the weather-resistant paint can be used for a long time in complex climate environments such as high temperature, high humidity and the like, and is strong in weather resistance; and the top layer is a core-shell hollow porous structure, the surface of the membrane layer is closed, and the anti-contamination property is excellent.
The above-described embodiments are preferred implementations of the present invention, and the present invention may be implemented in other ways without departing from the spirit of the present invention.
Claims (9)
1. A weather-resistant double-layer high anti-reflection coated glass is characterized in that: the glass substrate comprises a glass substrate, a bottom anti-reflection coating layer arranged on the upper surface of the glass substrate and a top anti-reflection coating layer arranged on the upper surface of the bottom anti-reflection coating layer, wherein the top anti-reflection coating layer is made of top anti-reflection coating liquid, the bottom anti-reflection coating layer is made of bottom anti-reflection coating liquid, and the bottom anti-reflection coating liquid comprises the following raw materials in parts by weight:
25-35 parts of silicon dioxide prepolymer
15-25 parts of silane coupling agent
15-20 parts of isopropanol
20-30 parts of cationic silica sol
1-2 parts of surfactant
4-8 parts of propylene glycol butyl ether
1-10 parts of epoxy silane oligomer;
the cationic silica sol is acidic silica sol which is obtained by treating the surfaces of silica sol particles with aluminum compounds, and the epoxy silane oligomer is an organic silicon oligomer containing epoxy functional groups.
2. The weather-resistant double-layer high anti-reflection coated glass according to claim 1, which is characterized in that: the silane coupling agent is at least one of methyltrimethoxysilane, 3-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane and 3-mercaptopropyltriethoxysilane.
3. The weather-resistant double-layer high anti-reflection coated glass according to claim 1, which is characterized in that: the surfactant is a cationic surfactant, and the cationic surfactant is at least one of cetyl trimethyl ammonium bromide, dodecyl benzyl dimethyl ammonium chloride and didodecyl dimethyl ammonium chloride.
4. The weather-resistant double-layer high anti-reflection coated glass according to claim 1, which is characterized in that: the pH value of the cation silica sol is 2-4, and the particle size is 10-30 nm.
5. The weather-resistant double-layer high anti-reflection coated glass according to claim 1, which is characterized in that: the silica prepolymer is prepared by the following steps:
according to the weight portion, 50-55 portions of ethyl silicate 40, 55-65 portions of isopropanol, 0.5-2 portions of glacial acetic acid and 15-20 portions of water are uniformly mixed, hydrolyzed for 40-50h at normal temperature, heated to 75-85 ℃ for reaction for 1.5-2.5h, and cooled to room temperature to prepare the silicon dioxide prepolymer.
6. The weather-resistant double-layer high anti-reflection coated glass according to claim 1, which is characterized in that: the preparation method of the bottom layer antireflection coating liquid comprises the following steps:
uniformly mixing the silicon dioxide prepolymer, the silane coupling agent, the isopropanol, the cationic silica sol, the surfactant and the propylene glycol butyl ether according to the parts by weight, releasing heat in the reaction process, heating a reaction system to 45-55 ℃, and then standing for 1-2 hours to naturally cool to the normal temperature; then adding epoxy silane oligomer, mixing uniformly to obtain a mixture, and finally diluting with isopropanol until the solid content of the mixture is 3-10% to prepare the bottom layer anti-reflection coating liquid.
7. The weather-resistant double-layer high anti-reflection coated glass as claimed in claim 1, which is characterized in that: the thickness of the top anti-reflection coating layer is 80-200nm, and the thickness of the bottom anti-reflection coating layer is 50-200 nm; the refractive index of the top anti-reflection coating layer is 1.10-1.30, and the refractive index of the bottom anti-reflection coating layer is 1.25-1.45.
8. A method for preparing the weather-resistant double-layer high anti-reflection coated glass as claimed in any one of claims 1 to 7, which is characterized in that: the method comprises the following steps:
step A: coating the bottom layer antireflection coating liquid on the upper surface of the glass substrate, and then carrying out primary curing to obtain the glass substrate coated with the bottom layer antireflection coating;
and B: and C, coating the top anti-reflection coating liquid on the upper surface of the bottom anti-reflection coating prepared in the step A, curing for the second time, and tempering to prepare the weather-proof double-layer high anti-reflection coated glass.
9. The preparation method of the weather-resistant double-layer high anti-reflection coated glass according to claim 8, characterized in that: in the step A, the curing temperature of the first curing is 60-250 ℃, and the curing time is 1-5 min; in the step B, the curing temperature of the second curing is 80-250 ℃, and the tempering temperature is 500-700 ℃.
