阅读说明：本技术 一种玻璃镀膜液及功能膜制备方法 (Glass coating liquid and functional film preparation method ) 是由 刘子英 田君伟 吕俊霞 于 2019-11-05 设计创作，主要内容包括：本发明公开了一种玻璃镀膜液及功能膜制备方法,所述玻璃镀膜液包括纳米分散液A和纳米分散液B,纳米分散液A主要包括以下组分：一维纳米无机颗粒、溶胶增稠剂、溶胶无机粘合剂、乙醇、甲醇和去离子水；纳米分散液B主要包括以下组分：球形或类球形纳米颗粒、溶胶增稠剂、溶胶无机粘合剂、乙醇、甲醇和去离子水；所述功能膜制备方法包括制备制备纳米分散液A和B以及在玻璃表面涂布玻璃镀膜液的步骤。本发明制备过程及应用方法简单,可常温干燥固化、成膜效果好、硬度高、透光率增加、耐受紫外线照射；可用于增透膜已经发生破损的玻璃表面进行抛光后重新涂布成膜,延长了光伏组件和玻璃的使用寿命。(The invention discloses a glass coating liquid and a functional film preparation method, wherein the glass coating liquid comprises a nano dispersion liquid A and a nano dispersion liquid B, and the nano dispersion liquid A mainly comprises the following components: one-dimensional inorganic nanoparticles, a sol thickener, a sol inorganic adhesive, ethanol, methanol and deionized water; the nano dispersion liquid B mainly comprises the following components: spherical or spheroidal nano-particles, a sol thickener, a sol inorganic adhesive, ethanol, methanol and deionized water; the preparation method of the functional film comprises the steps of preparing nanometer dispersion liquid A and nanometer dispersion liquid B and coating glass coating liquid on the surface of glass. The preparation process and the application method are simple, the coating can be dried and cured at normal temperature, the film forming effect is good, the hardness is high, the light transmittance is increased, and the coating can resist ultraviolet irradiation; the glass polishing solution can be used for polishing the surface of glass with a damaged antireflection film and then recoating the glass surface to form a film, so that the service lives of a photovoltaic module and the glass are prolonged.)

1. The glass coating liquid is characterized by comprising a nano dispersion liquid A and a nano dispersion liquid B, wherein:

the nano dispersion liquid A comprises the following components in parts by weight: 0.6-1.5 parts of one-dimensional nano inorganic particles, 1-9 parts of sol thickening agent, 2-6 parts of sol inorganic adhesive, 68.5-69.4 parts of mixed solution of ethanol and methanol and 15-27 parts of deionized water; the solid content of the nano dispersion liquid A is 0.9-3.0%;

the nano dispersion liquid B comprises the following components in parts by weight: 1-3 parts of spherical or sphere-like nano particles, 1-5 parts of sol thickening agent, 1-5 parts of sol inorganic adhesive, 67-69 parts of mixed solution of ethanol and methanol and 20-28 parts of deionized water; the solid content of the nano dispersion liquid B is 1.5-4.0%.

2. The glass coating solution of claim 1, wherein: the sol thickener is alumina sol or titania sol, and the inorganic sol adhesive includes silicic acid sol.

3. The glass coating solution of claim 1, wherein: the one-dimensional nano inorganic particles in the nano dispersion liquid A are needle-shaped nano SiO₂Needle-like nano TiO₂At least one of nano ZnO crystal whisker, nano hydroxyapatite, nano needle-shaped SiC and nano silver wire.

4. The glass coating solution of claim 3, wherein: the length of the one-dimensional nano inorganic particles is 0.2-2.0 um.

5. The glass coating solution of claim 4, wherein: the one-dimensional inorganic nanoparticles are a mixture of 0.2-0.5 um one-dimensional nanoparticles N1 and 0.6-2.0 um one-dimensional nanoparticles N2, and the weight ratio of N1 to N2 is 1: 0.2-5.0.

