CN114196321B - Preparation method of antireflection coating liquid for double-layer coating - Google Patents
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Abstract
The invention discloses a preparation method of an antireflection coating liquid for double-layer coating, which comprises the following steps: 1) stirring the silane polymer and the solvent in proportion until the materials are uniformly mixed to obtain a bottom layer coating liquid; the bottom layer coating liquid comprises 20-40 parts of silane polymer and 50-80 parts of solvent; 2) uniformly stirring and mixing the silica sol, the solvent and the nano microspheres to obtain a surface coating solution; the surface coating liquid comprises 20-30 parts of silica sol, 5-10 parts of nano microspheres and 45-75 parts of solvent; the silica sol is prepared from a silicon source by adopting a sol-gel method under the condition of an acidic catalyst, and the nano-microspheres are prepared by an emulsion polymerization method. According to the preparation method of the antireflection coating liquid, the mass ratio of the silica sol to the nano microspheres is controlled, so that the porosity of the film layer of the photovoltaic coated glass obtained by the double-layer coating liquid is moderate, and the film layer is ensured to have higher anti-reflection performance and weather resistance.
Description
The application is a divisional application of an invention patent application with the application date of 2021, 5 and 27, and the application number of 2021105877984, wherein the invention is entitled "antireflective coating liquid suitable for double-layer coating and a preparation method and application thereof".
Technical Field
The invention relates to the technical field of coating liquid, in particular to a preparation method of antireflection coating liquid suitable for double-layer coating.
Background
With rapid development of economy and aggravation of energy consumption and environmental problems, development and use of green energy become hot spots, and solar energy has huge development potential and broad development prospect and is concerned.
The photoelectric effect of the solar cell can convert light energy into electric energy, and thus it is important to improve the conversion efficiency. Besides the crystal silicon technology, the photovoltaic glass used as the photovoltaic module cover plate is also one of important factors influencing the conversion efficiency, and the generated power of the module can be effectively improved by improving the light transmittance of the photovoltaic glass.
The surface of the photovoltaic glass is plated with the antireflection film, the light transmittance of the photovoltaic glass can be improved by about 2.3% on the premise of ensuring weather resistance and dirt resistance by using the interference effect of light, but the single-layer film only has a good antireflection effect on light with a specific wavelength and in a nearby narrow band, and the residual reflection is relatively high. The method for performing double-layer or multi-layer coating on the surface of the photovoltaic glass by adopting the method with gradually changed refractive index can realize higher anti-reflection in a wide waveband range, has a more gentle light transmittance curve and has better optical performance than a single-layer coating.
For example, chinese patent 201610333647.5 provides a method for preparing a high-strength double-layer antireflection film, which comprises preparing a high-refractive-index titania sol and a low-refractive-index silica sol, respectively, plating a high-refractive-index titania sol on the surface of a photovoltaic glass to form a titania film, and plating a silica film on the surface of the titania film, although the method produces a double-layer SiO film 2 -TiO 2 The antireflection film is simple in process, can improve the absorption of ultraviolet light, but can inhibit the light transmittance of infrared light, influence the generated power of the photovoltaic module and cause a proper and opposite effect.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide an improved preparation method of an antireflection coating solution, two different prepared antireflection solutions can be used for successively coating a film on the surface of photovoltaic glass to form a highly antireflection coating layer, and the absorption of ultraviolet light and infrared light can be improved at the same time.
The invention adopts the following technical scheme:
an antireflection coating liquid suitable for double-layer coating comprises a bottom layer coating liquid and a surface layer coating liquid, wherein the bottom layer coating liquid comprises 20-40 parts by weight of silane polymer and 50-80 parts by weight of solvent, and the surface layer coating liquid comprises 20-30 parts by weight of silica sol, 5-10 parts by weight of nano microspheres and 45-75 parts by weight of solvent; the nano-microspheres are prepared by an emulsion polymerization method; the average grain diameter of the microspheres in the nano microspheres is less than or equal to 100 nm.
The bottom layer coating liquid is directly coated on the photovoltaic glass substrate, the bottom layer coating liquid is solidified to form a film on the photovoltaic glass, the surface layer coating liquid is coated on the surface of the bottom layer film, and a double-layer antireflection film layer is formed on the surface of the glass after solidification and toughening treatment.