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| CN112919821A (en) * | 2021-02-09 | 2021-06-08 | 信义光伏产业(安徽)控股有限公司 | AR coating liquid, coated glass and preparation method thereof |
| CN114804646B (en) * | 2021-05-27 | 2024-02-06 | 吴江南玻玻璃有限公司 | Preparation method of anti-reflection coating liquid |
| CN114196321B (en) * | 2021-05-27 | 2022-08-26 | 吴江南玻玻璃有限公司 | Preparation method of antireflection coating liquid for double-layer coating |
| CN114620950B (en) * | 2022-03-23 | 2023-09-29 | 东莞南玻太阳能玻璃有限公司 | High-hardness high-reflection-resistance double-layer antireflection film glass and preparation method thereof |
| CN114933820B (en) * | 2022-04-12 | 2023-05-09 | 东莞南玻太阳能玻璃有限公司 | High-weather-resistance coating film and preparation method and application thereof |
| CN115818973A (en) * | 2022-12-02 | 2023-03-21 | 中建材玻璃新材料研究院集团有限公司 | Monolayer aluminum phosphate antireflection film in visible light band and preparation method thereof |
| CN116081957B (en) * | 2022-12-15 | 2024-04-16 | 中建材玻璃新材料研究院集团有限公司 | Porous film and preparation method and application thereof |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4792732B2 (en) * | 2004-11-18 | 2011-10-12 | 株式会社日立製作所 | Antireflection film, optical component using antireflection film, and image display device using antireflection film |
| KR101021659B1 (en) * | 2009-12-07 | 2011-03-17 | 주식회사 에이치와이티씨 | Method for producing solar collector module coating solution |
| CN102531406B (en) * | 2012-01-17 | 2015-03-25 | 信义玻璃工程（东莞）有限公司 | Antireflective coating solution and preparation method thereof, as well as photovoltaic glass and preparation method of photovoltaic glass |
| CN102924984A (en) * | 2012-09-29 | 2013-02-13 | 彩虹集团公司 | Preparation method of high-transmittance nano coating sol |
| JP6008739B2 (en) * | 2012-12-27 | 2016-10-19 | 日揮触媒化成株式会社 | Substrate with water-repellent transparent coating and method for producing the same |
| KR101758420B1 (en) * | 2013-11-28 | 2017-07-14 | 제일모직주식회사 | Adhesive composition, adhesive film prepared using the same and optical display apparatus comprising the same |
| CN106277825B (en) * | 2015-05-12 | 2019-02-22 | 河南安彩高科股份有限公司 | A kind of glass baseplate and preparation method thereof containing silicon dioxide antireflective film layer |
| CN105440742B (en) * | 2015-06-09 | 2018-08-07 | 东莞南玻太阳能玻璃有限公司 | Low-cost silicon colloidal sol is anti-reflection anti-reflection coating liquid and its preparation and application |
| CN105504905B (en) * | 2016-02-03 | 2018-07-03 | 广州希森美克新材料科技有限公司 | A kind of high abrasion clear dope of metal surface |
| CN105964195B (en) * | 2016-05-06 | 2019-01-11 | 东莞南玻太阳能玻璃有限公司 | Nano core-shell silicon dioxide microsphere and anti-reflection anti-reflection Composite Coatings film liquid application and preparation |
| CN106966606A (en) * | 2017-03-10 | 2017-07-21 | 江苏好的节能光电科技有限公司 | A kind of preparation method of solar energy glass surface anti-reflection film |
| CN109694594B (en) * | 2018-11-14 | 2021-01-01 | 东莞南玻太阳能玻璃有限公司 | High-anti-reflection smudge-resistant antireflection coating liquid, preparation method thereof and solar photovoltaic cell packaging glass |
-
2020
- 2020-04-29 CN CN202010356629.5A patent/CN111362589B/en active Active
Non-Patent Citations (2)
| Title |
|---|
| Mesoporous silica hybrids as an antireflective coating to enhance light harvesting and achieve over 16% efficiency of organic solar cells;Yalun Wang et al;《Journal of Materials Chemistry C》;20191221;第7卷(第47期);第14962-14969页 * |
| Stability of anti-reflection coatings via the self-assembly encapsulation of silica nanoparticles by diazo-resins;Jonathan S.Metzman et al;《Journal of Physics and Chemistry of Solids》;20150908;第87卷;第271-277页 * |
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