6. The glass coating solution of claim 1, wherein: the spherical or sphere-like nano particles in the nano dispersion liquid B are nano SiO₂Anatase type nano TiO₂Nano ZrO2₂Nano MgO, nano aluminum doped zinc oxide AZO and nano gamma-Al₂O₃At least one of (1).

7. A method for preparing a functional film, wherein the functional film is formed by coating the glass coating liquid of any one of claims 1 to 6 on glass, comprising the following steps:

s1, preparing a nano dispersion liquid A and a nano dispersion liquid B respectively;

s2, coating the nano dispersion liquid A on the surface of glass, and naturally drying to form a first film layer; wherein the nano dispersion liquid A is coated on the glass with the solid content of 0.1-1.0 g/m²，

S3, continuously coating the nano dispersion liquid B on the first film layer, and naturally drying to form an anti-reflection functional film; wherein the nano dispersion liquid B is coated on the glass with the solid content of 0.21-1.0 g/m²。

8. The method for producing a functional film according to claim 7, wherein: step S1 specifically includes the following steps:

s11, preparation of silicic acid sol: dissolving tetraethyl orthosilicate in ethanol, adding the tetraethyl orthosilicate into a hydrochloric acid aqueous solution with the pH of 2-3 under a stirring state, keeping the temperature of the solution at 20-50 ℃, stirring for 5-20 minutes, and then standing for 24 hours;

s12, preparing a sol thickener: adding ethanol and deionized water into titanate or aluminum alkoxide, mixing, heating to 60-75 ℃, keeping the temperature, and stirring for 60-240 minutes;

s13, preparing nano dispersion liquid A: mixing one-dimensional nano inorganic particles, a sol thickener, a mixed solution of ethanol and methanol and deionized water, stirring and dispersing for 5-10 min, adding silicic acid sol, and stirring uniformly;

s14, preparing nano dispersion liquid B: mixing the nano inorganic oxide powder, the sol thickener, the mixed solution of ethanol and methanol and deionized water, stirring and dispersing for 10-30 min, adding the silicic acid sol, and stirring uniformly.

9. The method for preparing a functional film according to claim 7, wherein: the coating manner in steps S2 and S3 is curtain coating or spray coating.

Technical Field

The invention relates to the technical field of glass optical film materials, and in particular relates to a glass coating liquid and application thereof.

Background

The energy shortage and the environmental protection pressure in the world promote the rapid growth of the solar photovoltaic module market in all countries in the world. The crystalline silicon solar cell module is a core part in a solar power generation system, is formed by connecting a plurality of single cells in series and in parallel and tightly packaging, and comprises front plate glass, a packaging adhesive film, a cell string, a back plate, a junction box and the like. With the continuous optimization of solar photovoltaic modules, the conversion efficiency of crystalline silicon cell plates is close to the limit value, and glass is used as an important component of the module and plays a role in transmitting light and protecting a power generation main body (cell plate), wherein the front plate glass is generally ultra-white toughened glass, the light transmittance of 550nm reaches more than 91%, the light transmittance of 550nm of rear plate glass reaches more than 88%, and in order to further increase the light receiving quantity and the power generation quantity of the cell plate, technical measures are required to be further adopted to increase the light transmittance of the glass and reduce the surface reflectivity of the glass.

The existing antireflection films for photovoltaic glass and building glass mostly adopt dip-coating of film forming liquid and high-temperature curing processes, the main components of the common glass antireflection film forming liquid are silica sol and film forming auxiliary agents, glass is soaked in the film forming liquid and is pulled, and then the glass is dried and cured at 300-700 ℃ for 5-30 minutes to obtain the single-layer antireflection film. The high-temperature process is used for removing water and a high-molecular film forming agent in the silicic acid sol to form a porous film with silicon dioxide as a main component, and the process is suitable for the production process of glass, and cannot realize the setting of antireflection films of the installed building glass and the solar cell module with a finished laminated layer. In addition, the anti-reflection film layer of the glass is generally arranged towards the air, and can be partially disintegrated under the long-term action of water vapor, cold and hot alternation and microorganisms, so that the phenomena of whitening and flowering on the surface of the glass are caused.

