CN111875804A - Hole sealing agent, preparation method thereof and antireflection coating liquid - Google Patents
Hole sealing agent, preparation method thereof and antireflection coating liquid Download PDFInfo
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- CN111875804A CN111875804A CN202010771537.3A CN202010771537A CN111875804A CN 111875804 A CN111875804 A CN 111875804A CN 202010771537 A CN202010771537 A CN 202010771537A CN 111875804 A CN111875804 A CN 111875804A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
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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
- C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
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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
- C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
- C03C17/30—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with silicon-containing compounds
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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
- C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
- C03C17/32—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with synthetic or natural resins
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1687—Use of special additives
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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Abstract
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.
Description
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.
Example 1 hole sealing agent and method for preparing the same
The hole sealing agent in the embodiment comprises the following components:
the hydrogen content of the low hydrogen silicone oil in this example was 0.10%. The solvent is a mixed solvent of isopropanol and propylene glycol methyl ether acetate. 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.
In other embodiments, the low hydrogen silicone oil has a hydrogen content of 0.1 to 1.0%; the solvent is alcohol solvent and/or high boiling point solvent, wherein 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; 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, allyl polyoxyethylene acetate and heptamethyltrisiloxane; the fluorine-containing acrylate is one or more of hexafluorobutyl methacrylate, trifluoroethyl acrylate and trifluorobutyl methacrylate.
The preparation method of the hole sealing agent in the embodiment comprises the following steps:
(1) 55g of isopropanol, 5g of propylene glycol monomethyl ether acetate and 13g of low hydrogen silicone oil with the hydrogen content of 0.10 percent are added into a three-neck flask, the stirring speed is controlled at 60rpm, nitrogen is introduced into the three-neck flask for 1h, and the air in the system is replaced.
(2) Heating the system to 90 ℃, mixing 27g of allyl alcohol polyoxyalkyl ether F6 (molecular weight 2000, double key value ≧ 0.5mmol/g) and 1.4g of Speier catalyst, and adding into a dropping funnel; and adding 0.4g of trifluoroethyl methacrylate into the other dropping funnel, simultaneously opening the two dropping funnels, controlling the dropping speed to ensure that the dropping is finished within 1h, preserving the temperature for reacting for 5h after the dropping is finished, cooling, stopping introducing nitrogen, and finishing the reaction to obtain the hole sealing agent.
Example 2 antireflection coating solution and method for producing the same
The antireflection coating liquid in the embodiment comprises the following components:
the preparation method comprises the following steps:
method for preparing film-forming material
(1) 20g of ethyl orthosilicate, 160g of methyltriethoxysilane, 32g of vinyltriethoxysilane, 61g of water and 316g of isopropanol are added into a reaction kettle, mixed and stirred uniformly, 0.08g of hydrochloric acid solution is added, and stirring is continued.
In other embodiments, the silicon source is one or both of methyl orthosilicate and ethyl orthosilicate; the silane coupling agent is two or more than two of methyl triethoxysilane, methyl trimethoxysilane, vinyl triethoxysilane, dimethyl diethoxy silane, phenyl trimethoxysilane, gamma-glycidyl ether oxypropyl trimethoxysilane or gamma-methacryloxypropyl trimethoxysilane; the water is deionized water; the catalyst is one or more than two of hydrochloric acid, acetic acid, nitric acid, sulfuric acid, citric acid, oxalic acid, ammonia water, ethylamine and ethylenediamine; the solvent is one or more than two of methanol, ethanol, n-propanol, isopropanol, glycerol and ethylene glycol monobutyl ether.
(2) And (2) carrying out hydrolytic polycondensation on the solution prepared in the step (1) at the reaction temperature of 60 ℃, reacting for 4 hours, and cooling to room temperature to obtain the film-forming substance.
Preparation method of (II) pore-forming agent
100g of acrylic resin is evenly dispersed in 100g of propylene glycol methyl ether acetate and 300g of isopropanol, stirred for 30min and then kept stand for standby.
Preparation method of (III) auxiliary agent
Mixing 10g triethanolamine and 20g isopropanol, stirring for 30min, and standing. In other embodiments, the amine-containing auxiliary agent is selected from one or more of ammonia, monoethanolamine, diethanolamine, triethanolamine, ethylamine, diethylamine and triethylamine.
Preparation method of (IV) coating liquid
(1) Mixing 0.6g of the hole sealing agent prepared in the example 1, 30g of the film forming material prepared in the step (I) and 12g of the pore forming agent prepared in the step (II);
(2) and then 0.3g of the auxiliary agent prepared in the step (III) is added, and diluted by 57.1g of isopropanol to obtain the antireflection coating liquid with the solid content of 4% by mass, which is marked as coating liquid # 1.
