Functional ar coating solution and production method thereof

Abstract

The application relates to the technical field of AR coating liquid, and discloses a functional AR coating combined liquid and a production method thereof.The functional AR coating combined liquid is composed of AR coating combination A liquid, AR coating combination B liquid and AR coating combination C liquid; the AR coating combination A liquid is made of the following raw materials: functional silica sol and diluent; the AR coating combination B liquid is made of the following raw materials: doped silica sol and diluent; and the AR coating combination C liquid is made of the following raw material: ammonia.In use, the AR coating combination A liquid is a primer, the AR coating combination B liquid is a topcoat, and the AR coating combination C liquid is used when coating is heated and annealed.The AR coating glass surface layer prepared by using the AR coating liquid prepared by the application has excellent hardness, wear resistance and scratch resistance, can be used in a desert with more wind and sand, can resist static electricity and effectively prevent dust accumulation caused by static adsorption, and has excellent antireflection and transmittance increasing effect.

Description

TECHNICAL FIELD

[0001] The application relates to the technical field of AR coating liquid, in particular to a functional AR coating liquid and a production method thereof. BACKGROUND

[0002] The AR coating liquid, namely the anti-reflective coating liquid, can be used for special treatment of glass to reduce the reflection performance of the glass, and form coated glass with high transmittance and low reflectance, which is widely used in the solar photovoltaic industry.

[0003] The anti-reflective and transmittance-increasing is one of the core technical characteristics of the AR coating liquid, and the AR coating liquid with excellent anti-reflective and transmittance-increasing effect can make the photovoltaic module better capture and utilize sunlight, reduce light reflection, and make more light penetrate into the interior of the photovoltaic cell to be absorbed by the cell to be converted into electric energy, thereby reducing the gap between the actual photoelectric conversion efficiency and the theoretical photoelectric conversion efficiency, improving the overall power generation efficiency of the photovoltaic module, and maintaining high power generation performance under insufficient light conditions, which has great use value. However, the photovoltaic module is usually used outdoors and is subjected to wind and sand scratching. If the hardness of the AR coating liquid is not high, the surface of the coated glass is easily scratched, thereby affecting the light transmittance and further affecting the power generation performance. In long-term use, static electricity is easily generated on the surface of the coated glass, thereby adsorbing small dust and other pollutants, affecting the light transmittance area, and reducing the photoelectric conversion efficiency.

[0004] Most of the AR coating liquids on the market focus on improving the anti-reflective and transmittance-increasing characteristics. For example, the patent with the publication number CN114316795B discloses a photovoltaic glass, the surface of the photovoltaic glass has a double-layer anti-reflective film layer, two different anti-reflective coating liquids are coated on the surface of the glass to form high-transmittance anti-reflective coated glass, so that the prepared photovoltaic glass has high transmittance and weather resistance. However, the patent greatly enhances the transmittance of the photovoltaic glass, but does not consider the problem of dust and pollutant accumulation on the surface of the photovoltaic glass due to static electricity adsorption in actual use. Even if the dust is cleaned frequently, the friction on the surface of the coated glass during cleaning will also cause scratches. Therefore, although the photovoltaic glass prepared by the patent has high transmittance, the transmittance effect has a risk of decline with long-term use. The patent with the publication number CN105016624B discloses a hydrophilic self-cleaning coating liquid and a coating method, which can automatically slide down water when the substrate surface is washed by water, has super strong hydrophilicity without ultraviolet irradiation, can be cured at room temperature, and effectively saves energy. Although the patent can play a self-cleaning role on the surface of the coated glass, effectively clean dust and other pollutants, and has excellent scratch resistance, it does not improve the core performance of the anti-reflective and transmittance-increasing of the coated glass, and the transmittance effect needs to be improved. SUMMARY

[0005] The present application aims to provide a functional AR coating combination liquid and its production method, which solves the following technical problems: (1) the existing AR coating combination liquid is not anti-static and easy to absorb dust after being applied to the coated glass, which reduces the light transmission area and affects the antireflection performance of the coated glass; (2) the existing AR coating combination liquid has poor mechanical strength after coating, and is easy to be scratched during storage and use, affecting the antireflection performance; (3) the existing AR coating combination liquid has poor antireflection effect, which is difficult to meet the use requirements in various fields.

[0006] The purpose of the present application can be achieved by the following technical solutions:

[0007] A functional AR coating combination liquid is composed of AR coating combination A liquid, AR coating combination B liquid and AR coating combination C liquid; the AR coating combination A liquid is made of the following raw materials by weight: 30-50 parts of functional silica sol, 50-80 parts of diluent; the AR coating combination B liquid is made of the following raw materials by weight: 20-30 parts of doped silica sol, 35-50 parts of diluent; the AR coating combination C liquid is made of the following raw materials by weight: 10-12 parts of ammonia water.

[0008] Further, the diluent is an isopropyl alcohol aqueous solution with a mass fraction of 10-12%; the concentration of the ammonia water is 1-2 mol / L.