The preparation method of the bottom layer coating liquid comprises the following steps: adding the silane polymer and the solvent into a container according to a certain proportion, and stirring until the materials are uniformly mixed.
The preparation method of the surface layer coating liquid comprises the following steps: adding the silica sol, the solvent and the nano microspheres into a container, stirring, uniformly mixing the materials, and discharging. The silica sol is a reticular silica-oxygen-silicon structure with a large number of active hydroxyl groups formed by silane under an acid catalyst, and the nano-microspheres are prepared by an emulsion polymerization method and provide a moderate pore structure for a final film layer.
The solvent in the bottom layer coating liquid and the surface layer coating liquid can be selected from one or a composition of more than two of methanol, ethanol, isopropanol, ethylene glycol, propylene glycol, n-butanol, isobutanol, n-pentanol, isoamylol, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol methyl ether acetate and ethylene glycol methyl ether acetate. The solvents in the bottom layer coating liquid and the surface layer coating liquid are the same or different.
The bottom antireflection film is formed by coating a film on the surface of a glass substrate by a bottom layer coating liquid and curing, the structure of a bottom layer film layer is compact, a silane polymer is used as a core film forming substance, a silicon-oxygen-silicon network structure containing a large number of-OH and other active groups is formed by silane hydrolytic condensation under the condition of acid catalysis, good adhesion between the bottom layer film layer and the glass substrate and between the bottom layer film layer and a surface layer film layer are ensured, and the film layer is not easy to fall off. The bottom layer is formed by a silane polymer, a pore-forming agent is not added, the structure is compact, no pore is formed, the refractive index is high, and the improvement of the light transmittance of the double-layer coating film is facilitated. The surface antireflection film layer is a film layer which is formed on the surface of the bottom antireflection film layer, and the bottom layer structure is compact, the surface is closed, and the porosity in the surface layer is moderate after the double-layer film is coated, cured and tempered. The method is realized by controlling the porosity of the film layer, the bottom film layer is compact and has no pores, the refractive index is high, the surface film layer has certain porosity and low refractive index, and the refractive index of glass (1.5) > the refractive index of the bottom film layer > the refractive index of the surface film layer > air (1.0); the double-layer film layer is ensured to have high anti-reflection and good weather resistance within a 380-1100 nm broadband range.
According to some preferred embodiment aspects of the present invention, the raw material of the nano-microsphere includes a reactive monomer, the reactive monomer includes an acrylic substance and a silane substance, and the mass ratio of the acrylic substance to the silane substance in the reactive monomer is 1: 0.1-0.5.
According to some preferred embodiments of the present invention, the acrylic substance is selected from one or two or more of acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, isooctyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, styrene, acrylamide, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate; the silane material is selected from one or two or more of methacryloxypropyltrimethoxysilane, methacryloxypropyltriethoxysilane and vinyltriethoxysilane. The silicon-containing nanoparticles are prepared by adding silane substances into the active monomer and performing block copolymerization, and have the advantages of uniform particle size, rich hydroxyl functional groups on the surface, and good monodispersity and stability.
According to some preferred embodiments of the present invention, the nano-microspheres comprise the following raw material components in parts by weight: 8-18 parts of active monomer, 74-90.6 parts of water, 0.3-2 parts of emulsifier, 0.1-1 part of initiator and 1-5 parts of stabilizer.
According to some preferred embodiments of the present invention, the emulsion polymerization preparation of the nanospheres comprises the following steps: mixing and stirring an active monomer, water, an emulsifier and an initiator for emulsification, heating to 70-90 ℃, carrying out heat preservation reaction, adding a stabilizer, continuing the heat preservation reaction, and obtaining the nano-microsphere after the reaction is finished.
In some embodiments of the present invention, the emulsion polymerization preparation of the nanospheres comprises the steps of: according to the mass percentage, sequentially adding 8-18 parts of active monomer, 74-90.6 parts of water, 0.3-2 parts of emulsifier and 0.1-1 part of initiator into a reaction kettle, stirring at a high speed to completely emulsify reaction raw materials, starting heating, reacting at the temperature of 60-90 ℃ for 1-4 hours, then adding 1-5 parts of stabilizer, continuously preserving heat for 0.5-2 hours, and cooling after the reaction is finished.
