CN104671672B - A kind of antireflective coating liquid and preparation method thereof, photovoltaic glass and preparation method thereof, solar cell module - Google Patents
A kind of antireflective coating liquid and preparation method thereof, photovoltaic glass and preparation method thereof, solar cell module Download PDFInfo
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- CN104671672B CN104671672B CN201310606013.9A CN201310606013A CN104671672B CN 104671672 B CN104671672 B CN 104671672B CN 201310606013 A CN201310606013 A CN 201310606013A CN 104671672 B CN104671672 B CN 104671672B
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Abstract
The invention provides a kind of antireflective coating liquid, the antireflective coating liquid includes decentralized Ludox, hollow Ludox, linear colloidal sol, additive and solvent；On the basis of the total solid content of antireflective coating liquid, the content of decentralized Ludox is 30 60wt%, and the content of hollow Ludox is 30 60wt%, and the content of linear colloidal sol is 10 40wt%；On the basis of the gross mass of antireflective coating liquid, the content of additive is 0.2 2wt%；Average grain diameter of the average grain diameter of the decentralized Ludox less than the hollow Ludox.The photovoltaic glass and the preparation method of the photovoltaic glass that are obtained present invention also offers the preparation method of the antireflective coating liquid and with the antireflective coating liquid and the solar cell module containing the photovoltaic glass.The antireflective coating prepared with antireflective coating liquid of the invention has that anti-reflection rate high, anti-wear performance are good, pencil hardness is high, salt spray resistance good.
Description
Technical field
The invention belongs to area of solar cell, more particularly to a kind of antireflective coating liquid and preparation method thereof, photovoltaic glass
Glass and preparation method thereof, solar cell module.
Background technology
At present, with the fast development of global economy, world energy consumption increases severely, and traditional resource consumption is rapidly and increasingly
It is rare and exploit difficulty and be continuously increased, make global energy supply nervous.China is in the rapid economic development stage, right
The demand of the energy is big, and current oil is externally interdependent more than 50%, and energy supply is seriously nervous.Solar energy be a kind of cleaning, can
The renewable sources of energy, are radiated the solar energy up to 1.7*10 of earth surface every year5Hundred million kilowatts, be 3.5 ten thousand times of earth total energy consumption, right
It is inexhaustible for the mankind, is not had a rest with it.
Solar cell is a kind of device that sunshine is changed into electric energy, is a kind of reproducible eco-friendly power source.But mesh
Preceding solar cell is low to the utilization rate of sunshine, i.e., actual optoelectronic transformation efficiency is low.How actual light photoelectric transformation efficiency is reduced
With the gap of theoretical light photoelectric transformation efficiency, the photoelectric transformation efficiency for further improving solar cell is still anxious to be resolved and asks
Topic.
At present, using surface antireflection film technology be improve solar cell photoelectric transformation efficiency Main Means it
One.Antireflecting silicon dioxide film is antireflective coating the most frequently used at present, and antireflecting silicon dioxide film generally uses following two method systems
It is standby, 1, microporous membrane is prepared on substrate（Pore type）, introduce pore-foaming agent and form loose structure, adjusted by porosity and reflected
Rate；2nd, another kind is the film formed by spherical nanometer silicon dioxide particle（Granular pattern）, adjusted by spheric granules size
Section refractive index.Pore type silica antireflection film is difficult to obtain low refractive index, average anti-reflection general of coating single side
Have 2.5% or so, and being typically due to capillary condensation effect makes the light transmittance of film further reduce, anti-reflection film refractive index it is consistent
Property and stability are poor；The performances such as salt spray resistance, the rub resistance of granular pattern film are not good.
On the other hand, either granular pattern antireflective coating or pore type antireflection film, are required for preparing first corresponding
Coating liquid, current coating liquid performance there is also the problems such as filming performance is not good, bin stability is poor.
Meanwhile, the problem mutually restricted between the salt spray resistance and weather resistance and reflection preventing ability of existing antireflective coating,
Its reason is that in order that the refractive index of antireflective coating is reduced to 1.23, film must have certain porosity, but hole is caused
Membrane structure is loose, adhesion reduction, so that easily by outside contamination, scratch-resistant and does not come off easily.
Publication No. CN102531406A discloses a kind of antireflective coated solution, including following volumn concentration group
Point：Silicon dioxide gel 80.0-95.0%；TiO 2 sol 0.1-8.0%；Zirconia sol 0.1-5.0%；Ceria
And/or magnesia and/or alundum (Al2O3) 0-3.0%；Stabilizer 0.1-3.6%；Coating material 0.1-3.8%；Volatilization controlling agent
0-8.0%；Processing aid 0.2-4.5%.It is its salt spray resistance, resistance to although the patent can obtain the antireflective coating of high transmittance
Frictional behaviour is poor.
The content of the invention
The present invention is the existing antireflective coating salt spray resistance of solution and the technical problem of crocking resistance difference, there is provided a kind of salt tolerant
Mist and the good antireflective coating liquid of crocking resistance and preparation method thereof, photovoltaic glass and preparation method thereof, solar battery group
Part.
