CN104669717A - Anti-reflective film and preparation method thereof - Google Patents
Anti-reflective film and preparation method thereof Download PDFInfo
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- CN104669717A CN104669717A CN201310606352.7A CN201310606352A CN104669717A CN 104669717 A CN104669717 A CN 104669717A CN 201310606352 A CN201310606352 A CN 201310606352A CN 104669717 A CN104669717 A CN 104669717A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/554—Wear resistance
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/752—Corrosion inhibitor
Abstract
The invention provides an anti-reflective film including a glass substrate, and a linear silica layer, a hollow silica layer and a composite silicon oxide layer successively coating the surface of the glass substrate; the composite silicon oxide layer is one of a silicon titanium oxide layer, a silicon zirconium oxide layer, a silicon aluminum oxide layer, a silicon titanium zirconium oxide layer, a silicon titanium aluminum oxide layer, a silicon zirconium aluminum oxide layer and a silicon titanium zirconium aluminum oxide layer. The invention also provides a preparation method of the anti-reflective film. The anti-reflective film prepared by an anti-reflective film-plating liquid has high permeability improvement rate, good wear resistance, high pencil hardness and good salt fog performance.
Description
Technical field
The invention belongs to area of solar cell, particularly relate to a kind of antireflective coating and preparation method thereof.
Background technology
At present, along with the fast development of global economy, world energy consumption increases severely, and traditional resource consumption is rapid and day by day rare and exploit difficulty and constantly increase, and makes global energy supply nervous.China is in the rapid economic development stage, and large to the demand of the energy, current oil is externally interdependent more than 50%, and energy supply is seriously nervous.Solar energy is a kind of clean, regenerative resource, is radiated the solar energy of earth surface every year up to 1.7*10
5hundred million kilowatts, be 3.5 ten thousand times of earth total energy consumption, be inexhaustible concerning the mankind, with do not have a rest.
Solar cell is a kind of device sunshine being changed into electric energy, is a kind of reproducible eco-friendly power source.But the utilization rate of current solar cell to sunshine is low, i.e. actual photoelectricity low conversion rate.How to reduce the gap of actual light photoelectric transformation efficiency and theoretical light photoelectric transformation efficiency, the photoelectric transformation efficiency improving solar cell is further still problem anxious to be resolved.
At present, conventional settling mode is that this antireflective coating effectively can reduce the reflection of light, allows more light enter solar battery sheet and is absorbed, thus improves the efficiency of solar cell at glass baseplate surface coating antireflective coating.Antireflecting silicon dioxide film is antireflective coating the most frequently used at present, and antireflecting silicon dioxide film adopts the preparation of following two kinds of methods usually, 1, on substrate, prepare microporous membrane (pore type), and introduce pore-foaming agent and form loose structure, regulate refractive index by porosity; 2, another kind is the film (granular pattern) formed by spherical nanometer silicon dioxide particle, regulates refractive index by spheric granules size.Pore type silica antireflection film is difficult to obtain low refractive index, and the average anti-reflection of coating single side generally only has about 2.5%, and usually because capillary condensation effect makes the light transmittance of film reduce further, the uniformity of anti-reflection film refractive index and poor stability; The performance such as salt spray resistance, rub resistance of granular pattern film is not good.
According to Fresnel equation, the refractive index of glass is that the best that 1.49-1.52. can calculate antireflective coating sets refractive index as 1.23, but the refractive index of silica is 1.45, therefore, in order to make the refractive index of film be reduced to 1.23, film must have certain porosity, but hole makes membrane structure loosen, adhesion reduces, thus easily by outside contamination, and not scratch-resistant and easily coming off.
Publication number is that CN102617045A discloses a kind of silica dioxide antireflection film, comprises photovoltaic glass substrate and is coated in the thick silica nanometer hollow bead layer of the first thick silicon dioxide compact layer of 10-30nm on photovoltaic glass substrate, 50-300nm successively and is filled in the second silicon dioxide compact thing between the silica nanometer hollow bead in silica nanometer hollow bead layer in space; The filling total amount of the second described silicon dioxide compact thing is equal to the amount of silicon dioxide compact thing in the first thick silicon dioxide compact layer of 5-30nm.Combination between antireflection film inside configuration particle prepared by this patent not still defective tightness, and film surface is fine and close and hard not, affects endurance quality energy and the crocking resistance of film.
Summary of the invention
The present invention is the technical problem solving existing antireflective coating salt spray resistance and crocking resistance difference, provides a kind of salt spray resistance and the good antireflective coating liquid of crocking resistance and preparation method thereof.
The invention provides a kind of antireflective coating, described antireflective coating comprises glass substrate and is coated in the linear silicon dioxide layer of glass baseplate surface, hollow silicon dioxide layer and comprehensive silicon oxide skin(coating) successively; Described comprehensive silicon oxide skin(coating) is the one in titanium silicon oxide layer, silicon Zirconium oxide layer, sieve and silica-sesquioxide layer, silicon titanium Zirconium oxide layer, silicon titanium al oxide layer, silicon zirconium al oxide layer and silicon titanium zirconium al oxide layer.