The initiator comprises one or more of potassium persulfate, ammonium persulfate, sodium persulfate, benzoyl peroxide, azodiisobutyronitrile, azodiisobutyl amidine hydrochloride and the like.
The emulsifier comprises one or more of alkyl sulfate, alkylbenzene sulfonate, polyoxyethylene ether, polyoxypropylene ether, ethylene oxide and propylene oxide block copolymer, polyalcohol fatty acid ester, etc.
The stabilizer comprises one or more of polyvinylpyrrolidone, alkylphenol polyoxyethylene, sodium phosphate, polyethylene glycol, polyvinyl alcohol, hydroxypropyl cellulose and the like.
According to some preferred embodiments of the present invention, the silane polymer in the bottom coating solution comprises the following raw material components in parts by weight: 45-74 parts of solvent, 20-40 parts of silicon source, 6-15 parts of water and 0.001-0.1 part of catalyst.
The silane polymer is prepared by the following method: adding 45-74 parts of isopropanol, 20-40 parts of silicon source, 6-15 parts of water and 0.001-0.1 part of catalyst into a reaction kettle in sequence, stirring, heating to 50-70 ℃ for reaction for 3-5 hours, and cooling to room temperature after the reaction is finished to prepare the silane polymer.
According to some preferred embodiments of the present invention, the silica sol in the surface coating solution is prepared from a silicon source by a sol-gel method under an acidic catalyst.
According to some preferred embodiments of the present invention, the silica sol comprises the following raw material components in parts by weight: 38-65 parts of solvent, 30-47 parts of silicon source, 5-15 parts of water and 0.005-0.1 part of catalyst.
The silica sol is prepared by reacting a silicon source, water, isopropanol and a catalyst. The method mainly comprises the following steps: according to the mass percentage, 38-65 parts of isopropanol, 30-47 parts of silicon source, 5-15 parts of water and 0.005-0.1 part of catalyst are sequentially added into a reaction kettle, stirring and heating are started, the reaction temperature is 50-70 ℃, the reaction time is 3-6 hours, and the reaction is cooled to room temperature after the reaction is finished.
The silicon source in the silane polymer in the bottom layer coating liquid is selected from one or a combination of more of methyl orthosilicate, ethyl orthosilicate, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, dimethyldiethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane and the like. The silicon source in the silica sol in the surface layer coating liquid is one or more of methyl orthosilicate, ethyl orthosilicate, methyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane (KH-560), gamma-methacryloxypropyltrimethoxysilane (KH-570), phenyltrimethoxysilane, phenyltriethoxysilane, etc.
The catalyst in the silane polymer and silica sol is selected from hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, acetic acid, oxalic acid, citric acid, etc. The solvent in the silane polymer and the silica sol is selected from one or a combination of any two or more of methanol, ethanol, isopropanol, ethylene glycol, propylene glycol, n-butanol, isobutanol, n-pentanol, isoamyl alcohol, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol methyl ether acetate and ethylene glycol methyl ether acetate.
The raw material of the bottom layer coating liquid is silane polymer, the raw material of the surface layer coating liquid is silica sol, and the two components have different proportions. The reason is that the bottom film layer plays a role in bonding glass and the surface film layer, and the silane polymer of the bottom coating liquid contains a large amount of active groups so as to ensure the bonding performance of the film layer. The silica sol of the surface layer coating liquid contains a certain amount of active groups, and is chemically bonded with the bottom layer film layer in a curing stage, so that the adhesive force of the film layer is improved, and meanwhile, the silica sol and the nano microspheres interact to finally form a surface layer film layer with an independent pore structure and a closed surface, so that the high light transmittance and intentional dirt resistance and weather resistance of the film layer are ensured. By selecting the silicon source and controlling the proportion of the silicon source, the molar content (20-50%) of hydroxyl in the silane polymer of the bottom layer coating liquid is greater than the molar content (10-30%) of hydroxyl in the silica sol of the surface layer coating liquid, so as to achieve the aim.
