CN110204220A - A kind of coating liquid of double layer antireflection coating and preparation method thereof for photovoltaic glass - Google Patents
A kind of coating liquid of double layer antireflection coating and preparation method thereof for photovoltaic glass Download PDFInfo
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- CN110204220A CN110204220A CN201910587744.0A CN201910587744A CN110204220A CN 110204220 A CN110204220 A CN 110204220A CN 201910587744 A CN201910587744 A CN 201910587744A CN 110204220 A CN110204220 A CN 110204220A
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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
- C03C2217/00—Coatings on glass
- C03C2217/20—Materials for coating a single layer on glass
- C03C2217/29—Mixtures
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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
- C03C2217/00—Coatings on glass
- C03C2217/70—Properties of coatings
- C03C2217/73—Anti-reflective coatings with specific characteristics
- C03C2217/734—Anti-reflective coatings with specific characteristics comprising an alternation of high and low refractive indexes
-
- 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
- C03C2218/118—Deposition methods from solutions or suspensions by roller-coating
Abstract
The invention discloses a kind of coating liquids of double layer antireflection coating for photovoltaic glass, including first layer coating liquid and second layer coating liquid, first layer coating liquid by mass percentage, to be made of following raw material: silane 8-20%；Metallic compound 0.1-3.5%；Water 5-15%；Catalyst 0.1-5%；Curing agent 0.05-0.5%；Solvent 60-84%；Second layer coating liquid by mass percentage, is made of following raw material: silane 5-15%；Water 8-20%；Catalyst 0.1-2%；Activated monomer 0.5-2%；Initiator 0.01-0.2%；Emulsifier 0.05-0.5%；Molecular weight regulator 0.05-0.5%；Curing agent 0.01-0.2%；Solvent 60-84%.Application of the invention is so that the light transmittance of photovoltaic glass is higher, so that the generated output of component is higher；Weatherability two-layer coating is also more preferable with respect to single layer plated film, it is ensured that solar components keep steady and sustained generated output under various harsh environment.
Description
Technical field
The present invention relates to the coating liquid of a kind of coating liquid more particularly to a kind of double layer antireflection coating for photovoltaic glass and
Preparation method.
Background technique
In recent years, solar energy photovoltaic glass manufacturer mostly used roller coating technology, on solar energy photovoltaic glass surface
It is coated with one layer of anti-reflective coating, then in 700 DEG C or so progress tempering, so that the light transmittance of photovoltaic glass improves about 2-
2.4%, substantially increase the generating efficiency of solar battery.
About two-layer coating, the Chinese invention patent of Patent No. 201010150748.1 discloses a kind of plated with double-layer and subtracts
The photovoltaic glass preparation method of reflectance coating, is made of high refractive index oxide layer and porous silica.This double layer antireflection
The binding force for penetrating film and substrate of glass has obtained certain raising, but is only 95% in its peak reflectivity, and not to thin
The weatherability and mechanical strength of film are assessed；The Chinese invention patent of Patent No. 201110284088.0 discloses one kind three
The packaging glass of solar cell preparation method of layer anti-reflection film, the glass for being coated with three layers of anti-reflection film are big in visible region transmitance
In 98%, but for the coating liquid of first layer laminated film using the complex sol of two kinds of materials, performance is unstable in this method
(being easy to gel) is unfavorable for long-term large area production.And this method use it is being tested in optics K9 substrate of glass as a result,
The regular solar glass phase ratio of its transmitance and actual use, it is expensive although transmitance is higher, be not suitable for big rule
Mould uses；The Chinese invention of Patent No. 201410007684.8 disclose a kind of Weatherproof solar glass surface antireflective film and
Preparation method.The weatherability antireflective coating by be plated in solar energy glass surface compact structure high refractive index layer and
W type (λ/4 λ/2-) the optical film composition that low-index film is formed.But its low-index film is fine and close bifluoride magnesium
Either silica, the refractive index of film layer is still too high, and transmitance gain is little, and gain is two-sided only in 400nm-800nm
6%.And aforementioned all patents, carry out second of plated film again after first time plated film, curing time is all especially (200-300 DEG C long
Heat treatment 1 hour or 0.5 hour), can not achieve continuous production.