Present invention also offers a kind of preparation method of antireflective coating, the method comprises the steps:
S1, apply linear silica coating liquid on the glass substrate, then dry and obtain linear silicon dioxide layer;
S2, at linear silica surface coating hollow silicon dioxide coating liquid, dry and obtain hollow silicon dioxide layer;
S3, at hollow silicon dioxide layer surface coating silicon dioxide composite film coating liquid, dry and obtain comprehensive silicon oxide skin(coating);
S4, the glass substrate tempering being coated with linear silicon dioxide layer, hollow silicon dioxide layer and comprehensive silicon oxide skin(coating) that step S3 is obtained or solidification process;
Wherein, described hollow silicon dioxide coating liquid comprises hollow silicon dioxide colloidal sol, additive and solvent; Described silica composite film coating liquid comprises at least one in titanium colloidal sol, zirconium colloidal sol and Alumina gel and chain silicon dioxide gel.
Antireflective coating provided by the invention disperses landfill to form in comprehensive silicon oxide by hollow silicon dioxide.This antireflective coating is particularly suitable for cooperative achievement antireflective on photovoltaic glass, weather-proof, the multinomial excellent properties such as salt spray resistance and resistant, improve light utilization efficiency and the service life of photovoltaic cell component, increase the hardness of antireflective coating, make antireflective coating have super hydrophilic interaction and automatic cleaning action.
Detailed description of the invention
In order to make technical problem solved by the invention, technical scheme and beneficial effect clearly understand, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
The invention provides a kind of antireflective coating, described antireflective coating comprises glass substrate and is coated in the linear silicon dioxide layer of glass baseplate surface, hollow silicon dioxide layer and comprehensive silicon oxide skin(coating) successively; Described comprehensive silicon oxide skin(coating) is the one in titanium silicon oxide layer, silicon Zirconium oxide layer, sieve and silica-sesquioxide layer, silicon titanium Zirconium oxide layer, silicon titanium al oxide layer, silicon zirconium al oxide layer and silicon titanium zirconium al oxide layer.
Comprehensive silicon oxide skin(coating) of the present invention is the one in titanium silicon oxide layer, silicon Zirconium oxide layer, sieve and silica-sesquioxide layer, silicon titanium Zirconium oxide layer, silicon titanium al oxide layer, silicon zirconium al oxide layer and silicon titanium zirconium al oxide layer.Also comprehensive silicon oxide skin(coating) can ensure wearability and the hardness of this antireflective coating while the refractive index ensureing antireflective coating.
According to antireflective coating provided by the present invention, preferably, in described comprehensive silicon oxide skin(coating), silicon is counted in titanium dioxide, zirconium base zirconium dioxide in silica, titanium, aluminium is in alundum (Al2O3), the integral molar quantity of described titanium, zirconium and aluminium and the mol ratio of silicon are 1:1-5, and this ratio can ensure that film increases its endurance quality and crocking resistance under having the prerequisite of suitable refractive index.
According to antireflective coating provided by the present invention, in order to improve hardness and the anti-wear performance of antireflective coating further, preferably, described linear silicon dioxide layer is the one in titanium silicon oxide layer, silicon Zirconium oxide layer, sieve and silica-sesquioxide layer, silicon titanium Zirconium oxide layer, silicon titanium al oxide layer, silicon zirconium al oxide layer and silicon titanium zirconium al oxide layer.
According to antireflective coating provided by the present invention, preferably, in described linear silicon dioxide layer, silicon in silica, titanium in titanium dioxide, zirconium in zirconium dioxide, aluminium in alundum (Al2O3), the integral molar quantity of described titanium, zirconium and aluminium and the mol ratio of silicon are 1-3:5, concrete ratio is 1.23 exceed this ratio for the best with film in the refractive index of 550nm optical wavelength, and the refractive index of film will significantly promote, and film does not just have anti-reflection performance.
According to antireflective coating provided by the present invention, preferably, described hollow silicon dioxide layer is in silica, in described linear silicon dioxide layer and described comprehensive silicon oxide skin(coating), silicon is counted in titanium dioxide, zirconium base zirconium dioxide in silica, titanium, aluminium is in alundum (Al2O3), the integral molar quantity of described linear silicon dioxide layer and comprehensive silicon oxide and the mol ratio of hollow silicon dioxide are 1-5:1, and this ratio can ensure that film increases its endurance quality and crocking resistance under having the prerequisite of suitable refractive index.。
According to antireflective coating provided by the present invention, preferably, the thickness of described linear silicon dioxide layer is 5-20nm, and the thickness of described hollow silicon dioxide layer is 20-80nm, and the thickness of described comprehensive silicon oxide skin(coating) is 5-20nm.Described linear silicon dioxide layer is in described thickness range, attachment can be played and connect cushioning effect, described hollow silicon dioxide layer is in described thickness range, the effect reducing film refractive index can be played, described comprehensive silicon oxide skin(coating) is in described thickness range, can until the durability of enhanced film and the effect of rub resistance, and calculate known according to optical knowledge, the desirable gross thickness of anti-reflection film is good at about 100nm, and the optical function that each layer thickness that therefore the present invention limits has considered physical chemistry function sets.