The invention also provides a preparation method of the antireflection coating liquid, which comprises the following steps:
1.1) preparation of silane polymers: stirring, mixing and heating silane, a solvent, water and a catalyst for reaction to obtain a silane polymer after the reaction is finished;
1.2) uniformly mixing the silane polymer and a solvent to obtain the bottom layer coating liquid;
2.1) preparation of silica sol: stirring, mixing and heating silane, a solvent, water and a catalyst for reaction to obtain the silica sol after the reaction is finished;
2.2) preparing nano microspheres: mixing and stirring an active monomer, water, an emulsifier and an initiator for emulsification, heating to 70-90 ℃, carrying out heat preservation reaction, adding a stabilizer, continuing the heat preservation reaction, and obtaining the nano-microspheres after the reaction is finished;
2.3) preparing surface layer coating liquid: and uniformly mixing the silica sol and the nano microspheres to obtain the surface coating liquid.
The invention also provides application of the anti-reflection coating liquid in photovoltaic module glass. The antireflection coating liquid is applied to the surface of photovoltaic glass to form a double-layer antireflection coating, the bottom layer is formed by a silane polymer, a pore-forming agent is not added, the structure is compact, no pore is formed, the refractive index is high, and the improvement of the light transmittance of the double-layer coating is facilitated. The surface film layer has a certain porosity and a low refractive index, so that the refractive index of glass is (1.5) > the refractive index of the bottom film > the refractive index of the surface film > air (1.0); the double-layer film layer is ensured to have high anti-reflection and good weather resistance within a 380-1100 nm broadband range.
Due to the adoption of the technical scheme, compared with the prior art, the invention has the following advantages: according to the preparation method of the antireflection coating liquid, the block copolymerization nano microspheres are prepared by adopting an emulsion polymerization method, so that the particle size is controllable, the preparation process is simple, the reaction time is short, and the production efficiency is high; the mass ratio of the silica sol to the nano microspheres is controlled, so that the porosity of the film layer of the photovoltaic coated glass obtained by the double-layer coating liquid is moderate, the film layer is ensured to have higher anti-reflection and weather resistance, the anti-reflection at a wave band of 380-1100 nm reaches 2.60%, the surface of the film layer is sealed, and the photovoltaic coated glass has excellent dirt resistance and weather resistance.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings required to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the description below are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
Fig. 1 is a graph comparing light transmittance curves of an anti-reflection coating film and a single-layer coating film in preferred embodiment 1 of the present invention;
fig. 2 is an SEM picture of a cross section of the antireflection coating film in preferred embodiment 1 of the present invention.
Detailed Description
In order to make those skilled in the art better understand the technical solution of the present invention, the technical solution in the embodiment of the present invention will be clearly and completely described below with reference to the drawings in the embodiment of the present invention, and it is obvious that the described embodiment is only a part of the embodiment of the present invention, and not a whole embodiment. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The invention relates to a broadband high-permeability double-layer coating antireflection coating liquid for photovoltaic glass, wherein a preparation method of a bottom layer coating liquid comprises the following steps:
1) preparing a silane polymer in the bottom layer coating liquid:
1.1) preparation of silane polymers: adding 30 parts of ethyl orthosilicate, 5 parts of methyltriethoxysilane, 60 parts of isopropanol, 13 parts of water and 0.01 part of nitric acid into a reaction kettle in sequence while stirring, starting heating, raising the temperature to 60 ℃, reacting for 4 hours, and cooling for later use after the reaction is finished.
1.2) preparing a bottom layer coating liquid:
according to the mass parts, 25 parts of the silane polymer, 2 parts of propylene glycol methyl ether acetate and 54 parts of isopropanol are added while stirring, and the materials are uniformly mixed by stirring to obtain the bottom layer coating liquid.
2) The preparation method of the surface layer coating liquid comprises the following steps:
2.1) preparation method of silica sol for surface layer coating liquid:
the preparation method of the silica sol comprises the following steps: according to the mass parts, 24 parts of methyl orthosilicate, 13 parts of vinyl triethoxysilane, 47 parts of isopropanol, 11 parts of water and 0.02 part of hydrochloric acid are sequentially added into a reaction kettle under the stirring condition, the temperature is heated to 60 ℃, the reaction is carried out for 4 hours, and the temperature is reduced for standby after the reaction is finished.