This single antireflection plated film, even if sacrificing the hardness and resistance to soiling of film layer, anti-reflection benefit is also that can not exceed
2.5%.Due to the hardness and resistance to soiling of film layer to be taken into account, currently, the anti-reflection benefit of main product is 2.3% or so on the market.And
And is there is decaying, city bar none after the atmospheric exposure tests such as jelly overly moist, damp and hot, PCT in the single layer plated film of photovoltaic glass
Best product pad value is made on face also in 0.5% or more (national standard is less than < 1.0%).These atmospheric exposure tests are only
It is the performance of preliminary test plated film, and has really been put into various harsh extreme environments, 10 years, 20 years, decaying is much
It is not so little by little.Component factory has been found that crystalline substance all occurs in the coated glass of the client in the area of various Different climates
Spot falls off, serious to affect generated output.
Two-layer coating technology largely still rests on laboratory stage, and the test of system is not carried out to the performance of film layer,
Manufacture craft can not realize large batch of production.
Therefore, a kind of coating liquid of double layer antireflection coating and preparation method thereof for photovoltaic glass is researched and developed, ability is become
Field technique personnel's urgent problem to be solved.
Summary of the invention
The present invention is to provide a kind of coating liquid of double layer antireflection coating for photovoltaic glass to solve above-mentioned deficiency
And preparation method thereof.
Above-mentioned purpose of the invention is realized by technical solution below: a kind of double-layer reflection-decreasing for photovoltaic glass
The coating liquid of film, including first layer coating liquid and second layer coating liquid, it is characterised in that:
The first layer coating liquid by mass percentage, is made of following raw material:
Silane 8-20%；
Metallic compound 0.1-3.5%；
Water 5-15%；
Catalyst 0.1-5%；
Curing agent 0.05-0.5%；
Solvent 60-84%；
The first layer coating liquid the preparation method comprises the following steps: by silane 8-20%, metallic compound 0.1-3.5%, water 5-15%, catalysis
Agent 0.1-5% is sequentially added in reaction kettle, is stirred on one side, and one side oil bath heating maintains the reflux for 8h, so to 86 DEG C or so to reflux
After release spare A, then, curing agent 0.05-0.5% and solvent 60-84% are sequentially added in A, stir, stir while adding
Speed 100-1000r/min is mixed, the time is about 30min.
The second layer coating liquid by mass percentage, is made of following raw material:
Silane 5-15%；
Water 8-20%；
Catalyst 0.1-2%；
Activated monomer 0.5-2%；
Initiator 0.01-0.2%；
Emulsifier 0.05-0.5%；
Molecular weight regulator 0.05-0.5%；
Curing agent 0.01-0.2%；
Solvent 60-84%.
The second layer coating liquid the preparation method comprises the following steps: by silane 5%-15%, part water 4-10%, catalyst 0.1-2% according to
It in secondary addition reaction kettle, stirs on one side, one side oil bath heating maintains the reflux for 12h, then release spare to 86 DEG C or so to reflux
B；After activated monomer 0.5-2%, part water 4-10%, emulsifier 0.05-0.5% high-speed stirred are emulsified into, it is added to reaction kettle
In, it adds initiator 0.01-0.2%, molecular weight regulator 0.05-0.5% is sequentially added in reaction kettle, stirs on one side, on one side
Oil bath heating keeps the temperature 12h, then releases spare C to 80 DEG C or so；Toward be added while stirring inside B solvent 60-84%,
Curing agent 0.01-0.2% is eventually adding C, and 30min is mixed to get second layer coating liquid.