According to antireflective coating provided by the present invention, in order to obtain best refractive index, preferably, the gross thickness of linear silicon dioxide layer, hollow silicon dioxide layer and comprehensive silicon oxide skin(coating) is 80-120nm.
Antireflective coating of the present invention, described titanium silicon oxide layer, silicon Zirconium oxide layer, sieve and silica-sesquioxide layer, silicon titanium Zirconium oxide layer, silicon titanium al oxide layer, silicon zirconium al oxide layer and silicon titanium zirconium al oxide layer all can be mixed to get respectively by titanium colloidal sol, zirconium colloidal sol and Alumina gel and silicon dioxide gel.
The chain hydrolysate colloidal sol that described silicon dioxide gel is formed after referring to esters of silicon acis hydrolysis, sol dispersion is very little, and basic in strand state, colloidal sol clear appearance is transparent.Described titanium colloidal sol, zirconium colloidal sol and Alumina gel can be made by oneself or be commercially available.Homemade described titanium colloidal sol, zirconium colloidal sol and Alumina gel can be obtained by reacting by the catalytic action of acid or alkali and water respectively by the ester type compound of the chlorine oxonium compound of the ester type compound of titanium, zirconium and aluminium.
Described hollow silicon dioxide layer is applied by hollow silicon dioxide colloidal sol to be formed.It is hollow silicon dioxide gel that described hollow silicon dioxide colloidal sol refers to inner, and particle size is tens nanometers, and colloidal sol outward appearance is generally in light blue.Described hollow silicon dioxide colloidal sol can be commercially available.Such as be selected from and wave the methyl ethyl ketone silicon dioxide gel that the particle diameter that catalyst changes into bead commercial firm is 40-50nm, mass fraction is 20% day.
Present invention also offers a kind of preparation method of antireflective coating, the method comprises the steps:
S1, apply linear silica coating liquid on the glass substrate, then dry and obtain linear silicon dioxide layer;
S2, at linear silica surface coating hollow silicon dioxide coating liquid, dry and obtain hollow silicon dioxide layer;
S3, at hollow silicon dioxide layer surface coating silicon dioxide composite film coating liquid, dry and obtain comprehensive silicon oxide skin(coating);
S4, the glass substrate tempering being coated with linear silicon dioxide layer, hollow silicon dioxide layer and comprehensive silicon oxide skin(coating) that step S3 is obtained or solidification process;
Wherein, described hollow silicon dioxide coating liquid comprises hollow silicon dioxide colloidal sol, additive and solvent; Described silica composite film coating liquid comprises at least one in titanium colloidal sol, zirconium colloidal sol and Alumina gel and chain silicon dioxide gel.
In the present invention, described solvent can be water or organic solvent, and described organic solvent is as one or more in methyl alcohol, ethanol, isopropyl alcohol, propylene-glycol ethyl ether, propylene glycol monomethyl ether, ethyl acetate, butyl acetate, ethyl acetate, methyl ethyl ketone.
According to preparation method provided by the present invention, preferably, before step S1, activation process is carried out to glass substrate.The effect of described activation process makes glass substrate more easily by plated film liquid wetting, and make ground and film combine more firm.
According to preparation method provided by the present invention, preferably, described activation process is be dipped in by glass substrate in the mixed liquor of hydrogen peroxide and the concentrated sulfuric acid, then washes away mixed liquor with distilled water, dries up with inert gas.
According to preparation method provided by the present invention, preferably, at least one in titanium colloidal sol, zirconium colloidal sol and Alumina gel is also comprised in described linear silica coating liquid.
According to preparation method provided by the present invention, preferably, described additive is at least one in coalescents, surfactant, thickener and wetting agent.Described additive is not particularly limited, and if coalescents can be polyethylene glycol, glycerine etc., surfactant is organic silicon surfactant, non-ionic surface active agent etc., and thickener is hydroxyethylcellulose, and wetting agent is BYK346 etc.
According to preparation method provided by the present invention, preferably, with the gross mass of described hollow silicon dioxide coating liquid for benchmark, the content of described hollow silicon dioxide is 1-5wt%, and the content of described additive is 0.5-2wt%.
According to preparation method provided by the present invention, preferably, the method for described coating is the one in lift, roller coat, dip-coating, showering and spraying.