The invention provides a kind of antireflective coating liquid, the antireflective coating liquid includes decentralized Ludox, hollow silicon
Colloidal sol, linear colloidal sol, additive and solvent；On the basis of the total solid content of antireflective coating liquid, the decentralized Ludox
Content is 30-60wt%, and the content of the hollow Ludox is 30-60wt%, and the content of the linear colloidal sol is 10-40wt%；
On the basis of the gross mass of the antireflective coating liquid, the content of the additive is 0.2-2wt%；The decentralized Ludox
Average grain diameter less than the hollow Ludox average grain diameter.
Present invention also offers a kind of preparation method of described antireflective coating liquid, the method comprises the following steps：Will
Decentralized Ludox, hollow Ludox, linear colloidal sol, additive and solvent are well mixed to obtain antireflective coating liquid.
Present invention also offers a kind of photovoltaic glass, the photovoltaic glass includes glass substrate and positioned at the glass substrate
The antireflective coating on surface, the antireflective coating is formed by the coating of antireflective coating liquid；The antireflective coating liquid is institute of the present invention
The antireflective coating liquid stated.
Present invention also offers a kind of preparation method of photovoltaic glass, antireflective coating liquid is coated on a glass substrate, so
Drying, curing process obtain the photovoltaic glass with antireflective coating afterwards, and the antireflective coating liquid is anti-reflection of the present invention
Penetrate coating liquid.
Present invention also offers a kind of solar cell module, the solar cell module includes from top to bottom layer successively
Folded transparent glass, cell piece and backboard；The transparent glass is by photovoltaic glass of the present invention.
Contain the average of decentralized Ludox, hollow Ludox and decentralized Ludox in antireflective coating liquid of the invention
Less than the average grain diameter of the hollow Ludox, decentralized Ludox can allow the surface of antireflective coating to become fine and close to particle diameter, and
Hollow Ludox can reduce the reflectivity of antireflective coating, and the average grain diameter of decentralized Ludox is less than the hollow Ludox
Average grain diameter can be such that hole is sealed under film compact surfaces, so as to reach have concurrently low-refraction and surface compact degree high and
The requirement of high surface hardness, makes film have long-term stability.
Specific embodiment
In order that technical problem solved by the invention, technical scheme and beneficial effect become more apparent, below in conjunction with
Embodiment, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only used to explain
The present invention, is not intended to limit the present invention.
The invention provides a kind of antireflective coating liquid, the antireflective coating liquid includes decentralized Ludox, hollow silicon
Colloidal sol, linear colloidal sol, additive and solvent；On the basis of the total solid content of antireflective coating liquid, the decentralized Ludox
Content is 30-60wt%, and the content of the hollow Ludox is 30-60wt%, and the content of the linear colloidal sol is 10-40wt%；
On the basis of the gross mass of the antireflective coating liquid, the content of the additive is 0.2-2wt%；The decentralized Ludox
Average grain diameter less than the hollow Ludox average grain diameter.
The present invention combines the advantage of pore type and granular pattern antireflection film, removes the pore-foaming agent in pore type coating liquid,
Simultaneously by the full particle in granular pattern coating liquid instead of hollow bead, so that the aperture sections of final antireflection film
It is enclosed within the inside of nano SiO 2 particle.Particle of the particle size of the decentralized Ludox than the hollow Ludox
It is smaller, beneficial to the space filled between the hollow silicon dioxide particle, make film surface structure more closely knit, while can
To adjust the refractive index of film；The effect of the linear Ludox is the change for making decentralized silica and hollow silicon dioxide
Learn and combine more firmly, while the refractive index of film can also be adjusted.Therefore, the anti-reflection for being formed with antireflective coating liquid of the invention
Film is penetrated on the premise of with reflection preventing ability high, also with excellent weather resistance, salt spray resistance and crocking resistance, and
And technical process is simple, easily realizes mass production.
In the present invention, the decentralized Ludox and hollow Ludox oneself can also be prepared with commercially available.Such as decentralized
Ludox can be prepared by Stober methods or silica flour dissolution method or other methods, and specific preparation method is：By 100 mass parts
Described linear SiO2 colloidal sols be added dropwise in the alkali lye of 50 mass parts, the alkali lye is 0.5% ammonia spirit, in 50 DEG C
Lower ageing 4h, obtains the colloidal sol that silica particle diameter is 10nm.Hollow Nano SiO2 colloidal sols：Bead meeting is melted into selected from catalyst is waved day
The particle diameter of society is 40-50nm, the methyl ethyl ketone silicon dioxide gel that mass fraction is 20%.
According to antireflective coating liquid provided by the present invention, in order that obtaining antireflective coated surface consistency and refractive index
More matching, it is preferable that the weight ratio of the decentralized Ludox and the hollow Ludox is 0.5-1：1.