2.2) preparation method of nanometer microsphere for surface layer coating liquid:
according to the mass parts, 14 parts of methyl methacrylate, 2.4 parts of vinyl triethoxysilane, 0.6 part of dodecyl amine polyoxyethylene ether, 0.2 part of ammonium persulfate and 82.7 parts of water are added into a reaction kettle, the stirring speed is 200r/min, the reaction raw materials are dissolved and emulsified, the heating is started, the reaction temperature is 75 ℃, the reaction time is 2 hours, then 3 parts of polyvinylpyrrolidone is added, the heat is continuously preserved for 0.5 hour, the temperature is cooled after the reaction is finished, and the material is discharged for later use. The average particle size was 85 nm.
2.3) preparing surface layer coating liquid:
and (2) sequentially adding 22 parts of silica sol, 52 parts of isopropanol, 3 parts of propylene glycol methyl ether acetate and 6 parts of nano microspheres into a container at room temperature while stirring, stirring for about 30min, uniformly mixing the materials, and discharging to obtain the surface coating liquid.
After photovoltaic glass is cleaned, firstly plating a layer of bottom coating liquid on the surface of the glass, after curing and film forming, plating surface coating liquid on the surface of a bottom antireflection film, and after curing and toughening, forming a double-layer antireflection film layer on the surface of the photovoltaic glass. The refractive index of the bottom film layer is 1.35-1.45, and the refractive index of the surface film layer is 1.25-1.32.
Example 2
The invention relates to a broadband high-permeability double-layer coating antireflection coating liquid for photovoltaic glass, wherein a preparation method of a bottom layer coating liquid comprises the following steps:
1) preparing a silane polymer for a bottom layer coating solution:
1.1) preparation of silane polymers: adding 40 parts of tetraethoxysilane, 76 parts of isopropanol, 16 parts of water and 0.05 part of hydrochloric acid into a reaction kettle in sequence while stirring, starting to heat to 50 ℃, reacting for 5 hours, and cooling after the reaction is finished for later use.
1.2) preparing a bottom layer coating liquid:
and (3) adding 30 parts of the silane polymer, 62 parts of isopropanol and 4 parts of propylene glycol butyl ether by mass while stirring, uniformly mixing the materials, and discharging to obtain the bottom layer coating liquid.
2) The preparation method of the surface layer coating liquid comprises the following steps:
2.1) preparation method of silica sol:
the preparation method of the silica sol comprises the following steps: 23 parts of methyl orthosilicate, 15 parts of dimethyl diethoxysilane, 52.59 parts of isopropanol, 9.4 parts of water and 0.01 part of nitric acid are sequentially added into a reaction kettle under the condition of stirring, the temperature is heated to 65 ℃, the reaction is carried out for 4 hours, and the temperature is reduced for standby after the reaction.
2.2) preparation of nano microspheres:
according to the mass percentage, 13 parts of styrene, 3 parts of methacryloxypropyltrimethoxysilane, 1.0 part of sodium dodecyl sulfate, 0.4 part of potassium persulfate and 80.6 parts of water are added into a reaction kettle, the stirring speed is 200r/min, the reaction raw materials are dissolved and emulsified, the heating is started, the reaction temperature is 80 ℃, the reaction time is 3 hours, then 3 parts of polyvinylpyrrolidone is added, the heat preservation is continued for 1 hour, the cooling is carried out after the reaction is finished, and the material is discharged for standby. The particle size was 76 nm.
2.3) preparing surface layer coating liquid:
and (3) sequentially adding 28 parts of silica sol, 69 parts of isopropanol, 3.8 parts of propylene glycol methyl ether and 7.4 parts of nano microspheres into a container according to a proportion while stirring, stirring for about 30min, uniformly mixing the materials, and discharging to obtain the surface coating liquid.
After photovoltaic glass is cleaned, plating a bottom layer coating liquid on the surface of the glass, after the film layer is cured, plating a surface layer coating liquid on the surface of a bottom layer antireflection film, and forming a double-layer antireflection film layer on the surface of the photovoltaic glass after curing and toughening.