According to preparation method provided by the present invention, preferably, the temperature of described oven dry is 20-300 DEG C; Described solidification temperature is 300-500 DEG C, and the time is 30-120min; The temperature of described tempering is 500-700 DEG C, and the time is 2-10min.
Below by specific embodiment, the present invention is described in further detail.
Embodiment is raw materials used:
Silicon dioxide gel: by the nitric acid mix and blend 2h of the water of the ethyl orthosilicate of 10.8 mass parts, 50 mass parts and 0.5 mass parts.
Hollow Nano SiO2 colloidal sol: be selected from and wave the methyl ethyl ketone silicon dioxide gel that the particle diameter that catalyst changes into bead commercial firm is 40-50nm, mass fraction is 20% day.
Titanium colloidal sol: the nitric acid mix and blend of the butyl titanate of 10 weight portions, the water of 100 mass parts and 2 mass parts, ageing 24h at 50 DEG C.
Zirconium colloidal sol: the deionized water taking 200 mass parts, adds the basic zirconium chloride of 100 mass parts under agitation, and regulate pH to be 2.5 with ammoniacal liquor, after stirring at room temperature, ageing is stand-by.
Alumina gel: the nitric acid of the water of 200 mass parts, the aluminium isopropoxide of 20 mass parts and 1 mass parts, reacts 2h at 85 DEG C.
embodiment 1
1) linear silica coating liquid is applied
A () processing substrate: be dipped in by the glass substrate cleaned up in the mixed liquor of hydrogen peroxide and the concentrated sulfuric acid and complete activation process, then dries up with inert gas;
B () linear silica coating liquid: take a certain amount of above-mentioned prefabricated silicon dioxide gel, add water, makes the concentration of silica be 1wt%;
C () applies linear silica coating liquid: spray one deck shape silica coating liquid on the glass substrate, dry, obtain the linear silicon dioxide layer that thickness is 10nm at 200 DEG C of temperature;
2) hollow silicon dioxide coating liquid is applied
(a) preparation hollow silicon dioxide coating liquid: the hollow Nano SiO2 colloidal sol of 10 weight portions (is waved catalyst day and changed into bead commercial firm, 40-50nm, methyl iso-butyl ketone (MIBK) is decentralized medium, solid content 20%), adding water makes the mass fraction of hollow Nano SiO2 be 3%, and then adds the polyethylene glycol of each 1 mass parts, organic silicon surfactant, hydroxyethylcellulose and BYK346 wetting agent;
(b) coating hollow silicon dioxide coating liquid: in step S1) surface of linear silicon dioxide layer that obtains applies one deck hollow silicon dioxide coating liquid, and dry at 100 DEG C of temperature, obtain the hollow silicon dioxide layer that thickness is 90nm;
3) coating silicon dioxide colloidal sol
A () silica composite film coating liquid, is mixed to get coating liquid by silicon dioxide gel, titanium colloidal sol and water, wherein silicon dioxide gel in silica for, described titanium colloidal sol is in titanium dioxide, and the mol ratio of titanium colloidal sol and silicon dioxide gel is 1:5;
B () is in step 2) the surface spraying silica composite film coating liquid of the hollow silicon dioxide layer obtained, dry at 300 DEG C of temperature, obtain the comprehensive silicon oxide skin(coating) that thickness is 10nm;
4) glass substrate through step 3) process is carried out tempering process at 600 DEG C, processing time is 8min, the thickness of the finally obtain first linear SiO2 film is 10nm, the thickness of the second hollow SiO2 nanoparticle layers is 80nm, the thickness of trigram SiO2 film is 10nm, and gross thickness is the antireflection film A1 of 100nm.Hollow silicon dioxide layer is in silica, in linear silicon dioxide layer and comprehensive silicon oxide skin(coating), silicon is counted in titanium dioxide, zirconium base zirconium dioxide in silica, titanium, aluminium in alundum (Al2O3), the integral molar quantity of linear silicon dioxide layer and comprehensive silicon oxide and the mol ratio of hollow silicon dioxide are 1:1.
embodiment 2
Antireflective coating A2 is prepared according to the method for embodiment 1, difference is: the silica composite film coating liquid in step 3) is for be mixed to get coating liquid by silicon dioxide gel, titanium colloidal sol, zirconium colloidal sol, Alumina gel and water, wherein silicon dioxide gel in silica for, described titanium colloidal sol is in titanium dioxide, zirconium colloidal sol is in zirconia, Alumina gel is in alundum (Al2O3), and the integral molar quantity of titanium colloidal sol, zirconium colloidal sol and Alumina gel and the mol ratio of silicon dioxide gel are 1:3; The thickness of the linear silicon dioxide layer finally obtained is 10nm, and the thickness of hollow silicon dioxide layer is 80nm, and the thickness of comprehensive silicon oxide skin(coating) is 15nm, and gross thickness is the antireflective coating of 115nm.Hollow silicon dioxide layer is in silica, in linear silicon dioxide layer and comprehensive silicon oxide skin(coating), silicon is counted in titanium dioxide, zirconium base zirconium dioxide in silica, titanium, aluminium in alundum (Al2O3), the integral molar quantity of linear silicon dioxide layer and comprehensive silicon oxide and the mol ratio of hollow silicon dioxide are 2.1:1.