According to antireflective coating liquid provided by the present invention, it is preferable that the average grain diameter of the decentralized Ludox is 2-
20nm；The average grain diameter of the hollow Ludox is 20-100nm.The particle diameter of the decentralized Ludox is more molten than the hollow silicon
The particle diameter of glue is small, and their accumulation can to greatest extent make intergranular gap diminish；On the other hand, the grain of hollow Ludox
When footpath is larger, can increase the thickness adjustable extent of the inner space of hollow bead and spherical shell, to ensure that hollow bead has
Enough intensity.
According to antireflective coating liquid provided by the present invention, it is preferable that the additive is coalescents, surface-active
At least one in agent, thickener and wetting agent.The coalescents are not particularly limited, such as polyethylene glycol, glycerine；Institute
State surfactant to be not particularly limited, such as can be organic silicon surfactant, nonionic surfactant；The thickening
Agent is not particularly limited, and such as can be hydroxyethyl cellulose.The wetting agent has no particular limits, such as can for BYK346 or
DC-29。
According to antireflective coating liquid provided by the present invention, in order that antireflective plated film forms micron-sized thickness, while
Beneficial to coating, and dry film has nano level thickness, it is preferable that the solid content of the antireflective coating liquid is 2-5wt%.
According to antireflective coating liquid provided by the present invention, it is preferable that the linear colloidal sol is linear Ludox, linear titanium
At least one in colloidal sol, linear Alumina gel and linear zirconium colloidal sol.The linear Ludox, linear titanium colloidal sol, linear Alumina gel
Oneself can also be prepared with commercially available with linear zirconium colloidal sol, due to the extremely unstable property of the storage of linear colloidal sol, the linear colloidal sol
For oneself is prepared.Wherein described titanium colloidal sol, zirconium colloidal sol and Alumina gel can be closed by the oxychloride of the ester type compound of titanium, zirconium respectively
The ester type compound of thing and aluminium is reacted by acid or the catalytic action of alkali with water.For example, the preparation of linear Ludox
Method is：The nitric acid of the tetraethyl orthosilicate of 10.8 mass parts, the water of 50 mass parts and 0.5 mass parts is mixed into 2h.It is linear
The preparation method of titanium colloidal sol is：The nitric acid of the butyl titanate of 10 weight portions, the water of 100 mass parts and 2 mass parts is mixed,
In being aged 24h at 50 DEG C.The preparation method of linear zirconium colloidal sol is：The deionized water of 200 mass parts is weighed, is added under agitation
Enter the basic zirconium chloride of 100 mass parts, it is 2.5 to adjust pH with ammoniacal liquor, is aged after being stirred at room temperature stand-by.The preparation side of linear Alumina gel
Method is：The nitric acid of the water of 200 mass parts, the aluminium isopropoxide of 20 mass parts and 1 mass parts, in reacting 2h at 85 DEG C.
According to antireflective coating liquid provided by the present invention, in order that decentralized silicon dioxide granule and hollow silicon dioxide
Connection between particle is more closely knit, while making particle " be absorbed in " inside of film, it is preferable that in the antireflective coating liquid also
Including surface conditioning agent.The surface conditioning agent is the one kind or several in silane coupler, tetraethyl orthosilicate and methyl silicate
Kind, the hydrolysate after surface conditioning agent hydrolysis is attached to the decentralized silicon dioxide granule and hollow silicon dioxide particle table
Face, in the wet film drying process after film, these hydrolysates further crosslink reaction, make combination between particle more
Plus firmly.Solvent can be water or organic solvent in antireflective coating liquid of the invention.In general, solvent can all include
Machine solvent and water, simply ratio is different, can be needed suitably to be adjusted according to coating process.When organic solvent content is more,
The silane couplers such as KH550, KH570 can be added to decentralized silicon dioxide granule and hollow silicon dioxide nanoparticle surface
Modified.Specific method is, in the colloidal sol containing decentralized Nano particles of silicon dioxide and hollow silicon dioxide nano-particle
In, appropriate silane coupler is added dropwise, addition with SiO2 as calculating benchmark, decentralized silica and hollow silicon dioxide
Gross mass is 1 with the mass ratio of silane coupler：0.1-0.5.When water content is more, can be processed with surface hydroxylation, specifically
Method is to be added dropwise over tetraethyl orthosilicate or methyl silicate under acid or alkaline conditions to be received to containing decentralized silica
In the hydrosol of rice corpuscles and hollow silicon dioxide nano-particle, addition with SiO2 as calculating benchmark, decentralized silica
And the gross mass of hollow silicon dioxide and the mass ratio of tetraethyl orthosilicate or methyl silicate are 1：0.1-0.5.Certain above-mentioned two
In kind of processing method, can individually process decentralized silica and hollow silicon dioxide, but in order to it is easy to operate simultaneously
The saving time, it is main using it is existing decentralized silica is mixed with hollow silicon dioxide after again together with carry out surface conditioning agent and change
Property.
