阅读说明：本技术 一种封孔剂及其制备方法和减反射镀膜液 (Hole sealing agent, preparation method thereof and antireflection coating liquid ) 是由 乔仁静 康正辉 游芳芳 于 2020-08-04 设计创作，主要内容包括：本发明公开了一种提高减反射镀膜抗脏污性能的封孔剂及其制备方法和一种减反射镀膜液,以质量百分含量计,所述封孔剂包括如下组分：低含氢硅油10-40％、烯丙基聚醚25-35％、溶剂30-60％、催化剂10-20ppm。本发明中制备的提高减反射镀膜玻璃抗污脏性能的封孔剂,其表面能低,添加到减反射镀膜液中,易迁移至膜层表面,高温固化过程中,可与镀膜液中的有机硅树脂交联,形成致密结构,进而在膜层表面起到封孔的作用,降低EVA胶膜、密封硅胶等介质与膜层表面基团的结合力,将其应用于减反射镀膜中在保证膜层高透过率的基础上,提供了优异的抗脏污性能。(The invention discloses a sealant for improving the anti-fouling performance of an antireflection coating, a preparation method thereof and an antireflection coating liquid, wherein the sealant comprises the following components in percentage by mass: 10-40% of low hydrogen silicone oil, 25-35% of allyl polyether, 30-60% of solvent and 10-20ppm of catalyst. The hole sealing agent for improving the anti-fouling performance of the anti-reflection coated glass, which is prepared by the invention, has low surface energy, is added into the anti-reflection coating liquid, is easy to migrate to the surface of the film layer, can be crosslinked with organic silicon resin in the coating liquid in a high-temperature curing process to form a compact structure, further plays a hole sealing role on the surface of the film layer, reduces the binding force between media such as EVA (ethylene vinyl acetate) glue films and sealing silica gel and the like and the surface group of the film layer, and provides excellent anti-fouling performance on the basis of ensuring the high transmittance of the film layer when being applied to the anti-reflection coating.)

1. The hole sealing agent is characterized by comprising the following components in percentage by mass:

2. the sealant according to claim 1, wherein the sealant further comprises 0 to 5% by mass of a fluorine-containing acrylate.

3. The sealant according to claim 2, wherein the mass ratio of the allyl polyether to the fluoroacrylate is 30 to 80: 1.

4. the sealant according to claim 2, wherein the fluoroacrylate is one or more of hexafluorobutyl methacrylate, trifluoroethyl acrylate, and trifluorobutyl methacrylate.

5. The sealant according to claim 1, wherein the hydrogen content of the low hydrogen silicone oil is 0.1 to 1.0%.

6. The sealant according to claim 5, wherein the molar ratio of active hydrogen in the low hydrogen-containing silicone oil to C ═ C in the allyl polyether is 1: 0.5-1.2.

7. The hole sealing agent according to claim 1, wherein the solvent is an alcohol solvent and/or a high boiling point solvent, and the high boiling point solvent is one or more of propylene glycol methyl ether acetate, propylene glycol methyl ether, propylene glycol diacetate and butyl acetate.

8. A method of preparing the sealant according to claim 1, wherein the method of preparing the sealant comprises the steps of:

(1) adding low-hydrogen silicone oil into a solvent, stirring, introducing inert gas, and replacing air in the system;

(2) under the protection of inert gas, heating the reaction system in the step (1) to 80-120 ℃, mixing allyl polyether and a catalyst in proportion, controlling the proportion of the allyl polyether to fluoroacrylate, slowly dropwise adding the mixed solution of the allyl polyether and the catalyst and the fluoroacrylate into the reaction system in the step (1), after dropwise adding, keeping the temperature for reaction, and cooling to obtain the hole sealing agent.

9. The method for preparing the hole sealing agent according to claim 8, wherein the reaction temperature when the mixed solution of allyl polyether and the catalyst and the fluoroacrylate are added dropwise is 80 to 120 ℃, and the stirring speed is 80 to 200 rpm.

10. An antireflection coating liquid characterized by comprising the hole sealing agent according to any one of claims 1 to 7.

Technical Field

The invention relates to the technical field of solar cell module packaging glass and coating liquid, in particular to a hole sealing agent for improving anti-fouling performance of an anti-reflection coating, a preparation method thereof and an anti-reflection coating liquid comprising the hole sealing agent.