Silane in the first layer coating liquid and second layer coating liquid, including positive quanmethyl silicate, tetraethyl orthosilicate,
Positive n-propyl silicate, methyltrimethoxysilane, methyltriethoxysilane, methyl tripropoxy silane, ethyl trimethoxy
Silane, ethyl triethoxysilane, ethyl tripropoxy silane, phenyltrimethoxysila,e, phenyl triethoxysilane, phenyl
Tripropoxy silane, 3- aminopropyl trimethoxysilane, 3- aminopropyl triethoxysilane, 3- aminopropyltriethoxy diethoxy silicon
Alkane, diethylenetriamine base propyl-triethoxysilicane, 3- urea propyl trimethoxy silicane, 3- urea propyl-triethoxysilicane, N-
Phenyl amino propyl trimethoxy silane, n-butyl amine base propyl trimethoxy silicane, the third oxygen of 3-(2,3 epoxy) propyl trimethoxy
Silane, the third oxygen of 3-(2,3 epoxy) propyl-triethoxysilicane, the third oxygen of 3-(2,3 epoxy) hydroxypropyl methyl diethoxy silane, 3-
(methacryloxy) propyl trimethoxy silicane, 3-(methacryloxy) propyl-triethoxysilicane, 3-(methyl-prop
Alkene acyloxy) a kind of either their mixture etc. such as hydroxypropyl methyl diethoxy silane.
Catalyst in the first layer coating liquid and second layer coating liquid includes various acid: hydrochloric acid, nitric acid, sulfuric acid, phosphorus
Acid, oxalic acid, citric acid, acetic acid, malic acid, maleic acid etc., various alkali: ammonium hydroxide, tetramethyl aqua ammonia, sodium hydroxide, hydrogen-oxygen
Change potassium, monoethanolamine, diethanol amine, triethanolamine, AMP-95, a propylamine, di-n-propylamine, tripropyl amine (TPA), 2- allylamine, cyclopropylamine,
Acrylamide, n-butylamine, triethylamine, diethylenetriamine, cyclic ethylene imines, piperazine, morpholine etc., Yi Jiqian, cobalt, tin, iron and
The solubility salt of other metals.
Metallic compound in the first layer coating liquid includes the compound, the compound containing aluminium, stanniferous chemical combination of titaniferous
Object, iron containing compounds, contains manganese compound, zinc compound, cobalt compound at antimony containing compounds.
Curing agent in the first layer coating liquid and second layer coating liquid, including ammonium hydroxide, monoethanolamine, diethanol amine,
Triethanolamine, AMP-95, tetramethyl aqua ammonia, sodium hydroxide, potassium hydroxide, a propylamine, di-n-propylamine, tripropyl amine (TPA), 2- propylene
Amine, cyclopropylamine, acrylamide, n-butylamine, ethylenediamine, hexamethylene diamine, triethylamine, diethylenetriamine, triethylene tetramine, cyclic ethylene
Imines, piperazine, morpholine.
Solvent in the first layer coating liquid and second layer coating liquid, comprising: methanol, ethyl alcohol, isopropanol, normal propyl alcohol,
Isopropanol, n-butanol, acetone, diacetone alcohol, propylene glycol monomethyl ether, propylene-glycol ethyl ether, ethylene glycol monomethyl ether, ethylene glycol ethyl ether, the third two
Alcohol methyl ether acetate, glycol methyl ether acetate are one or several kinds of.
Activated monomer in the first layer coating liquid and second layer coating liquid includes: acrylic acid, methacrylic acid, propylene
Sour methyl esters, ethyl acrylate, n-propyl, isopropyl acrylate, butyl acrylate, Isooctyl acrylate monomer, metering system
Sour methyl esters, ethyl methacrylate, isopropyl methacrylate, n propyl methacrylate, n-butyl acrylate, metering system
Sour isobutyl ester, isooctyl methacrylate, hydroxy-ethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, metering system
Sour hydroxypropyl acrylate, phenoxyethyl acrylate, phenoxyethyl methacrylate, glycidyl methacrylate, metering system
Sour isobornyl thiocyanoacetate, lauryl acrylate, methacryloxypropyl, vinyltriethoxysilane etc. one
Kind is several.
Initiator in the second layer coating liquid includes: lauroyl peroxide, benzoyl peroxide, ammonium persulfate, over cure
Sour potassium, isopropyl benzene hydroperoxide, tert-butyl hydroperoxide, di-t-butyl peroxide, cumyl peroxide, perbenzoic acid
The tert-butyl ester, peroxidating trimethylacetic acid tertiary butyl ester, methyl ethyl ketone peroxide, cyclohexanone peroxide, di-isopropyl peroxydicarbonate, mistake
It is one or two kinds of to aoxidize two dicyclohexyl carbonates, sodium hydrogensulfite, azodiisobutyronitrile, azobisisoheptonitrile etc..