Present invention also offers a kind of preparation method of antireflective coating liquid, the method comprises the following steps：By decentralized
Ludox, hollow Ludox, linear colloidal sol, additive and solvent are well mixed to obtain antireflective coating liquid.
According to the preparation method of antireflective coating liquid provided by the present invention, it is preferable that before mixing to decentralized silicon
Colloidal sol and hollow Ludox are surface-treated.The surface treatment is to be processed using surface conditioning agent, specific treatment
Detailed description has been carried out above for method, and here is omitted.
Present invention also offers a kind of photovoltaic glass, the photovoltaic glass includes glass substrate and positioned at the glass substrate
The antireflective coating on surface, the antireflective coating is formed by the coating of antireflective coating liquid；The antireflective coating liquid is institute of the present invention
The antireflective coating liquid stated.
According to photovoltaic glass provided by the present invention, it is preferable that the glass substrate has matte, the antireflective coating shape
Into on matte.
According to photovoltaic glass provided by the present invention, in order to further improve the high rigidity of antireflective coating, rub resistance, from clear
Clean, anti-condensation, it is preferable that in the layer function film layer of the antireflective coating coating surface one, the feature film layer is titanium dioxide
The film layer of at least one formation in silicon, titanium dioxide, zirconium dioxide and alundum (Al2O3).It is further preferred that the function
Property film layer thickness be 5-20nm.
Present invention also offers a kind of preparation method of photovoltaic glass, antireflective coating liquid is coated on a glass substrate, so
Drying, curing process obtain the photovoltaic glass with antireflective coating afterwards, and the antireflective coating liquid is anti-reflection of the present invention
Penetrate coating liquid.
According to preparation method provided by the present invention, the method for the coating has no particular limits, and can be this area
One kind in conventional various painting methods, such as lifting, roller coat, dip-coating, showering and spraying.
According to preparation method provided by the present invention, in order to preferably, also include at tempering after the curing process
Reason step.
According to preparation method provided by the present invention, it is preferable that the temperature of the drying is 20-300 DEG C；At the tempering
The temperature of reason is 500-700 DEG C, and the time is 2-10min；The temperature of the curing process is 300-500 DEG C, and the time is 30-
120min。
According to preparation method provided by the present invention, in order to further improve the high rigidity of antireflective coating, rub resistance, from clear
Clean, anti-condensation, it is preferable that in the coating surface feature film layer of antireflective coating.The feature film layer is silica, dioxy
Change the film layer of at least one formation in titanium, zirconium dioxide and alundum (Al2O3).It is further preferred that the feature film layer
Thickness is 5-20nm.The preparation method of the feature film layer is：It is by least one in titanium colloidal sol, zirconium colloidal sol and Alumina gel
Coating liquid, is coated by coating methods such as lifting or roller coat and obtained.Further, titanium colloidal sol, zirconium are molten in the coating liquid
The mol ratio of glue and Alumina gel is 1：1：1.
Present invention also offers a kind of solar cell module, the solar cell module includes from top to bottom layer successively
Folded transparent glass, cell piece and backboard；The transparent glass is photovoltaic glass of the present invention.
Below by specific embodiment, the present invention is described in further detail.
Embodiment is raw materials used：
Linear Ludox：The nitric acid of the tetraethyl orthosilicate of 10.8 mass parts, the water of 50 mass parts and 0.5 mass parts is mixed
Stirring 2h.
Decentralized Ludox：The described linear SiO2 colloidal sols of 100 mass parts are added dropwise in the alkali lye of 50 mass parts,
The alkali lye is 0.5% ammonia spirit, in 4h is aged at 50 DEG C, obtains the colloidal sol that silica particle diameter is 10nm.
Hollow Nano SiO2 colloidal sols：Selected from wave day catalyst chemical conversion bead commercial firm particle diameter be 40-50nm, mass fraction be
20% methyl ethyl ketone silicon dioxide gel.
Linear titanium colloidal sol：The nitric acid of the butyl titanate of 10 weight portions, the water of 100 mass parts and 2 mass parts is mixed,
In being aged 24h at 50 DEG C.
Linear zirconium colloidal sol：The deionized water of 200 mass parts is weighed, the oxychloride of 100 mass parts is added under agitation
Zirconium, it is 2.5 to adjust pH with ammoniacal liquor, is aged after being stirred at room temperature stand-by.
Linear Alumina gel：The nitric acid of the water of 200 mass parts, the aluminium isopropoxide of 20 mass parts and 1 mass parts, in anti-at 85 DEG C
Answer 2h.