embodiment 3
Antireflective coating A3 is prepared according to the method for embodiment 1, difference is: the silica composite film coating liquid in step 3) is for be mixed to get coating liquid by silicon dioxide gel, zirconium colloidal sol, Alumina gel and organic solvent, wherein silicon dioxide gel in silica for, described zirconium colloidal sol is in zirconia, Alumina gel is in alundum (Al2O3), and the integral molar quantity of zirconium colloidal sol and Alumina gel and the mol ratio of silicon dioxide gel are 1:4; The thickness of the linear silicon dioxide layer finally obtained is 10nm, and the thickness of hollow silicon dioxide layer is 80nm, and the thickness of comprehensive silicon oxide skin(coating) is 20nm, and gross thickness is the antireflective coating of 120nm.Hollow silicon dioxide layer is in silica, in linear silicon dioxide layer and comprehensive silicon oxide skin(coating), silicon is counted in titanium dioxide, zirconium base zirconium dioxide in silica, titanium, aluminium in alundum (Al2O3), the integral molar quantity of linear silicon dioxide layer and comprehensive silicon oxide and the mol ratio of hollow silicon dioxide are 1.6:1.
embodiment 4
Antireflective coating A4 is prepared according to the method for embodiment 1, difference is: the silica composite film coating liquid in step 3) is for be mixed to get coating liquid by silicon dioxide gel, titanium colloidal sol, zirconium colloidal sol, Alumina gel and water, wherein silicon dioxide gel is in silica, described titanium colloidal sol is in titanium dioxide, zirconium colloidal sol is in zirconia, Alumina gel is in alundum (Al2O3), and the integral molar quantity of titanium colloidal sol, zirconium colloidal sol and Alumina gel and the mol ratio of silicon dioxide gel are 1:2; The thickness of the linear silicon dioxide layer finally obtained is 15nm, and the thickness of hollow silicon dioxide layer is 80nm, and the thickness of comprehensive silicon oxide skin(coating) is 15nm, and gross thickness is the antireflective coating of 120nm.Hollow silicon dioxide layer is in silica, in linear silicon dioxide layer and comprehensive silicon oxide skin(coating), silicon is counted in titanium dioxide, zirconium base zirconium dioxide in silica, titanium, aluminium in alundum (Al2O3), the integral molar quantity of linear silicon dioxide layer and comprehensive silicon oxide and the mol ratio of hollow silicon dioxide are 2.4:1.
embodiment 5
Prepare antireflective coating A5 according to the method for embodiment 1, difference is: also containing titanium colloidal sol, zirconium colloidal sol and Alumina gel in the linear silica coating liquid of step 1); Wherein linear silicon dioxide gel in silica for, described titanium colloidal sol is in titanium dioxide, and zirconium colloidal sol is in zirconia, and Alumina gel is in alundum (Al2O3), and the integral molar quantity of titanium colloidal sol, zirconium colloidal sol and Alumina gel and the mol ratio of silicon dioxide gel are 1:5;
Silica composite film coating liquid in step 3) is for be mixed to get coating liquid by silicon dioxide gel, titanium colloidal sol, zirconium colloidal sol, Alumina gel and water, wherein silicon dioxide gel in silica for, described titanium colloidal sol is in titanium dioxide, zirconium colloidal sol is in zirconia, Alumina gel is in alundum (Al2O3), and the integral molar quantity of titanium colloidal sol, zirconium colloidal sol and Alumina gel and the mol ratio of silicon dioxide gel are 1:1; The thickness of the linear silicon dioxide layer finally obtained is 5nm, and the thickness of hollow silicon dioxide layer is 80nm, and the thickness of comprehensive silicon oxide skin(coating) is 5nm, and gross thickness is the antireflective coating of 90nm.Hollow silicon dioxide layer is in silica, in linear silicon dioxide layer and comprehensive silicon oxide skin(coating), silicon is counted in titanium dioxide, zirconium base zirconium dioxide in silica, titanium, aluminium in alundum (Al2O3), the integral molar quantity of linear silicon dioxide layer and comprehensive silicon oxide and the mol ratio of hollow silicon dioxide are 3:1.