Molecular weight regulator in the second layer coating liquid include: lauryl mercaptan, mercaptoethanol, thioacetic acid,
3- isooctyl mercaptopropionate IOMP, 2,4- diphenyl -4-methyl-1-pentene etc..
Emulsifier in the second layer coating liquid includes sorbitan fatty acid ester polyoxyethylene ether, fatty alcohol polyoxy
Vinethene, condensation compound of alkyl phenol and epoxy ethane, nonylphenol polyoxyethylene ether, castor oil polyoxyethylene ether, fatty acid polyoxy second
One in enester, polyethylene glycol, polypropylene glycol, ethoxylated fatty amines, sucrose alcohol stearate, glyceryl tristearate etc.
Kind or two kinds.
First layer coating liquid of the invention forms fine and close silica body structure, thicknesses of layers 60nm-120nm,
Plated film refractive index is 1.44-1.48(sodium yellow light, and wavelength is 5893 angstroms)；The second layer forms porous silica body structure,
Pore size is 5-50nm, porosity 15%-50%, thickness 90nm-140nm, refractive index 1.25-1.32(sodium yellow light, and wavelength is
5893 angstroms).
First layer coating liquid of the invention is applied on photovoltaic glass, in 150-200 DEG C of solidification 30S-120S, can be carried out
The roller coating of second layer coating liquid enters annealing furnace again after 150-200 DEG C of solidification 30S-120S and carries out tempering, the bilayer of formation
Membrane structure has higher light transmission rate gain, reaches 2.5% or more；With better weatherability, antireflective coating it is damp and hot, wet
The test light transmittance decaying such as jelly, PCT is smaller than 0.5%, veritably ensures that solar components keep steady under various harsh environment
Fixed lasting generated output.
Compared with the prior art, the advantages of the invention are
1. breaking the bottleneck of single antireflection film anti-reflective effect, two layers of coating liquid of the invention is plated on photovoltaic glass, energy
Light transmission rate, single layer plated film light transmittance 2-2.4% are greatly improved, two-layer coating increases AM1.5 spectrum dimmer reflecting 2.5% or more
Benefit is greater than 2.5% or more；
2. two layers of coating liquid of the invention is plated on photovoltaic glass, light transmission rate-wavelength curve of monofilm is improved, so that
The transmitance of infrared region greatly increases and PERC cell piece response curve more coincide, it is possible to so that the entire hair of component
Electrical power is higher, and generating efficiency is also higher under low light condition；
3. two layers of coating liquid of the invention is plated on photovoltaic glass, solve the problems, such as that single antireflection film weatherability is poor,
So that the test light transmittance decaying such as damp and hot, the wet jelly of antireflective coating, PCT is smaller than 0.5%, veritably ensure that solar components exist
Steady and sustained generated output is kept under various harsh environment；
4. first layer plated film of the invention only need at a temperature of 150-200 degree the dry solidification short 30-120 second, can carry out
Second of plated film, plated film, a tempering greatly reduce production cost, simplify technique twice.
Detailed description of the invention
Fig. 1 be in existing coated photovoltaic glass production technology addition one plated film coating machine, a curing apparatus into
Then the coating of row first layer coating liquid is coated with the flow chart of second layer antireflective coating according to prior art.
Fig. 2 is the film layer structure schematic diagram carried out after two layers of coating liquid coating.
Specific embodiment
The present invention is described in further detail below with reference to embodiment.
Embodiment 1:
A kind of coating liquid of double layer antireflection coating for photovoltaic glass of the invention, including first layer coating liquid and second layer plating
Film liquid, wherein
The formula of first layer coating liquid:
3-(methacryloxy) propyl-triethoxysilicane 12.5%
3- aminopropyltriethoxy diethoxy silane 1%
Water 10%
Oxalic acid 0.3%
Titanium acetylacetone 1.0%
Acrylamide 0.1%
Normal propyl alcohol 70.1%
Diacetone alcohol 5%
By 3-(methacryloxy positive in above-mentioned formula) propyl-triethoxysilicane 12.5%, 3- aminopropyltriethoxy diethoxy
Silane 1%, titanium acetylacetone 1.0%, water 10%, oxalic acid 0.3% sequentially add in reaction kettle, stir on one side, one side oil bath heating is extremely
86 DEG C or so, to reflux, maintain the reflux for 8h, then release spare A.Acrylamide 0.1%, normal propyl alcohol are sequentially added in A
70.1%, diacetone alcohol 5% stirs while adding, and mixing speed 100-1000r/min, the time is about 30min.