Embodiment 1
1st, antireflective coating liquid is prepared
Be the decentralized Ludox of 10nm by particle diameter, particle diameter be the hollow Ludox of 50nm, linear Ludox, linear titanium it is molten
Glue, linear Alumina gel, linear zirconium colloidal sol, ethylene glycol, surfactant Qula logical -100, wetting agent BYK346 mixing, Ran Houjia
Enter the water and ethanol of phase homogenous quantities, the solids level concentration for adjusting coating liquid is 3wt%, that is, obtain antireflective coating liquid A1.Wherein,
The solid content of decentralized Ludox accounts for the 40wt% of total solid content, and the solid content of hollow Ludox accounts for the 40wt% of total solid content, line
Shape Ludox, linear titanium colloidal sol, linear Alumina gel, the solid content of linear zirconium colloidal sol respectively account for the 5% of total solid content respectively, ethylene glycol,
The mass fraction that surfactant Qula logical -100, wetting agent BYK346 accounts for coating liquid respectively is 0.5%, 0.2%, 0.3%.
2nd, photovoltaic glass is prepared
Prepare photovoltaic glass B1：One layer of antireflective coating liquid A1 is sprayed on a glass substrate, then in 100 DEG C of drying,
400 degrees Celsius of solidification 100min obtain thickness for 100nm antireflection film layers.
Embodiment 2
1st, antireflective coating liquid is prepared
Method according to embodiment 1 prepares antireflective coating liquid A2, and difference is：KH550 is added dropwise to decentralized titanium dioxide
The surface of silicon is modified, and with SiO2 content meters, makes the Silane coupling agent KH550 of addition and the mass ratio of decentralized silica
It is 0.2；KH550 is added dropwise to modify the surface of hollow silicon dioxide, with SiO2 content meters, makes the silane coupler of addition
KH550 is 0.2 with the mass ratio of hollow silicon dioxide；Amount of alcohol is added for 2 times of water, and makes the concentration of coating liquid be
3wt%。
2nd, photovoltaic glass is prepared
Prepare photovoltaic glass B2：One layer of antireflective coating liquid A2 is sprayed on a glass substrate, then in 20 DEG C of drying,
300 DEG C of solidification 120min obtain the antireflection film layer that thickness is 110nm.
Embodiment 3
1st, antireflective coating liquid is prepared
Method according to embodiment 1 prepares antireflective coating liquid A3, and difference is：Methyl silicate is added dropwise to decentralized two
The surface of silica is modified, and with SiO2 content meters, makes the methyl silicate of addition and the mass ratio of decentralized silica
It is 0.2；Methyl silicate is added dropwise to modify the surface of hollow silicon dioxide, with SiO2 content meters, makes the positive silicic acid of addition
Methyl esters is 0.2 with the mass ratio of hollow silicon dioxide；Amount of alcohol is added for 0.5 times of water, and makes the concentration of coating liquid be
3wt%。
2nd, photovoltaic glass is prepared
Prepare photovoltaic glass B3：One layer of antireflective coating liquid A3 is sprayed on a glass substrate, then in 300 DEG C of drying,
600 DEG C of tempering 5min obtain the antireflection film layer that thickness is 120nm.
Embodiment 4
1st, antireflective coating liquid is prepared
Method according to embodiment 1 prepares antireflective coating liquid A4, and difference is：By decentralized silica and hollow two
KH550 is added dropwise after silica mixing to modify the surface of decentralized silica and hollow silicon dioxide, with SiO2 contents
Meter, makes decentralized silica and hollow silicon dioxide gross mass be 2 with the mass ratio of the Silane coupling agent KH550 of addition；Plus
It is 2 times of water to enter amount of alcohol, and makes the concentration of coating liquid be 2wt%.Wherein, the solid content of decentralized Ludox is accounted for and always contained admittedly
The 30wt% of amount, the solid content of hollow Ludox accounts for the 30wt% of total solid content, and linear Ludox, linear titanium colloidal sol, linear aluminium are molten
Glue, the solid content of linear zirconium colloidal sol respectively account for the 10% of total solid content, ethylene glycol, surfactant Qula logical -100, wetting agent respectively
The mass fraction that BYK346 accounts for coating liquid respectively is 0.5%, 0.2%, 0.3%.
2nd, photovoltaic glass is prepared
Prepare photovoltaic glass B4：One layer of antireflective coating liquid A4 is sprayed on a glass substrate, then in 200 DEG C of drying,
700 DEG C of tempering 2min obtain the antireflection film layer that thickness is 90nm.
Embodiment 5
1st, antireflective coating liquid is prepared
Method according to embodiment 1 prepares antireflective coating liquid A5, and difference is：By decentralized silica and hollow two
KH550 is added dropwise after silica mixing to modify the surface of decentralized silica and hollow silicon dioxide, with SiO2 contents
Meter, makes decentralized silica and hollow silicon dioxide gross mass be 10 with the mass ratio of the Silane coupling agent KH550 of addition；Plus
It is 2 times of water to enter amount of alcohol, and makes the concentration of coating liquid be 5wt%.Wherein, the solid content of decentralized Ludox is accounted for and always contained admittedly
The 60wt% of amount, the solid content of hollow Ludox accounts for the 30wt% of total solid content, and linear Ludox, linear titanium colloidal sol, linear aluminium are molten
Glue, the solid content of linear zirconium colloidal sol respectively account for the 2.5% of total solid content, ethylene glycol, surfactant Qula logical -100, wetting respectively
The mass fraction that agent BYK346 accounts for coating liquid respectively is 0.5%, 0.2%, 0.3%.