embodiment 6
Prepare antireflective coating A6 according to the method for embodiment 1, difference is: also containing titanium colloidal sol, zirconium colloidal sol and Alumina gel in the linear silica coating liquid of step 1); Wherein linear silicon dioxide gel in silica for, described titanium colloidal sol is in titanium dioxide, and zirconium colloidal sol is in zirconia, and Alumina gel is in alundum (Al2O3), and the integral molar quantity of titanium colloidal sol, zirconium colloidal sol and Alumina gel and the mol ratio of silicon dioxide gel are 3:5;
Silica composite film coating liquid in step 3) is for be mixed to get coating liquid by silicon dioxide gel, titanium colloidal sol, zirconium colloidal sol, Alumina gel and water, wherein silicon dioxide gel in silica for, described titanium colloidal sol is in titanium dioxide, zirconium colloidal sol is in zirconia, Alumina gel is in alundum (Al2O3), and the integral molar quantity of titanium colloidal sol, zirconium colloidal sol and Alumina gel and the mol ratio of silicon dioxide gel are 1:2; The thickness of the linear silicon dioxide layer finally obtained is 20nm, and the thickness of hollow silicon dioxide layer is 50nm, and the thickness of comprehensive silicon oxide skin(coating) is 20nm, and gross thickness is the antireflective coating of 90nm.Hollow silicon dioxide layer is in silica, in linear silicon dioxide layer and comprehensive silicon oxide skin(coating), silicon is counted in titanium dioxide, zirconium base zirconium dioxide in silica, titanium, aluminium in alundum (Al2O3), the integral molar quantity of linear silicon dioxide layer and comprehensive silicon oxide and the mol ratio of hollow silicon dioxide are 5:1.
embodiment 7
Prepare antireflective coating A7 according to the method for embodiment 1, difference is: also containing titanium colloidal sol, zirconium colloidal sol and Alumina gel in the linear silica coating liquid of step 1); Wherein linear silicon dioxide gel in silica for, described titanium colloidal sol is in titanium dioxide, and zirconium colloidal sol is in zirconia, and Alumina gel is in alundum (Al2O3), and the integral molar quantity of titanium colloidal sol, zirconium colloidal sol and Alumina gel and the mol ratio of silicon dioxide gel are 2:5;
Silica composite film coating liquid in step 3) is for be mixed to get coating liquid by silicon dioxide gel, titanium colloidal sol, zirconium colloidal sol, Alumina gel and water, wherein silicon dioxide gel in silica for, described titanium colloidal sol is in titanium dioxide, zirconium colloidal sol is in zirconia, Alumina gel is in alundum (Al2O3), and the integral molar quantity of titanium colloidal sol, zirconium colloidal sol and Alumina gel and the mol ratio of silicon dioxide gel are 1:3; The thickness of the linear silicon dioxide layer finally obtained is 5nm, and the thickness of hollow silicon dioxide layer is 65nm, and the thickness of comprehensive silicon oxide skin(coating) is 10nm, and gross thickness is the antireflective coating of 80nm.Hollow silicon dioxide layer is in silica, in linear silicon dioxide layer and comprehensive silicon oxide skin(coating), silicon is counted in titanium dioxide, zirconium base zirconium dioxide in silica, titanium, aluminium in alundum (Al2O3), the integral molar quantity of linear silicon dioxide layer and comprehensive silicon oxide and the mol ratio of hollow silicon dioxide are 2:1.
embodiment 8
Prepare antireflective coating A8 according to the method for embodiment 1, difference is: also containing titanium colloidal sol, zirconium colloidal sol and Alumina gel in the linear silica coating liquid of step 1); Wherein linear silicon dioxide gel in silica for, described titanium colloidal sol is in titanium dioxide, and zirconium colloidal sol is in zirconia, and Alumina gel is in alundum (Al2O3), and the integral molar quantity of titanium colloidal sol, zirconium colloidal sol and Alumina gel and the mol ratio of silicon dioxide gel are 2:5;
Silica composite film coating liquid in step 3) is for be mixed to get coating liquid by silicon dioxide gel, titanium colloidal sol, zirconium colloidal sol, Alumina gel and water, wherein silicon dioxide gel in silica for, described titanium colloidal sol is in titanium dioxide, zirconium colloidal sol is in zirconia, Alumina gel is in alundum (Al2O3), and the integral molar quantity of titanium colloidal sol, zirconium colloidal sol and Alumina gel and the mol ratio of silicon dioxide gel are 1:4; The thickness of the linear silicon dioxide layer finally obtained is 20nm, and the thickness of hollow silicon dioxide layer is 80nm, and the thickness of comprehensive silicon oxide skin(coating) is 20nm, and gross thickness is the antireflective coating of 120nm.Hollow silicon dioxide layer is in silica, in linear silicon dioxide layer and comprehensive silicon oxide skin(coating), silicon is counted in titanium dioxide, zirconium base zirconium dioxide in silica, titanium, aluminium in alundum (Al2O3), the integral molar quantity of linear silicon dioxide layer and comprehensive silicon oxide and the mol ratio of hollow silicon dioxide are 1.8:1.
comparative example 1
To disperse shape Ludox for coating liquid, with the standby Ludox of Stober legal system for main component, add appropriate surfactant again, compound concentration is the Ludox coating liquid of 3%, then this antireflective coating liquid is sprayed on a glass substrate, then at 600 DEG C, carry out tempering process, the processing time is 5min, obtains the antireflective coating CA1 that thickness is 110nm.
comparative example 2
The method in CN102617045A embodiment 1 is adopted to prepare antireflective coating CA2.
performance test
(1) light transmittance test
Adopt LCD-5200 photoelectric characteristic tester, scanning 380-780nm wave band, according to each wave band distribution character of sunshine disclosed in GBT 2680-1994, tests the light transmittance of each antireflective coating A1-A8 and CA1-CA2, and calculates its initial anti-reflection rate.The results are shown in Table 1.