Example 3 hole sealing agent and method of preparing the same
The hole sealing agent in the embodiment comprises the following components:
the hydrogen content of the low hydrogen silicone oil in this example was 0.18%. The solvent is a mixed solvent of isopropanol and butyl acetate.
The preparation method of the hole sealing agent in the embodiment comprises the following steps:
(1) 25g of isopropanol, 5g of butyl acetate and 36.91g of low-hydrogen silicone oil with the hydrogen content of 0.18 percent are added into a three-neck flask, the stirring speed is controlled at 90rpm, nitrogen is introduced into the three-neck flask for 1h, and the air in the system is replaced.
(2) The system was warmed to 100 ℃ and 33.17g of allyl polyethylene glycol methyl ether AEM-10 (molecular weight 498, pure EO structure) and 2.8g of Karstedt's catalyst were mixed and added to one dropping funnel; and adding 1.02g of hexafluorobutyl acrylate into the other dropping funnel, simultaneously opening the two dropping funnels, controlling the dropping speed, ensuring that the dropping is finished within 1.5h, preserving heat for reacting for 4.5h after the dropping is finished, cooling, stopping introducing nitrogen, and finishing the reaction to obtain the hole sealing agent.
Example 4 antireflection coating solution and method for producing the same
The antireflection coating liquid in the embodiment comprises the following components:
the preparation method comprises the following steps:
method for preparing film-forming material
(1) Adding 29g of ethyl orthosilicate, 142g of methyltriethoxysilane, 34g of vinyltriethoxysilane, 63g of water and 303g of isopropanol into a reaction kettle, uniformly mixing and stirring, adding 0.08g of hydrochloric acid solution, and continuously stirring.
(2) And (2) carrying out hydrolytic polycondensation on the solution prepared in the step (1) at the reaction temperature of 60 ℃, reacting for 3 hours, and cooling to room temperature to obtain the film-forming substance.
Preparation method of (II) pore-forming agent
100g of acrylic resin is evenly dispersed in 200g of propylene glycol methyl ether acetate and 200g of isopropanol, stirred for 30min and then kept stand for standby.
Preparation method of (III) auxiliary agent
10g of diethanolamine and 20g of isopropanol are mixed and stirred for 30min and then kept stand for standby.
Preparation method of (IV) coating liquid
(1) 0.5g of the sealing agent prepared in example 3, 30g of the film-forming material prepared in the step (one), and 16g of the pore-forming agent prepared in the step (two) were mixed.
(2) Then 0.30g of the auxiliary agent prepared in the step (III) is added, and diluted by 53.2g of isopropanol to obtain the antireflection coating liquid with the solid content of 4% by mass, which is marked as coating liquid # 2.
Comparative examples 1 and 2
Comparative example 1 is substantially the same as example 2 except that no pore sealing agent is added to the coating solution of comparative example 1, and is marked as comparative example #1, and the preparation method thereof is substantially the same as example 2.
Comparative example 2 is substantially the same as example 4 except that no pore sealing agent is added to the coating solution of comparative example 2, and is labeled as comparative example #2, and the preparation method thereof is substantially the same as example 4.
Example 5 evaluation of the Properties of antireflection coating solution
(1) Measuring the transmittance of the coating liquid:
the coating liquid prepared in the embodiment 2, the embodiment 4 and the comparative examples 1 and 2 is coated on the super white solar embossed glass with the light transmittance Y/T of 91.84/91.80 and the thickness of 3.2mm in a rolling way, the super white solar embossed glass is cured by a curing furnace (150 ℃ C. and 200 ℃ C.), finally the glass is toughened at the temperature of 650 ℃ C. and 700 ℃ C. for 2min to obtain a film layer with the film thickness of 120nm, and the film layer is tested by an air floatation bench type spectral transmittance test system, the light transmittance Y/T value is 91.65%/91.30% according to the standard ISO9050-2003, and the test coefficient is 0.983 coating.
(2) Determination of the Properties of the film
1) And (3) testing pencil hardness: according to the national standard GB/T3098.1-2015, the hardness is required to be higher than 3H.
2) Testing of 3M tape: A3M Scotch610-1PK type adhesive tape is used for rapid testing, the testing method comprises the steps of flatly laying the 3M adhesive tape and adhering the 3M adhesive tape to the surface of a film layer, forcibly extruding and grinding the adhesive tape by using dust-free cloth, then vertically tearing the adhesive tape at 90 degrees, and judging the adhesive tape to be 1-5 grade, 1 grade without mark, 2 grade to be very slight, 3 grade to be obvious, 4 grade residual white and bright marks and 5 grade degumming, wherein the larger the grade is, the worse the dirt resistance is.