2nd, photovoltaic glass is prepared
Prepare photovoltaic glass B5：One layer of antireflective coating liquid A5 is sprayed on a glass substrate, then in 200 DEG C of drying,
500 DEG C of tempering 10min obtain the antireflection film layer that thickness is 120nm.
Embodiment 6
1st, antireflective coating liquid is prepared
Method according to embodiment 1 prepares antireflective coating liquid A6, and difference is：By decentralized silica and hollow two
Methyl silicate is added dropwise after silica mixing to modify the surface of decentralized silica and hollow silicon dioxide, with SiO2
Content meter, makes decentralized silica and hollow silicon dioxide gross mass be 2 with the mass ratio of the methyl silicate of addition；Add
Amount of alcohol is 0.5 times of water, and makes the concentration of coating liquid be 4wt%.Wherein, the solid content of decentralized Ludox is accounted for and always contained admittedly
The 30wt% of amount, the solid content of hollow Ludox accounts for the 60wt% of total solid content, and linear Ludox, linear titanium colloidal sol, linear aluminium are molten
Glue, the solid content of linear zirconium colloidal sol respectively account for the 2.5% of total solid content, ethylene glycol, surfactant Qula logical -100, wetting respectively
The mass fraction that agent BYK346 accounts for coating liquid respectively is 0.5%, 0.2%, 0.3%.
2nd, photovoltaic glass is prepared
Prepare photovoltaic glass B6：One layer of antireflective coating liquid A6 is sprayed on a glass substrate, then in 200 DEG C of drying,
500 DEG C of tempering 10min obtain the antireflection film layer that thickness is 115nm, and then on antireflective coating surface, coating mol ratio is 1：1：1
Titanium colloidal sol, zirconium colloidal sol and Alumina gel, solidification obtains the composite oxides function of titanium dioxide, zirconium dioxide, alundum (Al2O3)
Layer, the thickness of oxide functional layer is 10nm.
Embodiment 7
1st, antireflective coating liquid is prepared
Method according to embodiment 1 prepares antireflective coating liquid A7, and difference is：By decentralized silica and hollow two
Methyl silicate is added dropwise after silica mixing to modify the surface of decentralized silica and hollow silicon dioxide, with SiO2
Content meter, makes decentralized silica and hollow silicon dioxide gross mass be 10 with the mass ratio of the methyl silicate of addition；Plus
It is 0.5 times of water to enter amount of alcohol, and makes the concentration of coating liquid be 3wt%.Wherein, the solid content of decentralized Ludox accounts for total solid
The 50wt% of content, the solid content of hollow Ludox accounts for the 40wt% of total solid content, linear Ludox, linear titanium colloidal sol, linear aluminium
Colloidal sol, the solid content of linear zirconium colloidal sol respectively account for the 2.5% of total solid content, ethylene glycol, surfactant Qula logical -100, profit respectively
The mass fraction that humectant BYK346 accounts for coating liquid respectively is 0.1%, 0.05%, 0.05%.
2nd, photovoltaic glass is prepared
Prepare photovoltaic glass B7：One layer of antireflective coating liquid A7 is sprayed on a glass substrate, then in 200 DEG C of drying,
500 DEG C of tempering 10min obtain the antireflection film layer that thickness is 110nm, and then on antireflective coating surface, coating mol ratio is 1：1：1
Titanium colloidal sol, zirconium colloidal sol and Alumina gel, solidification obtains the composite oxides function of titanium dioxide, zirconium dioxide, alundum (Al2O3)
Layer, the thickness of functional layer is 20nm.
Embodiment 8
1st, antireflective coating liquid is prepared
Be the decentralized Ludox of 10nm by particle diameter, particle diameter be the hollow Ludox of 50nm, linear Ludox, linear titanium it is molten
Glue, linear Alumina gel, linear zirconium colloidal sol, ethylene glycol, surfactant Qula logical -100, wetting agent BYK346 mixing, Ran Houjia
Enter the water and ethanol of phase homogenous quantities, the solids level concentration for adjusting coating liquid is 3wt%, that is, obtain antireflective coating liquid A8.Wherein,
The solid content of decentralized Ludox accounts for the 40wt% of total solid content, and the solid content of hollow Ludox accounts for the 50wt% of total solid content, line
Shape Ludox, linear titanium colloidal sol, linear Alumina gel, the solid content of linear zirconium colloidal sol respectively account for the 2.5% of total solid content, second two respectively
The mass fraction that alcohol, surfactant Qula logical -100, wetting agent BYK346 account for coating liquid respectively is 1%, 0.5%, 0.5%.