The light transmittance of the substrate of glass of the light transmittance-cleaning of initial anti-reflection rate=self-cleaning anti-reflective glass sample.
(2) rub resistance test
Wet cotton (the liquid detergent aqueous solution of 5wt%) is adopted to rub each 10000 times of each antireflective coating A1-A8 and CA1-CA2.Pressure is 200 g/cm2, and rubbing angle is 90 degree.After 10000 frictions, detect the light transmittance of each glass sample.If each glass sample light transmittance reduced value, within 0.5%, is designated as OK, otherwise is NG.The results are shown in Table 1.
(3) pencil hardness test
Method disclosed in GB 6739-2006 is adopted to carry out pencil hardness test to each antireflective coating A1-A8 and CA1-CA2.The results are shown in Table 1.
(4) salt spray resistance test
Adopt GB/T 18912-2002/IEC 61701:1995 (photovoltaic module salt spray corrosion test).
Neutral salt spray 96 hours, salt fog composition is the NaCl solution of 5%.If the light transmittance reduced value of sample is within 0.5% after salt mist experiment, then it is qualified to judge.The results are shown in Table 1.
Table 1
| Anti-reflection rate | Rub resistance | Pencil hardness | Salt spray resistance | |
| A1 | 3% | OK | 5 | OK |
| A2 | 3.2% | OK | 5 | OK |
| A3 | 3% | OK | 5 | OK |
| A4 | 3% | OK | 5 | OK |
| A5 | 3.1% | OK | 5 | OK |
| A6 | 3.4% | OK | 6 | OK |
| A7 | 3.3% | OK | 5 | OK |
| A8 | 3.1% | OK | 6 | OK |
| CA1 | 2.5% | NG | 2 | NG |
| CA2 | 2.8% | NG | 3 | NG |
As can be seen from Table 1, the anti-reflection rate of the antireflective coating tool prepared with antireflective coating liquid of the present invention reaches more than 3%, pencil hardness more than 5, rub resistance and salt spray resistance are good; And the anti-reflection rate of the antireflective coating prepared with the antireflective coating liquid of comparative example 1 be 2.5%, pencil hardness is 2, anti-wear performance and salt spray resistance poor; The anti-reflection rate of the antireflective coating prepared with the antireflective coating liquid of comparative example 2 is 2.8%, pencil hardness is 3, anti-wear performance and salt spray resistance poor; Therefore, illustrate with the antireflective coating that antireflective coating liquid of the present invention prepares there is high anti-reflection rate, anti-wear performance is good, pencil hardness is high, salt spray resistance is good.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Claims (17)
1. an antireflective coating, is characterized in that, described antireflective coating comprises glass substrate and is coated in the linear silicon dioxide layer of glass baseplate surface, hollow silicon dioxide layer and comprehensive silicon oxide skin(coating) successively; Described comprehensive silicon oxide skin(coating) is the one in titanium silicon oxide layer, silicon Zirconium oxide layer, sieve and silica-sesquioxide layer, silicon titanium Zirconium oxide layer, silicon titanium al oxide layer, silicon zirconium al oxide layer and silicon titanium zirconium al oxide layer.
2. antireflective coating according to claim 1, it is characterized in that, in described comprehensive silicon oxide skin(coating), silicon is counted in titanium dioxide, zirconium base zirconium dioxide in silica, titanium, aluminium in alundum (Al2O3), the integral molar quantity of described titanium, zirconium and aluminium and the mol ratio of silicon are 1:1-5.
3. antireflective coating according to claim 1, it is characterized in that, described linear silicon dioxide layer is the one in titanium silicon oxide layer, silicon Zirconium oxide layer, sieve and silica-sesquioxide layer, silicon titanium Zirconium oxide layer, silicon titanium al oxide layer, silicon zirconium al oxide layer and silicon titanium zirconium al oxide layer.
4. antireflective coating according to claim 3, it is characterized in that, in described linear silicon dioxide layer, silicon is counted in titanium dioxide, zirconium base zirconium dioxide in silica, titanium, aluminium in alundum (Al2O3), the integral molar quantity of described titanium, zirconium and aluminium and the mol ratio of silicon are 1-3:5.