The existing antireflection film manufacturing patent processes are not suitable for construction of laying antireflection films again on installed building glass and photovoltaic modules due to the fact that high-temperature treatment is needed. For example, Chinese patent CN107986636A, a manufacturing method of a self-cleaning film of a photovoltaic module, adopts 35-70 parts of inorganic oxide and 20-60 parts of functional nano-scale dioxide particles to be mixed, and after spraying on the surface of glass before leaving factory, the mixture is cured at the temperature of 200-; chinese patent CN109575649A "A solar glass antireflection coating with an anti-dust function, a preparation method thereof and an anti-dust high antireflection solar glass" comprises an organic adhesive and functional nano-particle components: the functional nano particle component comprises 10 parts of needle-rod-shaped nano ATO or/and carbon nano tube, 10 parts of nano NTO, and the higher proportion of needle-rod-shaped nano particles influences the light trapping and anti-reflection effect of the film layer, and the coating also needs to be baked and cured at 80-250 ℃, and finally is tempered with the glass base material at 500-700 ℃ for 3-5 min, and the processing conditions are strict.

Disclosure of Invention

The invention aims to solve the technical problem of providing a glass coating liquid and application thereof, and aims to solve the problems that the temperature condition required by the existing production process is too high, and the glass cannot be subjected to coating construction again after an anti-reflection film fails, so that the anti-reflection rate is improved, the process steps and the production conditions are simplified, and the effects of good film forming effect and good adhesion are achieved.

In order to solve the technical problems, the invention provides a glass coating liquid and a preparation method of a functional film.

A glass coating liquid comprises a nano dispersion liquid A and a nano dispersion liquid B, wherein:

the nano dispersion liquid A comprises the following components in parts by weight: 0.6-1.5 parts of one-dimensional nano inorganic particles, 1-9 parts of sol thickening agent, 2-6 parts of sol inorganic adhesive, 68.5-69.4 parts of mixed solution of ethanol and methanol and 15-27 parts of deionized water; the solid content of the nano dispersion liquid A is 0.9-3.0%.

The nano dispersion liquid B comprises the following components in parts by weight: 1-3 parts of spherical or sphere-like nano particles, 1-5 parts of sol thickening agent, 1-5 parts of sol inorganic adhesive, 67-69 parts of mixed solution of ethanol and methanol and 20-28 parts of deionized water; the solid content of the nano dispersion liquid B is 1.5-4.0%.

Further, the sol thickener is alumina sol or titanium dioxide sol, and the sol inorganic binder comprises silicic acid sol.

Further, the one-dimensional nano inorganic particles in the nano dispersion liquid A are at least one of needle-shaped nano SiO2, needle-shaped nano TiO2, nano ZnO crystal whisker, nano hydroxyapatite, nano needle-shaped SiC and nano silver wire.

Further, the length of the one-dimensional nano inorganic particles is 0.2-2.0 um.

Furthermore, the one-dimensional inorganic nanoparticles are a mixture of 0.2-0.5 um one-dimensional nanoparticles N1 and 0.6-2.0 um one-dimensional nanoparticles N2, and the weight ratio of N1 to N2 is 1: 0.2-5.0.

Further, the spherical or sphere-like nanoparticles in the nano dispersion liquid B are at least one of nano SiO2, anatase type nano TiO2, nano ZrO2, nano MgO, nano aluminum doped zinc oxide AZO and nano gamma-Al 2O 3.

The invention also provides a preparation method of the functional film, the functional film is formed by coating the glass coating liquid on glass, and the preparation method specifically comprises the following steps:

s1, preparing a nano dispersion liquid A and a nano dispersion liquid B respectively;

s2, coating the nano dispersion liquid A on the surface of glass, and naturally drying to form a first film layer; wherein the nano dispersion liquid A is coated on the glass with the solid content of 0.1-1.0 g/m²，

S3, continuously coating the nano dispersion liquid B on the first film layer, and naturally drying to form an anti-reflection functional film; wherein the nano dispersion liquid B is coated on the glass with the solid content of 0.21-1.0 g/m²。