2nd, photovoltaic glass is prepared
Prepare photovoltaic glass B8：One layer of antireflective coating liquid A8 is sprayed on a glass substrate, then in 200 DEG C of drying,
500 DEG C of tempering 10min obtain the antireflection film layer that thickness is 110nm, and then on antireflective coating surface, coating mol ratio is 1：1：1
Titanium colloidal sol, zirconium colloidal sol and Alumina gel, solidification obtains the composite oxides function of titanium dioxide, zirconium dioxide, alundum (Al2O3)
Layer, the thickness of functional layer is 5nm.
Comparative example 1
Prepare antireflective coating liquid CA1：To disperse shape Ludox to be coating liquid, the solid content of the decentralized Ludox is
3%, ethanol is solvent, and plus accounts for the surfactant Triton X-100 that total coating liquid quality is 1%.
Prepare photovoltaic glass CB1：Antireflective coating liquid CA1 is coated with a glass substrate, is carried out at tempering at 600 DEG C
Reason, process time is 5min.
Comparative example 2
Antireflective coating liquid CA2 is prepared using the method in CN102531406A embodiments 1；Then apply on a glass substrate
Cloth antireflective coating liquid CA2, carries out tempering treatment at 600 DEG C, and process time obtains photovoltaic glass CB2 for 5min.
Performance test
（1）Light transmittance is tested
Using LCD-5200 photoelectric characteristic testers, 380-780nm wave bands are scanned, according to disclosed in GBT 2680-1994
Each wave band distribution character of sunshine, tests the light transmittance of each photovoltaic glass B1-B8 and CB1-CB2, 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 is tested
Using wet cotton（The liquid detergent aqueous solution of 5wt%）Rub each 10000 times of each photovoltaic glass B1-B8 and CB1-CB2.
Pressure is 200 g/cm2, and rubbing angle is 90 degree.After 10000 frictions, the light transmittance of each glass sample is detected.If each glass
Sample transmittance reduced value is designated as OK within 0.5%, is otherwise NG.The results are shown in Table 1.
（3）Pencil hardness test
Pencil hardness survey is carried out to each photovoltaic glass B1-B8 and CB1-CB2 using method disclosed in GB 6739-2006
Examination.The results are shown in Table 1.
（4）Salt spray resistance is tested
Using GB/T 18912-2002/IEC 61701:1995 (photovoltaic module salt spray corrosion tests).
Neutral salt spray 96 hours, salt fog composition is 5% NaCl solution.If the light transmittance of sample is reduced after salt mist experiment
Value is within 0.5%, 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 | |
| B1 | 3% | OK | 5 | OK |
| B2 | 3.2% | OK | 5 | OK |
| B3 | 3% | OK | 5 | OK |
| B4 | 3.1% | OK | 5 | OK |
| B5 | 2.9% | OK | 5 | OK |
| B6 | 3.3% | OK | 6 | OK |
| B7 | 3.1% | OK | 6 | OK |
| B8 | 3.2% | OK | 6 | OK |
| CB1 | 2.5% | NG | 2 | NG |
| CB2 | 2.8% | NG | 3 | NG |
From table 1 it follows that being reached with the anti-reflection rate that the antireflective coating that antireflective coating liquid of the invention is prepared has
It is good to more than 3%, pencil hardness more than 5, rub resistance and salt spray resistance；And prepared with the antireflective coating liquid of comparative example 1
Antireflective coating anti-reflection rate for 2.5%, pencil hardness be that 2, anti-wear performance and salt spray resistance are poor；With the antireflective of comparative example 2
The anti-reflection rate of the antireflective coating that coating liquid is prepared is that 2.8%, pencil hardness is that 3, anti-wear performance and salt spray resistance are poor；Cause
This, illustrates that the antireflective coating prepared with antireflective coating liquid of the invention has that anti-reflection rate high, anti-wear performance be good, pencil
Hardness is high, salt spray resistance is good.
Presently preferred embodiments of the present invention is the foregoing is only, is not intended to limit the invention, it is all in essence of the invention
Any modification, equivalent and improvement made within god and principle etc., should be included within the scope of the present invention.
Claims (19)
1. a kind of antireflective coating liquid, it is characterised in that the antireflective coating liquid includes that decentralized Ludox, hollow silicon are molten
Glue, linear colloidal sol, additive and solvent；On the basis of the total solid content of antireflective coating liquid, the decentralized Ludox contains
It is 30-60wt% to measure, and the content of the hollow Ludox is 30-60wt%, and the content of the linear colloidal sol is 10-40wt%；With
On the basis of the gross mass of the antireflective coating liquid, the content of the additive is 0.2-2wt%；The decentralized Ludox
Average grain diameter of the average grain diameter less than the hollow Ludox.
2. antireflective coating liquid according to claim 1, it is characterised in that the decentralized Ludox and the hollow silicon
The weight ratio of colloidal sol is 0.5-1：1.
3. antireflective coating liquid according to claim 1, it is characterised in that the average grain diameter of the decentralized Ludox is
2-20nm；The average grain diameter of the hollow Ludox is 20-100nm.