5. antireflective coating according to claim 3, it is characterized in that, described hollow silicon dioxide layer is in silica, in described linear silicon dioxide layer and described comprehensive silicon oxide skin(coating), silicon is counted in titanium dioxide, zirconium base zirconium dioxide in silica, titanium, aluminium in alundum (Al2O3), the integral molar quantity of described linear silicon dioxide layer and comprehensive silicon oxide and the mol ratio of hollow silicon dioxide are 1-5:1.
6. antireflective coating according to claim 1, is characterized in that, the thickness of described linear silicon dioxide layer is 5-20nm.
7. antireflective coating according to claim 1, is characterized in that, the thickness of described hollow silicon dioxide layer is 20-80nm.
8. antireflective coating according to claim 1, is characterized in that, the thickness of described comprehensive silicon oxide skin(coating) is 5-20nm.
9. antireflective coating according to claim 1, is characterized in that, the gross thickness of described linear silicon dioxide layer, hollow silicon dioxide layer and comprehensive silicon oxide skin(coating) is 80-120nm.
10. a preparation method for the antireflective coating described in claim 1-9 any one, is characterized in that, the method comprises the steps:
S1, apply linear silica coating liquid on the glass substrate, then dry and obtain linear silicon dioxide layer;
S2, at linear silica surface coating hollow silicon dioxide coating liquid, dry and obtain hollow silicon dioxide layer;
S3, at hollow silicon dioxide layer surface coating silicon dioxide composite film coating liquid, dry and obtain comprehensive silicon oxide skin(coating);
S4, the glass substrate tempering being coated with linear silicon dioxide layer, hollow silicon dioxide layer and comprehensive silicon oxide skin(coating) that step S3 is obtained or solidification process;
Wherein, described hollow silicon dioxide coating liquid comprises hollow silicon dioxide colloidal sol, additive and solvent; Described silica composite film coating liquid comprises at least one in titanium colloidal sol, zirconium colloidal sol and Alumina gel and chain silicon dioxide gel.
11. preparation methods according to claim 10, is characterized in that, before step S1, carry out activation process to glass substrate.
12. preparation methods according to claim 11, is characterized in that, described activation process is be dipped in by glass substrate in the mixed liquor of hydrogen peroxide and the concentrated sulfuric acid, then washes away mixed liquor with distilled water, dries up with inert gas.
13. preparation methods according to claim 10, is characterized in that, also comprise at least one in titanium colloidal sol, zirconium colloidal sol and Alumina gel in described linear silica coating liquid.
14. preparation methods according to claim 10, is characterized in that, described additive is at least one in coalescents, surfactant, thickener and wetting agent.
15. preparation methods according to claim 14, is characterized in that, with the gross mass of described hollow silicon dioxide plated film liquid film liquid for benchmark, the content of described hollow silicon dioxide is 1-5wt%, and the content of described additive is 0.5-2wt%.
16. preparation methods according to claim 10, is characterized in that, the method for described coating is the one in lift, roller coat, dip-coating, showering and spraying.
17. preparation methods according to claim 10, is characterized in that, the temperature of described oven dry is 20-300 DEG C; Described solidification temperature is 300-500 DEG C, and the time is 30-120min; The temperature of described tempering is 500-700 DEG C, and the time is 2-10min.
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| CN106671509A (en) * | 2016-12-21 | 2017-05-17 | 蚌埠玻璃工业设计研究院 | Spectrum-selected reflection type thermal-insulation film |
| CN107546279A (en) * | 2017-07-14 | 2018-01-05 | 合肥文胜新能源科技有限公司 | A kind of solar panel antireflective coating |
| CN108155253A (en) * | 2017-12-16 | 2018-06-12 | 天津市职业大学 | A kind of design and preparation method of electro-conductive glass antireflective coating |
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| CN102617045A (en) * | 2012-04-01 | 2012-08-01 | 中国科学院宁波材料技术与工程研究所 | SiO2 antireflection thin film and preparation method thereof |
| CN102875032A (en) * | 2011-07-15 | 2013-01-16 | 比亚迪股份有限公司 | Sol composition, preparation method thereof, method for forming self-cleaning and anti-reflective film on glass and self-cleaning and anti-reflective glass |
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| CN102027599A (en) * | 2008-03-10 | 2011-04-20 | 法国圣戈班玻璃厂 | Transparent substrate with anti-reflection coating |
| CN102875032A (en) * | 2011-07-15 | 2013-01-16 | 比亚迪股份有限公司 | Sol composition, preparation method thereof, method for forming self-cleaning and anti-reflective film on glass and self-cleaning and anti-reflective glass |
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| CN106671509A (en) * | 2016-12-21 | 2017-05-17 | 蚌埠玻璃工业设计研究院 | Spectrum-selected reflection type thermal-insulation film |
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| CN108155253A (en) * | 2017-12-16 | 2018-06-12 | 天津市职业大学 | A kind of design and preparation method of electro-conductive glass antireflective coating |
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