Further, step S1 specifically includes the following steps:

s11, preparation of silicic acid sol: dissolving tetraethyl orthosilicate in ethanol, adding the tetraethyl orthosilicate into a hydrochloric acid aqueous solution with the pH of 2-3 under a stirring state, keeping the temperature of the solution at 20-50 ℃, stirring for 5-20 minutes, and then standing for 24 hours;

s12, preparing a sol thickener: adding ethanol and deionized water into titanate or aluminum alkoxide, mixing, heating to 60-75 ℃, keeping the temperature, and stirring for 60-240 minutes;

s13, preparing nano dispersion liquid A: mixing one-dimensional nano inorganic particles, a sol thickener, a mixed solution of ethanol and methanol and deionized water, stirring and dispersing for 5-10 min, adding silicic acid sol, and stirring uniformly;

s14, preparing nano dispersion liquid B: mixing the nano inorganic oxide powder, the sol thickener, the mixed solution of ethanol and methanol and deionized water, stirring and dispersing for 10-30 min, adding the silicic acid sol, and stirring uniformly.

Furthermore, the coating mode is curtain coating or spraying.

Due to the adoption of the technical scheme, the technical progress of the invention is as follows.

The glass coating liquid provided by the invention is an aqueous dispersion liquid composition, comprises a nano dispersion liquid A and a nano dispersion liquid B, can be used for coating construction on the outer surface of building glass and the surfaces of front plate glass and rear plate glass of a component of a photovoltaic power station, is dried and cured under a normal temperature condition, has simple operation steps, and has the advantages of ultraviolet irradiation resistance, high film hardness and high light transmittance. For glass and photovoltaic modules with the problem of antireflection film disintegration, the surfaces of the glass and the photovoltaic modules can be polished and coated with film forming liquid again to obtain antireflection functional films with good film forming effect and good adhesion, so that the service lives of the photovoltaic modules and the glass are prolonged, and the economic expenditure is reduced.

Drawings

FIG. 1 is a graph showing the EQE test results of two comparative examples in which the glass coating solutions prepared in examples 1 to 7 are coated on a photovoltaic module;

FIG. 2 is a surface view of an antireflective coating formed on a photovoltaic module using example 1;

FIG. 3 is a surface view of an antireflective coating formed on a photovoltaic module using comparative example 2.

Detailed Description

The invention provides a glass coating liquid and application thereof, wherein the coating liquid is an inorganic nano water-based film forming liquid and comprises a nano dispersion liquid A and a nano dispersion liquid B.

The nano dispersion liquid A comprises the following components in parts by weight: 0.6-1.5 parts of one-dimensional nano inorganic particles, 1-9 parts of sol thickening agent, 2-6 parts of sol inorganic adhesive, 68.5-69.4 parts of mixed solution of ethanol and methanol and 15-27 parts of deionized water. The solid content of the nano dispersion liquid A is 0.9-3.0%.

In the invention, the one-dimensional inorganic nanoparticles in the nano dispersion liquid A are monodisperse one-dimensional inorganic nanoparticles with the length of 0.2-2.0 um and comprise acicular nano SiO₂Needle-like nano TiO₂Nano ZnO crystal whisker, nano hydroxyapatite and nanoAt least one of needle-shaped silicon carbide and nano silver wires. The monodisperse one-dimensional inorganic nanoparticles comprise one-dimensional nanoparticles N1 with the length of preferably 0.2-0.5 um and one-dimensional inorganic nanoparticles N2 with the length of preferably 0.6-2.0 um, wherein the weight ratio of the one-dimensional nanoparticles N1 to the one-dimensional nanoparticles N2 is preferably 1: 0.2-5.0, and more preferably 1.0: 1.0 to 3.0. The too short one-dimensional particles can not play a role in separating the surface of the glass substrate, and the longer one-dimensional nanoparticles N2 and the shorter one-dimensional nanoparticles N1 are mixed, so that the uniformity of separation of the surface of the substrate can be improved, the uniform spreading of the low-viscosity nano dispersion liquid on the surface of the glass can be facilitated, and high-precision spraying and dip-coating lifting processes are not needed.