Comparative example 1
1.1) the composition and preparation method of the silane polymer in the underlayer coating liquid in the antireflective coating liquid of this comparative example are different from those of example 1, and the others are the same. The preparation of the silane polymer in the bottom layer coating solution of the comparative example: adding 5 parts of ethyl orthosilicate, 30 parts of methyltriethoxysilane, 60 parts of isopropanol, 13 parts of water and 0.01 part of nitric acid into a reaction kettle in sequence while stirring, starting heating, raising the temperature to 60 ℃, reacting for 4 hours, and cooling for later use after the reaction is finished.
In the comparative example, 5 parts of ethyl orthosilicate and 30 parts of methyltriethoxysilane are added to reduce the molar content of hydroxyl in the silane polymer of the bottom layer coating solution.
Comparative example 2
In this comparative example:
1) the bottom layer coating solution is the same as the bottom layer coating solution in example 2;
2) the preparation method of the surface layer coating liquid comprises the following steps:
2.1) the same silica sol as in example 2;
2.2) preparation of nano microspheres:
according to the mass percentage, 20 parts of styrene, 5 parts of methacryloxypropyltrimethoxysilane, 1.0 part of sodium dodecyl sulfate, 0.4 part of potassium persulfate and 70 parts of water are added into a reaction kettle, the stirring speed is 200r/min, the reaction raw materials are dissolved and emulsified, the heating is started, the reaction temperature is 80 ℃, the reaction time is 3 hours, then 3 parts of polyvinylpyrrolidone is added, the heat preservation is continued for 1 hour, the cooling is carried out after the reaction is finished, and the material is discharged for standby. The particle size is 200 nm.
The comparative example has a larger comonomer content, and the particle size of the microspheres gradually increases with the comonomer content during the polymerization reaction. The average particle size of the nanospheres is about 200 nm.
2.3) preparation of surface coating solution the same as example 2.
Comparative example 3
In this comparative example:
1) the bottom layer coating liquid is the same as that in example 1;
2) the preparation method of the surface layer coating liquid comprises the following steps:
2.1) silica Sol the same silica Sol as in example 1
2.2) preparation of the nano-microsphere:
adding 18 parts by mass of methyl methacrylate, 0.6 part by mass of dodecyl amine polyoxyethylene ether, 0.2 part by mass of ammonium persulfate and 82.7 parts by mass of water into a reaction kettle, stirring at a speed of 200r/min to dissolve and emulsify reaction raw materials, starting heating at a reaction temperature of 75 ℃ for 2 hours, then adding 3 parts by mass of polyvinylpyrrolidone, continuing to keep the temperature for 0.5 hour, cooling after the reaction is finished, and discharging for later use. The average particle size was 100 nm.
2.3) preparation of surface coating solution the same as in example 1.
In the comparative example, only acrylic acid monomer and no silane monomer are contained in the monomers of the nano-microsphere.
Example 3
Cleaning photovoltaic glass, plating a layer of bottom coating liquid on the surface of the glass to form a bottom coating layer, curing to form a film, plating a layer of surface coating liquid on the surface of a bottom antireflection film, curing and toughening to form a double-layer antireflection film on the surface of the photovoltaic glass. The anti-reflection, stain-resistant and weather-resistant performance tests of the coated glass show that the results are shown in the following table:
remarking: the stain resistance is divided into 1-5 grades according to the shallow weight of the residual imprints on the membrane surface, and the higher the grade number is, the worse the stain resistance is, the grade is less than or equal to 3, and the grade is qualified.
The test results in the table show that the double-layer coated glass obtained by the antireflection solution prepared by the method has higher light transmittance, excellent dirt resistance and weather resistance; and the light transmittance of the long wave band (infrared) can be obviously improved, namely, the absorption of ultraviolet and infrared light is simultaneously improved, and the light transmittance curve (figure 1) can be seen from the attached figure.