4. antireflective coating liquid according to claim 1, it is characterised in that the additive is that coalescents, surface are lived
At least one in property agent, thickener and wetting agent.
5. antireflective coating liquid according to claim 1, it is characterised in that the solid content of the antireflective coating liquid is 2-
5wt%。
6. antireflective coating liquid according to claim 1, it is characterised in that the linear colloidal sol is linear Ludox, line
At least one in shape titanium colloidal sol, linear Alumina gel and linear zirconium colloidal sol.
7. antireflective coating liquid according to claim 1, it is characterised in that also include surface in the antireflective coating liquid
Inorganic agent, the surface conditioning agent is one or more in silane coupler, tetraethyl orthosilicate and methyl silicate.
8. a kind of preparation method of the antireflective coating liquid described in claim 1-7 any one, it is characterised in that the method bag
Include following steps：Decentralized Ludox, hollow Ludox, linear colloidal sol, additive and solvent are well mixed and obtain anti-reflection
Penetrate coating liquid.
9. preparation method according to claim 8, it is characterised in that before mixing to decentralized Ludox and hollow silicon
Colloidal sol is surface-treated.
10. a kind of photovoltaic glass, it is characterised in that the photovoltaic glass includes glass substrate and positioned at the glass substrate surface
Antireflective coating, the antireflective coating by antireflective coating liquid coating form；The antireflective coating liquid is appointed for claim 1-7
Antireflective coating liquid described in meaning one.
11. photovoltaic glass according to claim 10, it is characterised in that the glass substrate has matte, the anti-reflection
Film is penetrated to be formed on matte.
12. photovoltaic glass according to claim 11, it is characterised in that in the layer function of antireflective coating coating surface one
Property film layer, the feature film layer is at least one formation in silica, titanium dioxide, zirconium dioxide and alundum (Al2O3)
Film layer.
13. photovoltaic glass according to claim 12, it is characterised in that the thickness of the feature film layer is 5-20nm.
14. a kind of preparation methods of photovoltaic glass, it is characterised in that coat antireflective coating liquid on a glass substrate, then dry
Dry, curing process obtains the photovoltaic glass with antireflective coating, and the antireflective coating liquid is claim 1-7 any one institute
The antireflective coating liquid stated.
15. preparation methods according to claim 14, it is characterised in that described to be applied to lifting, roller coat, dip-coating, showering
With the one kind in spraying.
16. preparation methods according to claim 14, it is characterised in that also include at tempering after the curing process
Reason step.
17. preparation methods according to claim 16, it is characterised in that the temperature of the drying is 20-300 DEG C；It is described
The temperature of tempering treatment is 500-700 DEG C, and the time is 2-10min；The temperature of the curing process is 300-500 DEG C, and the time is
30-120min。
18. preparation methods according to claim 14, it is characterised in that in the coating surface functional membrane of antireflective coating
Layer.
A kind of 19. solar cell modules, the solar cell module includes the transparent glass, the electricity that stack gradually from top to bottom
Pond piece and backboard；Characterized in that, photovoltaic glass of the transparent glass as described in claim any one of 10-13.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101184815A (en) * | 2005-06-02 | 2008-05-21 | 旭硝子株式会社 | Dispersion containing hollow SiO2, coating composition and substrate with antireflection coating film |
| CN101786801A (en) * | 2009-01-22 | 2010-07-28 | 中国科学院理化技术研究所 | Super-hydrophilic anti-fog anti-reflection coating and preparation method and application thereof |
| CN103057194A (en) * | 2011-10-24 | 2013-04-24 | 比亚迪股份有限公司 | Antireflection film and preparation method thereof |
| CN103305036A (en) * | 2013-06-18 | 2013-09-18 | 武汉绿凯科技有限公司 | POSS (Polysilsesquioxane)-containing antireflective film coating liquid and preparation method and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011088787A (en) * | 2009-10-22 | 2011-05-06 | Hitachi Maxell Ltd | Composition for antireflection film, antireflection film, method for producing antireflection film, and substrate with antireflection film |
-
2013
- 2013-11-26 CN CN201310606013.9A patent/CN104671672B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101184815A (en) * | 2005-06-02 | 2008-05-21 | 旭硝子株式会社 | Dispersion containing hollow SiO2, coating composition and substrate with antireflection coating film |
| CN101786801A (en) * | 2009-01-22 | 2010-07-28 | 中国科学院理化技术研究所 | Super-hydrophilic anti-fog anti-reflection coating and preparation method and application thereof |
| CN103057194A (en) * | 2011-10-24 | 2013-04-24 | 比亚迪股份有限公司 | Antireflection film and preparation method thereof |
| CN103305036A (en) * | 2013-06-18 | 2013-09-18 | 武汉绿凯科技有限公司 | POSS (Polysilsesquioxane)-containing antireflective film coating liquid and preparation method and application thereof |
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