Second layer plated film formula of liquid:
Tetraethyl orthosilicate 8%
Phenyl triethoxysilane 3%
Water 13%
Citric acid 0.5%
Methacrylic acid 1%
Methylpropenyl propyl-triethoxysilicane 0.3%
Benzoyl peroxide 0.02%
Condensation compound of alkyl phenol and epoxy ethane 0.04%
Lauryl mercaptan 0.06%
Morpholine 0.05%
Isopropanol 74.03%
Tetraethyl orthosilicate 8%, phenyl triethoxysilane 3%, water 6%, citric acid 0.5% in above-mentioned formula are sequentially added into reaction
It in kettle, stirs on one side, one side oil bath heating maintains the reflux for 12h, then release spare B to 86 DEG C or so to reflux.By active first
Base acrylic acid 1%, methylpropenyl propyl-triethoxysilicane 0.3%, part water 7%, condensation compound of alkyl phenol and epoxy ethane
It after 0.04% high-speed stirred is emulsified into, is added in reaction kettle, adds benzoyl peroxide 0.02%, molecular weight regulator dodecane
Base mercaptan 0.06% sequentially adds in reaction kettle, stirs on one side, and one side oil bath heating keeps the temperature 12h, then release to 80 DEG C or so
Spare C.Isopropanol 74.03%, morpholine 0.05% are added while stirring inside toward B, is eventually adding C, 30min is mixed.
First layer coating liquid is coated in the solar energy glass of 10 35mm*90mm*3.2mm with solar energy glass pulling machine
On print, heats 2 minutes and solidify through 180 DEG C, obtain nattier blue solar energy antireflective coating glass.Again with glass pulling machine by the
It above, is then calcined 140 seconds or so at 700 DEG C of Muffle furnace or so, obtains the solar energy of bluish violet by two layers of coating liquid coating
Antireflective coating glass sample.Anti-reflection performance, strength character, weather resistance test are carried out to print, as a result such as following table.
| Detection project | Qualified grade |
| Light transmittance value added | >2.5% |
| Adhesive force test | It is excellent |
| Pencil hardness | 3H passes through |
| Resistant | It is excellent |
| Salt spray test | It is excellent |
| Hydrothermal aging | It is excellent |
| Wet jelly recycles aging | It is excellent |
Embodiment 2:
A kind of coating liquid of double layer antireflection coating for photovoltaic glass of the invention, including first layer coating liquid and second layer plating
Film liquid, wherein
First layer plated film formula of liquid:
3- urea propyl-triethoxysilicane 1.5%
The third oxygen of 3-(2,3 epoxy) propyl trimethoxy silicane 12%
Water 8%
Citric acid 0.5%
Aluminium acetylacetonate 1.0%
Hexamethylene diamine 0.1%
Normal propyl alcohol 71.9%
Diacetone alcohol 5%
By 3- urea propyl-triethoxysilicane 1.5%, the third oxygen of 3-(2,3 epoxy in above-mentioned formula) propyl trimethoxy silicane 12%,
Aluminium acetylacetonate 1.0%, water 8%, citric acid 0.5% sequentially add in reaction kettle, stir on one side, one side oil bath heating to 86 DEG C of left sides
The right side maintains the reflux for 8h, then releases spare A to reflux.Hexamethylene diamine 0.1%, normal propyl alcohol 71.9%, diacetone are sequentially added in A
Alcohol 5% stirs while adding, and mixing speed 100-1000r/min, the time is about 30min.