In the prior art, a layer of antireflection film is plated on the surface of photovoltaic glass by utilizing the interference effect of light, a single layer of antireflection film can only realize higher antireflection for specific wavelength and a narrow band range nearby, the residual reflectivity is higher, the antireflection is limited, and the power generation capacity of an assembly is influenced to a certain extent. In order to overcome the defects and shortcomings of the prior art, the invention aims to provide the preparation method of the double-layer high-permeability antireflection coated glass, which is simple in preparation process, high in production efficiency and good in weather resistance. The double-layer antireflection coating liquid of the invention comprises the following components: 1. the refractive indexes of the bottom layer and the surface film layer are matched, the anti-reflection of the double-layer coated glass is higher (the anti-reflection is more than 2.60%) in a wider wave band range, and a light transmittance curve is smoother than that of a single-layer film, so that the power generation power of the assembly is effectively improved as shown in figures 1 and 2; 2. the nano-microspheres for the surface antireflection solution are prepared by an emulsion polymerization method through molecular design, so that the operation is simple and the production efficiency is high; 3. the bottom film layer is compact, the surface of the surface layer is closed, the porosity is moderate, the permeability is high, and the weather resistance and the weathering resistance are good.
The above embodiments are merely illustrative of the technical concept and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the content of the present invention and implement the invention, and not to limit the scope of the invention, and all equivalent changes or modifications made according to the spirit of the present invention should be covered by the scope of the present invention.
Claims (5)
1. A preparation method of an antireflection coating liquid for double-layer coating is characterized by comprising the following steps:
1) stirring the silane polymer and the solvent in proportion until the materials are uniformly mixed to obtain a bottom layer coating liquid; the bottom layer coating liquid comprises 20-40 parts of silane polymer and 50-80 parts of solvent;
2) uniformly stirring and mixing the silica sol, the solvent and the nano microspheres to obtain a surface coating solution; the surface coating liquid comprises 20-30 parts of silica sol, 5-10 parts of nano microspheres and 45-75 parts of solvent;
the silica sol is prepared from a silicon source by adopting a sol-gel method under the condition of an acidic catalyst; the nano-microspheres are prepared by an emulsion polymerization method and are used for providing a pore structure for the film layer;
the molar content of hydroxyl in the silane polymer of the bottom layer coating liquid is greater than that of hydroxyl in the silica sol of the surface layer coating liquid;
the molar content of hydroxyl in the silane polymer of the bottom layer coating liquid is 20-50%, and the molar content of hydroxyl in the silica sol of the surface layer coating liquid is 10-30%;
the nano-microsphere comprises the following raw material components in parts by weight: 8-18 parts of active monomer, 74-90.6 parts of water, 0.3-2 parts of emulsifier, 0.1-1 part of initiator and 1-5 parts of stabilizer;
the raw materials of the nano-microspheres comprise active monomers, the active monomers comprise acrylic substances and silane substances, and the mass ratio of the acrylic substances to the silane substances in the active monomers is 1: 0.1-0.5;
the silane polymer in the bottom layer coating liquid comprises the following raw material components in parts by weight: 45-74 parts of solvent, 20-40 parts of silicon source, 6-15 parts of water and 0.001-0.1 part of catalyst;
the silica sol comprises the following raw material components in parts by weight: 38-65 parts of solvent, 30-47 parts of silicon source, 5-15 parts of water and 0.005-0.1 part of catalyst;
the silicon source in the silane polymer in the bottom layer coating liquid is selected from one or a combination of more of methyl orthosilicate, ethyl orthosilicate, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, dimethyldiethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane and the like;
the silicon source in the silica sol in the surface layer coating liquid is selected from one or more of methyl orthosilicate, ethyl orthosilicate, methyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane and the like.
2. The preparation method of claim 1, wherein the active monomer is 10-20% of the total mass of the nanospheres.
3. The preparation method of claim 1, wherein the emulsion polymerization preparation of the nanospheres comprises the following steps: mixing and stirring an active monomer, water, an emulsifier and an initiator for emulsification, heating to 70-90 ℃, carrying out heat preservation reaction, adding a stabilizer, continuing the heat preservation reaction, and obtaining the nano-microsphere after the reaction is finished.
4. The method according to claim 1, wherein the catalyst in the silane polymer and the silica sol is selected from the group consisting of hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, acetic acid, oxalic acid, and citric acid.
5. The method according to claim 1, wherein the solvent in the silane polymer and the silica sol is selected from one or a combination of two or more of methanol, ethanol, isopropanol, ethylene glycol, propylene glycol, n-butanol, isobutanol, n-pentanol, isoamyl alcohol, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol methyl ether acetate and ethylene glycol methyl ether acetate.
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