3) Testing of polyethylene-vinyl acetate polymer (EVA) adhesive films: cleaning and drying the coated glass,three pieces of glass with an area of about 2.5cm were placed on the glass surface2The 3M polyethylene-vinyl acetate copolymer (EVA) adhesive film is prepared by placing a coated glass sample sheet with EVA in an oven (with the temperature set at 150 ℃), baking for 30min, taking out and cooling to room temperature, tearing off the EVA adhesive film on the surface of the glass by using tweezers, wiping with alcohol, observing whether the film surface has marks, judging the film surface to be 1-3 grade according to the depth of the marks on the residual surface, judging the film surface to be 1 grade without marks to have no change, judging the film surface to be 2 grade with slight marks to have light color, and judging the film surface to be 3 grade with obvious white marks, wherein the film surface color cannot be seen. The larger the number of stages, the worse the fouling resistance of the membrane surface.
4) Testing of the solar sealing silica gel: cleaning and drying coated glass, coating a round solar sealing silica gel with the diameter of about 10cm on the surface of the glass, standing for 10min at normal temperature, wiping with alcohol, observing whether marks are left on the film surface, judging the marks to be 1-5 levels according to the depths of the marks on the residual surface, judging the marks to be 1-5 levels, judging the marks to be 1 level, judging the 2 levels to be very slight, judging the 3 levels to be more obvious round spots, judging the marks to be white and bright on the 4 levels, degumming the 5 levels, and indicating that the larger the level is, the worse the dirt resistance of.
5) Testing handprints: cleaning and drying the coated glass, pressing a fingerprint at the center of the surface of the glass, putting a coated glass sample wafer with the fingerprint into an oven (with the temperature set at 150 ℃), baking for 30min, taking out and cooling to room temperature, wiping with alcohol, observing whether the mark is left on the film surface, judging the mark to be 1-5 grade, 1 grade without mark, 2 grade with very slight mark, 3 grade with slight mark, 4 grade with relatively clear mark and 5 grade with very clear mark according to the depth of the residual surface mark. The larger the number of stages, the worse the fouling resistance of the membrane surface.
Table 1 results of various performance tests of the anti-reflective coating liquid
As can be seen from Table 1, the results of the change in the visible light transmittance before and after examples 2 and 4 are: the light transmittance was increased by Δ T/Δ Y of 2.23/2.54. Here, the transmittance is measured as the average transmittance TE in the range of 380-1100 nm. The hole sealing agents prepared in the embodiments 1 and 3 are added into the coating liquid, namely the coating liquid #1 and the coating liquid #2, so that the film surface antireflection and hardness, the adhesive tape print and the handprint are not influenced, and the performances of the film surface anti-EVA adhesive film and the solar sealing silica gel can be improved. The film surface EVA adhesive film test result and the solar sealing silica gel test result of the comparative sample #1 and the comparative sample #2 which are not added with the sealant are poor.
The prior art for improving the anti-fouling performance of the antireflection coated glass has the following technical defects: (1) ti is added to form a super-hydrophilic structure, and if the addition amount is too low, the anti-fouling performance of the membrane surface cannot be effectively improved; but the addition amount exceeds a certain value, the permeability increasing rate of the film surface can be obviously reduced; (2) the method has the advantages that the thickness of the film layer is easy to control, but the sputtering method is high in cost, and the difficulty of large-area film coating production is high. 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.
Compared with the prior art, the invention has the following advantages:
(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 method grafts fluorine on the silicone oil branched chain, so that the hole sealing agent is further ensured to have low surface energy and can easily migrate to the surface of the membrane layer along with the volatilization of the solvent in the curing process;
(4) the antireflection coating obtained by the prepared antireflection coating liquid can effectively prevent pollutants or water vapor in the environment from entering due to the compact structure of the film layer, reduce the binding force between media such as an EVA (ethylene vinyl acetate) film, sealing silica gel and the like and surface groups of the film layer, and has anti-fouling performance when applied to antireflection coating liquid glass;
(5) the antireflection coating liquid prepared by the invention can adopt a roll coating process in the application process, is suitable for large-area coating of packaging glass for solar cells, has low raw material and manufacturing cost and high production efficiency, and provides excellent anti-fouling performance on the basis of ensuring high transmittance of a film layer.
The above embodiments are merely illustrative of the technical concept and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the content of the present invention and implement the invention, and not to limit the scope of the invention, and all equivalent changes or modifications made according to the spirit of the present invention should be covered by the scope of the present invention.
Claims (10)
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.
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