Background

Anti-reflection films (Anti-reflection coatings) have been widely used in the fields of display screens, optical lenses, high-energy laser windows, automobile and building glass, etc. as a surface optical treatment technology, and mainly have the effect of reducing the reflection of light by an interface. The preparation method of the anti-reflection film mainly comprises a chemical method, a physical method and a chemical physical method. The sol-gel method is the most common process at present, and has the main advantages of simple equipment, low cost and no need of specific vacuum environment at normal temperature and normal pressure. Because the weatherability of organosilicon polymer is poor, after the coating liquid is formed on the surface of glass and other materials, a film surface structure mainly comprising Si-O-Si is obtained through high-temperature calcination treatment.

The sol-gel method takes an organic silicon monomer with high chemical activity as a precursor, adds a solvent, water and an acid or alkali catalyst, forms a stable and transparent sol system in a solution through hydrolysis and condensation chemical reactions, and finally forms gel with a three-dimensional network structure after the sol is aged and slowly polymerized. Because the intermolecular acting force is weaker, after the antireflection coating liquid is coated on the surface of glass, the organic silicon prepolymer and the functional resin in the antireflection coating liquid are generally subjected to high-temperature calcination treatment to form a film.

The antireflection coating liquid in the current market mainly improves the glass transmittance by controlling a porous structure, but pollutants or water vapor in the environment easily enter the film or adhere to the surface of the film, so that the anti-fouling performance of the film is influenced. In addition, a large number of hydroxyl groups exist on the surface of the inorganic silicon dioxide anti-reflection film, and the surface activity is high, so that pollutants are easy to adhere to the film surface. In the production process of the photovoltaic module, the glass surface is easily adhered with module sealing silica gel or an EVA (ethylene vinyl acetate) adhesive film used in the packaging process, and the module sealing silica gel or the EVA adhesive film is remained on the surface of the film layer and is tightly combined with the film layer through high-temperature lamination and is difficult to remove.

In order to solve the above problems, the following two solutions are available:

firstly, Ti is added to form a super-hydrophilic structure, but if the addition amount is too low, the anti-fouling performance of the membrane surface cannot be effectively improved; however, when the amount of the surfactant added exceeds a certain value, the permeability of the film surface is remarkably decreased.

And secondly, forming a micro-nano structure on the surface of the glass by a sputtering method, and improving the anti-fouling performance of the film surface. Therefore, a technique capable of effectively improving the anti-fouling performance of the surface of the antireflection coating is needed.

Disclosure of Invention

In view of the above, in order to overcome the defects of the prior art, the present invention aims to provide a sealant for improving the anti-fouling performance of an anti-reflective coating, a preparation method thereof, and an anti-reflective liquid prepared by using the sealant.

In order to achieve the purpose, the invention adopts the following technical scheme:

the hole sealing agent comprises the following components in percentage by mass:

wherein the solvent is alcohol and/or high boiling point solvent, and the alcohol solvent is one or more of isopropanol, ethanol and n-butanol; the high boiling point solvent is one or more of propylene glycol methyl ether acetate, propylene glycol methyl ether, propylene glycol diacetate and butyl acetate. In some embodiments, isopropanol and propylene glycol methyl ether acetate may be used. Isopropanol and propylene glycol methyl ether acetate with higher boiling point are used, so that benzene solvents or acetone with higher toxicity is avoided, the boiling point of a mixed solvent in the reaction is higher than the reaction temperature, and meanwhile, reactants and products can be dissolved in the solvent.

The catalyst is a platinum-carrying catalyst, and the dosage of the catalyst accounts for 10-20ppm of the total reactant mass. The platinum-carrying catalyst comprises a speier or Karstedt catalyst, such as a chloroplatinic acid catalyst.

According to some preferred aspects of the present invention, the sealant further comprises 0-5% by mass of a fluorine-containing acrylate.

Preferably, the mass ratio of the allyl polyether to the fluorine-containing acrylate is 30-80: 1.

preferably, the fluorine-containing acrylate is one or more of hexafluorobutyl methacrylate, trifluoroethyl acrylate and trifluorobutyl methacrylate.

According to some preferred aspects of the present invention, the hydrogen content of the low hydrogen silicone oil is 0.1 to 1.0%. Specifically, the hydrogen content of the low hydrogen silicone oil is one or more of 0.10%, 0.18%, 0.2%, 0.3% and 0.80%. Such as heptamethyl tridylene oxide, the hydrogen content of which is 0.44 percent, belongs to low hydrogen silicone oil.