Second layer plated film formula of liquid:
Tetraethyl orthosilicate 6%
Vinyltriethoxysilane 7%
Water 13%
Citric acid 0.5%
N-butyl acrylate 1%
Methylpropenyl propyl-triethoxysilicane 0.3%
Peroxidized t-butyl perbenzoate 0.02%
Ethoxylated fatty amines 0.04%
Lauryl mercaptan 0.06%
Triethylene tetramine 0.05%
Isopropanol 72.03%
Tetraethyl orthosilicate 6%, vinyltriethoxysilane 7%, water 6%, citric acid 0.5% in above-mentioned formula are sequentially added instead
It answers in kettle, stirs on one side, one side oil bath heating maintains the reflux for 12h, then release spare B to 86 DEG C or so to reflux.It will be active
N-butyl acrylate 1%, methylpropenyl propyl-triethoxysilicane 0.3%, part water 7%, ethoxylated fatty amines 0.04%
It after high-speed stirred is emulsified into, is added in reaction kettle, adds peroxidized t-butyl perbenzoate 0.02%, molecular weight regulator ten
Dialkyl group mercaptan 0.06% sequentially adds in reaction kettle, stirs on one side, and one side oil bath heating keeps the temperature 12h, then to 80 DEG C or so
Release spare C.Isopropanol 72.03%, triethylene tetramine 0.05% are added while stirring inside toward B, is eventually adding C, mixes
Stir 30min.
First layer coating liquid is coated in the solar energy glass of 10 35mm*90mm*3.2mm with solar energy glass pulling machine
On print, heats 2 minutes and solidify through 180 DEG C, obtain nattier blue solar energy antireflective coating glass.Again with glass pulling machine by the
Two layers of coating liquid are coated in above, are then calcined 140 seconds or so it at 700 DEG C of Muffle furnace or so, are obtained the sun of bluish violet
It can antireflective coating glass sample.Anti-reflection performance, strength character, weather resistance test are carried out to print, as a result such as following table.
| Detection project | Qualified grade |
| Light transmittance value added | >2.5% |
| Adhesive force test | It is good |
| Pencil hardness | 3H passes through |
| Resistant | It is good |
| Salt spray test | It is excellent |
| Hydrothermal aging | It is excellent |
| Wet jelly recycles aging | It is excellent |
As shown in Figure 1, a plated film coating machine is added in existing coated photovoltaic glass production technology, a solidification is set
Then the standby coating for carrying out first layer coating liquid in the present invention (subtracts according to the second layer coating liquid in the original process coating present invention
Reflectance coating).
First layer coating liquid main component is organosilicon preformed polymer, and the wet-film thickness of formation is 90nm-180nm, at 200 DEG C
It is 25 DEG C -35 DEG C by air-cooled or water cooling to glass temperature surface, then carry out second of plating after left and right solidification 30S-120S
Film.Second layer coating liquid main component is siloxane prepolymer and organic polymer activated centre, in 200 DEG C or so solidification 30S-
After 120S, forms inorganic siloxanes and be wrapped in nanometer structure in organic polymer activated centre, into annealing furnace tempering.Tempering
Afterwards, first layer forms fine and close silicon dioxide structure, thicknesses of layers 60nm-120nm, and plated film refractive index is 1.44-1.48(sodium
Yellow light, wavelength are 5893 angstroms)；The second layer forms porous silicon dioxide structure, pore size 5-50nm, porosity 15%-
50%, thickness 90nm-140nm, refractive index 1.25-1.32(sodium yellow light, wavelength are 5893 angstroms), film layer structure is as shown in Figure 2.
The above description is only an embodiment of the present invention, is not intended to limit the scope of the invention, all to utilize this hair
Equivalent structure or equivalent flow shift made by bright specification and embodiment content, it is relevant to be applied directly or indirectly in other
Technical field is included within the scope of the present invention.