The nano dispersion liquid B comprises the following components in parts by weight: 1-3 parts of spherical or sphere-like nano particles, 1-5 parts of sol thickening agent, 1-5 parts of sol inorganic adhesive, 67-69 parts of mixed solution of ethanol and methanol and 20-28 parts of deionized water. The solid contents of the nano dispersion liquid B are respectively as follows: 1.5 to 4.0 percent.

The spherical or sphere-like nano particles in the nano dispersion liquid B are nano SiO₂Anatase type nano TiO₂Nano ZrO2₂Nano MgO, nano aluminum doped zinc oxide AZO and nano gamma-Al₂O₃At least one of (1).

The sol thickening agent in the nano dispersion liquid A and the nano dispersion liquid B is alumina sol or titanium dioxide sol, and the sol inorganic adhesive is silicic acid sol.

The glass coating liquid comprises the following specific preparation steps:

s1, preparation of silicic acid sol: dissolving tetraethyl orthosilicate in ethanol, adding the tetraethyl orthosilicate into hydrochloric acid aqueous solution with the pH of 2-3 under a stirring state, keeping the temperature of the solution at 20-50 ℃, stirring the solution for 5-20 minutes, and then standing the solution for 24 hours.

S2, preparing a sol thickener: and (3) adding ethanol and deionized water into titanate or aluminum alkoxide, mixing, heating to 60-75 ℃, keeping the temperature, and stirring for 60-240 minutes. Commercially available alumina sols or titania sols can also be used to adjust the solids content to the desired concentration.

S3, preparing nano dispersion liquid A: and mixing monodisperse one-dimensional nano inorganic particles, an alumina or titanium dioxide sol thickener with the solid content of 10%, a mixed solution of ethanol and methanol and deionized water, stirring and dispersing at 1000-2000 rpm for 5-10 min, adding a silicic acid sol with the solid content of 10%, and uniformly stirring.

S4, preparing nano dispersion liquid B: mixing inorganic oxide nanopowder, a thickening agent of alumina or titanium dioxide sol with solid content of 10%, a mixed solution of ethanol and methanol and deionized water, stirring and dispersing at a high speed of 5000-10000 rpm for 10-30 min, adding silicic acid sol with solid content of 10%, and stirring uniformly.

The invention also provides an application method of the glass coating liquid, namely a functional film is formed by coating the glass coating liquid on the surface of glass, and the preparation method of the functional film is as follows.

Coating the film coating liquid on the surface of the glass to form an anti-reflection functional film so as to improve the light transmittance of the glass. Firstly, the nano dispersion liquid A is coated on the surface of glass, preferably by curtain coating, and the coating solid amount per unit area is 0.1-1.0 g/m²Preferably, the coating is 0.1 to 0.5g/m²After natural drying, the nano dispersion B is continuously coated, preferably by curtain coating, and the coating solid amount per unit area is 0.21-1.0 g/m²Preferably 0.21 to 0.80g/m²And naturally drying to form a new anti-reflection functional film on the surface of the glass and increase the light transmittance of the glass.

The film forming liquid provided by the invention is an aqueous dispersion liquid composition, and a layer of sphere-like nano-particle dispersion liquid is continuously coated and dried to form a film after the dispersion liquid containing one-dimensional nano inorganic particles is coated and dried, so that a uniform and consistent porous film can be formed under the condition that an organic dispersing agent and a high-molecular film forming agent are not added, the film is uniform and has no cracks, the hardness of the film is more than 2H, and the film can resist ultraviolet irradiation and cannot be decomposed.

Polishing and removing the anti-reflection functional film after the anti-reflection functional film is damaged and loses efficacy by wind and sand impact, and repeatedly coating the anti-reflection functional film according to the application method, so that the service life of the anti-reflection glass is effectively prolonged, and the power generation efficiency of a photovoltaic power station and the light transmittance of building glass are improved.

The present invention will be described in further detail with reference to specific examples and comparative examples.