Preferably, the molar ratio of active hydrogen in the low hydrogen-containing silicone oil to C ═ C in the allyl polyether is 1: 0.5-1.2. More preferably, the molar ratio of active hydrogen in the low hydrogen silicone oil to C ═ C in the allyl polyether is 1: 1-1.2. The amount of allyl polyether is not preferably too high because of isomerization of the allyl polyether. When the amount of allyl polyether is increased, the conversion rate of the hydrogen-containing silicone oil is reduced. And the residual silicon-hydrogen bond is relatively active, which easily causes the stability of the product to be poor.

According to some preferred aspects of the invention, the allyl polyether is one or more of allyl alcohol polyoxyalkyl ether, allyl polyoxyethylene polyoxypropylene methyl ether, allyl polyoxyethylene polyoxypropylene propyl ether, allyl polyoxyethylene epoxy ether, allyl polyoxyethylene polyoxypropylene butyl ether, and allyl polyoxyethylene acetate.

The invention also provides a preparation method of the sealant for improving the anti-fouling performance of the antireflection coating, which comprises the following steps:

(1) adding low-hydrogen silicone oil into a mixed solvent of an alcohol solvent such as isopropanol and a high-boiling point solvent such as propylene glycol methyl ether acetate, stirring the solution at the rotating speed of 60-200rpm, introducing nitrogen into a reaction kettle, and displacing air in the system for 30min-1 h;

(2) heating the reaction system of the step (1) to 80-120 ℃ under the protection of nitrogen, and reacting according to the molar ratio of active hydrogen in the low-hydrogen silicone oil to C ═ C in the allyl polyether of 1: 0.5-1.2, mixing allyl polyether and platinum-carrying catalyst, and controlling the mass ratio of allyl polyether to fluorine-containing acrylate such as hexafluorobutyl acrylate to be 30-80: 1, the dosage of the platinum-carrying catalyst is 10-20ppm of the total mass of hydrogen-containing silicone oil, allyl polyether and hexafluorobutyl acrylate, the mixed solution of the allyl polyether and the platinum-carrying catalyst and fluorine-containing acrylate are simultaneously and slowly dripped into the reaction system in the step (1), the dripping time is controlled to be 0.5-1.5h, after the dripping is finished, the reaction is carried out for 5.0-8.0h by heat preservation, the temperature is reduced, the nitrogen introduction is stopped, and the hole sealing agent is obtained after the reaction is finished.

According to some preferred aspects of the present invention, the reaction temperature when the mixed solution of allyl polyether and catalyst and fluoroacrylate are added dropwise is 80 to 120 ℃, and the stirring speed is 80 to 200 rpm. The hydrosilylation reaction already occurs at the reaction temperature of 70 ℃, the higher the reaction temperature is, the higher the conversion rate of the hydrogen-containing silicone oil is, the reaction temperature is continuously increased, the conversion rate of the hydrogen-containing silicone oil is not greatly increased, and therefore, the temperature is optimally selected to be 85-95 ℃. The stirring speed affects the conversion rate of the hydrosilylation reaction, and the higher the stirring speed, the higher the conversion rate of the side reaction, so the conversion rate is optimally controlled to be 80-100 rpm.

The invention also provides an anti-reflection coating liquid for improving the anti-fouling performance of the anti-reflection coating glass, and the anti-reflection coating liquid comprises the hole sealing agent.

Due to the adoption of the technical scheme, compared with the prior art, the invention has the following benefits:

(1) the hole sealing agent for improving the anti-fouling performance of the antireflection coated glass is co-modified by polyether and polyester, has low surface energy, is added into antireflection coating liquid, is easy to migrate to the surface of a film layer, can be crosslinked with organic silicon resin in the coating liquid in a high-temperature curing process to form a compact structure, and can be used for sealing the antireflection film layer;

(2) according to the hole sealing agent prepared by the method, the allyl polyether modified silicone oil is grafted with the allyl polyether branched chain on the silicone oil, so that the hole sealing agent can have alcohol solubility, and the compatibility with film forming substances, pore forming agents and the like in a film coating liquid is improved;

(3) the hole sealing agent prepared by the invention grafts fluorine on the silicone oil branched chain, so that the hole sealing agent is further ensured to have low surface energy, and can be easily migrated to the surface of the membrane layer along with the volatilization of the solvent in the curing process.

Detailed Description

In order to make those skilled in the art better understand the technical solution of the present invention, the technical solution in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.