Claims (10)
1. a kind of coating liquid of the double layer antireflection coating for photovoltaic glass, including first layer coating liquid and second layer coating liquid,
It is characterized by:
The first layer coating liquid by mass percentage, is made of following raw material:
Silane 8-20%；
Metallic compound 0.1-3.5%；
Water 5-15%；
Catalyst 0.1-5%；
Curing agent 0.05-0.5%；
Solvent 60-84%；
The first layer coating liquid the preparation method comprises the following steps: by silane 8-20%, metallic compound 0.1-3.5%, water 5-15%, catalysis
Agent 0.1-5% is sequentially added in reaction kettle, is stirred on one side, and one side oil bath heating maintains the reflux for 8h, so to 86 DEG C or so to reflux
After release spare A, then, curing agent 0.05-0.5% and solvent 60-84% are sequentially added in A, stir, stir while adding
Speed 100-1000r/min is mixed, the time is about 30min；
The second layer coating liquid by mass percentage, is made of following raw material:
Silane 5-15%；
Water 8-20%；
Catalyst 0.1-2%；
Activated monomer 0.5-2%；
Initiator 0.01-0.2%；
Emulsifier 0.05-0.5%；
Molecular weight regulator 0.05-0.5%；
Curing agent 0.01-0.2%；
Solvent 60-84%；
The second layer coating liquid the preparation method comprises the following steps: silane 5%-15%, part water 4-10%, catalyst 0.1-2% are successively added
Enter in reaction kettle, stir on one side, one side oil bath heating maintains the reflux for 12h, then release spare B to 86 DEG C or so to reflux；It will
After activated monomer 0.5-2%, part water 4-10%, emulsifier 0.05-0.5% high-speed stirred are emulsified into, it is added in reaction kettle, then
Addition initiator 0.01-0.2%, molecular weight regulator 0.05-0.5% are sequentially added in reaction kettle, are stirred on one side, one side oil bath
80 DEG C or so are heated to, 12h is kept the temperature, then releases spare C；Solvent 60-84%, solidification is added inside toward B while stirring
Agent 0.01-0.2% is eventually adding C, and 30min is mixed to get second layer coating liquid.
2. a kind of coating liquid of double layer antireflection coating for photovoltaic glass according to claim 1, it is characterised in that: institute
State the silane in first layer coating liquid and second layer coating liquid, including positive quanmethyl silicate, tetraethyl orthosilicate, positive silicic acid positive third
Ester, methyltrimethoxysilane, methyltriethoxysilane, methyl tripropoxy silane, ethyl trimethoxy silane, ethyl three
Ethoxysilane, ethyl tripropoxy silane, phenyltrimethoxysila,e, phenyl triethoxysilane, phenyl tripropoxy silicon
Alkane, 3- aminopropyl trimethoxysilane, 3- aminopropyl triethoxysilane, 3- aminopropyltriethoxy diethoxy silane, divinyl
Three aminocarbonyl propyl triethoxysilanes, 3- urea propyl trimethoxy silicane, 3- urea propyl-triethoxysilicane, N- phenyl amino third
Base trimethoxy silane, n-butyl amine base propyl trimethoxy silicane, the third oxygen of 3-(2,3 epoxy) propyl trimethoxy silicane, 3-(2,
3 the third oxygen of epoxy) propyl-triethoxysilicane, the third oxygen of 3-(2,3 epoxy) hydroxypropyl methyl diethoxy silane, 3-(methacryl
Oxygroup) propyl trimethoxy silicane, 3-(methacryloxy) propyl-triethoxysilicane, 3-(methacryloxy) third
The one kind such as ylmethyl diethoxy silane or their mixture.
3. a kind of coating liquid of double layer antireflection coating for photovoltaic glass according to claim 1, it is characterised in that: institute
Stating the catalyst in first layer coating liquid and second layer coating liquid includes various acid: hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, oxalic acid, lemon
Lemon acid, acetic acid, malic acid, maleic acid etc., various alkali: ammonium hydroxide, tetramethyl aqua ammonia, sodium hydroxide, potassium hydroxide, an ethyl alcohol
Amine, diethanol amine, triethanolamine, AMP-95, a propylamine, di-n-propylamine, tripropyl amine (TPA), 2- allylamine, cyclopropylamine, acrylamide, just
Butylamine, triethylamine, diethylenetriamine, cyclic ethylene imines, piperazine, morpholine etc., Yi Jiqian, cobalt, tin, iron and other metals can
Dissolubility salt.
4. a kind of coating liquid of double layer antireflection coating for photovoltaic glass according to claim 1, it is characterised in that: institute
State the compound, the compound containing aluminium, sn-containing compound, chemical combination containing antimony that the metallic compound in first layer coating liquid includes titaniferous
Object, contains manganese compound, zinc compound, cobalt compound at iron containing compounds.
5. a kind of coating liquid of double layer antireflection coating for photovoltaic glass according to claim 1, it is characterised in that: institute
State the curing agent in first layer coating liquid and second layer coating liquid, including ammonium hydroxide, monoethanolamine, diethanol amine, triethanolamine,
AMP-95, tetramethyl aqua ammonia, sodium hydroxide, potassium hydroxide, a propylamine, di-n-propylamine, tripropyl amine (TPA), 2- allylamine, cyclopropylamine,
Acrylamide, n-butylamine, ethylenediamine, hexamethylene diamine, triethylamine, diethylenetriamine, triethylene tetramine, cyclic ethylene imines, piperazine,
Morpholine.
6. a kind of coating liquid of double layer antireflection coating for photovoltaic glass according to claim 1, it is characterised in that: institute
State the solvent in first layer coating liquid and second layer coating liquid, comprising: methanol, ethyl alcohol, isopropanol, normal propyl alcohol, isopropanol, positive fourth
Alcohol, acetone, diacetone alcohol, propylene glycol monomethyl ether, propylene-glycol ethyl ether, ethylene glycol monomethyl ether, ethylene glycol ethyl ether, propylene glycol monomethyl ether acetic acid
Ester, glycol methyl ether acetate are one or several kinds of.
7. a kind of coating liquid of double layer antireflection coating for photovoltaic glass according to claim 1, it is characterised in that: institute
Stating the activated monomer in first layer coating liquid and second layer coating liquid includes: acrylic acid, methacrylic acid, methyl acrylate, third
Olefin(e) acid ethyl ester, n-propyl, isopropyl acrylate, butyl acrylate, Isooctyl acrylate monomer, methyl methacrylate, first
Base ethyl acrylate, isopropyl methacrylate, n propyl methacrylate, n-butyl acrylate, Isobutyl methacrylate,
Isooctyl methacrylate, hydroxy-ethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxy propyl methacrylate,
Phenoxyethyl acrylate, phenoxyethyl methacrylate, glycidyl methacrylate, methacrylic acid isoborneol
Ester, lauryl acrylate, methacryloxypropyl, vinyltriethoxysilane etc. are a kind of or several
Kind.
8. a kind of coating liquid of double layer antireflection coating for photovoltaic glass according to claim 1, it is characterised in that: institute
Stating the initiator in second layer coating liquid includes: lauroyl peroxide, benzoyl peroxide, ammonium persulfate, potassium peroxydisulfate, isopropylbenzene
Hydrogen peroxide, tert-butyl hydroperoxide, di-t-butyl peroxide, cumyl peroxide, peroxidized t-butyl perbenzoate, peroxide
Change trimethylacetic acid tertiary butyl ester, methyl ethyl ketone peroxide, cyclohexanone peroxide, di-isopropyl peroxydicarbonate, dicetyl peroxydicarbonate
Dicyclohexyl maleate, sodium hydrogensulfite, azodiisobutyronitrile, azobisisoheptonitrile etc. are one or two kinds of.
9. a kind of coating liquid of double layer antireflection coating for photovoltaic glass according to claim 1, it is characterised in that: institute
Stating the molecular weight regulator in second layer coating liquid includes: lauryl mercaptan, mercaptoethanol, thioacetic acid, 3- mercaptopropionic acid
Different monooctyl ester IOMP, 2,4- diphenyl -4-methyl-1-pentene.
10. a kind of coating liquid of double layer antireflection coating for photovoltaic glass according to claim 1, it is characterised in that:
Emulsifier in the second layer coating liquid include sorbitan fatty acid ester polyoxyethylene ether, fatty alcohol polyoxyethylene ether,
Condensation compound of alkyl phenol and epoxy ethane, castor oil polyoxyethylene ether, polyoxyethylene carboxylate, gathers at nonylphenol polyoxyethylene ether
One of ethylene glycol, polypropylene glycol, ethoxylated fatty amines, sucrose alcohol stearate, glyceryl tristearate etc. or
Two kinds.
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