[0009] Further, the preparation method of the functional silica sol comprises the following steps:

[0010] S1: mix ethanol, ammonia water and deionized water uniformly, add tetraethyl orthosilicate, stir and react at room temperature for 3-5 h, then age for 72-96 h, stand still for 12-24 h after refluxing for 10-12 h, repeat the refluxing reaction for 3-5 times, and collect the product to obtain silica sol;

[0011] S2: put methyl hydrogen-containing silicone oil and allyltrimethoxysilane in propyl alcohol, pass nitrogen, add a catalyst, heat to 75-85 DEG C and react for 8-10 h, remove low-boiling substances by distillation under reduced pressure, and collect the product to obtain modified silicone oil;

[0012] S3: mix deionized water, ethanol and modified silicone oil, add glacial acetic acid, heat and react, age for 18-24 h, and obtain a pre-hydrolysis sol of modified silicone oil;

[0013] S4: mix the silica sol and the pre-hydrolysis sol of modified silicone oil, ultrasonically treat at room temperature for 1-2 h, age for 12-18 h, and obtain a functional silica sol.

[0014] In the scheme, under the catalysis of ammonia water, tetraethyl orthosilicate undergoes hydrolysis and condensation reaction to generate silica sol, under the action of the catalyst, the silicon hydrogen bond in the methyl hydrogen-containing silicone oil structure and the alkenyl in the allyltrimethoxysilane structure undergo silicon hydrogen addition reaction to obtain modified silicone oil containing methoxy groups, the modified silicone oil is pre-hydrolyzed under the action of glacial acetic acid to form a pre-hydrolysis sol of the modified silicone oil, and after mixing with the silica sol, ultrasonic treatment is performed, the methoxy groups in the structure react with the silicon hydroxyl groups on the surface of the silica sol to obtain functional silica sol with pores inside.

[0015] Further, in step S2, the hydrogen content of the methyl hydrogen-containing silicone oil is 1.55-2.55%.

[0016] Further, in step S2, the catalyst is chloroplatinic acid.

[0017] Further, in step S3, the reaction temperature is 55-65 DEG C, and the time is 1.5-3h.

[0018] Further, the preparation method of the doped silica sol is:

[0019] SS1: Put zinc borate in ethanol, ultrasonic dispersion for 20-30min to form a mixed solution;

[0020] SS2: The mixed solution, tetraethyl orthosilicate and deionized water are mixed uniformly, ammonia water with a concentration of 1.5-3mol / L is added to adjust the pH, ultrasonic dispersion is carried out for 10-20min, then reflux reaction is carried out for 5-8h, and the product is collected after the reaction to obtain the doped silica sol.

[0021] In the scheme, zinc borate is uniformly dispersed in ethanol under the action of ultrasonic to form a mixed solution, the mixed solution is added during the hydrolysis and condensation reaction of tetraethyl orthosilicate under the promotion of ammonia water, so that the zinc borate is doped into the silica sol to form a doped silica sol containing boron and zinc elements.

[0022] Further, in step SS2, the pH is adjusted to 8-10.

[0023] A functional AR coating combined liquid is prepared by the following production method:

[0024] Step one, the functional silica sol and the diluent are mixed uniformly, and the AR coating combined A liquid is obtained after packaging;

[0025] Step two, the doped silica sol and the diluent are mixed uniformly, and the AR coating combined B liquid is obtained after packaging;

[0026] Step three, the ammonia water is packaged to obtain the AR coating combined C liquid.

[0027] The beneficial effects of the present application are:

[0028] (1) The present application uses allyl trimethoxysilane to produce bridging effect, combines hydrogen-containing silicone oil with silica sol, so that the functional silica sol has excellent surface activity, can reduce the surface tension of liquid, improve the wettability and flowability of the plating solution, and can improve the flatness of the coating without adding additional surfactants, thereby effectively reducing light scattering, so that the plating combination A liquid has the performance of reducing reflection and increasing transmission, and because there is a certain incompatibility between the hydrogen-containing silicone oil and the silica sol, the porosity of the plating combination A liquid can be further enhanced, thereby enhancing the permeability of the coating and strengthening the effect of reducing reflection and increasing transmission of the plating solution.

[0029] (2) Zinc borate is added as a dopant in the preparation process of silica sol to prepare a doped silica sol. The doping of zinc borate can not only enhance the mechanical properties of the plating combination liquid, but also the boron element has excellent repair effect. After the film layer formed by the solidification of the plating combination B liquid is subjected to high temperature treatment, the micro cracks generated on the surface of the film layer can be repaired, the compactness of the surface of the film layer is enhanced, and the hardness of the film layer is improved. The zinc element has good conductivity and can play an antistatic role when the film layer is used, effectively preventing dust and pollutants caused by static adsorption, reducing the area of light transmission and thereby affecting the effect of reducing reflection and increasing transmission of the film layer.

[0030] (3) The present application uses the plating combination A liquid as the base coating liquid, which has good wettability and flowability, the coating is flat and has good adhesion with the substrate, the porosity is high, and the effect of reducing reflection and increasing transmission is good. The plating combination B liquid is coated thereon, and the two have good interfacial compatibility, forming a double-layer plating film layer, effectively enhancing the light transmittance. At the same time, the plating combination B liquid plays a certain hole sealing effect on the pores of the surface layer of the plating combination A liquid, effectively improving the compactness of the film layer. In the annealing process, the plating combination C liquid is used. Ammonia gas is generated under high temperature, which can further hydrolyze the unhydrolyzed ethoxyl groups in the plating combination A liquid and the plating combination B liquid to form silicon hydroxyl groups. Under the condition of heating and annealing, condensation reaction occurs between the silicon hydroxyl groups, the distance between the micro particles is reduced, the pore size is reduced, the compactness of the film layer is improved, and the hole sealing effect of the surface layer is promoted, thereby enhancing the mechanical strength of the film.

[0031] Of course, it is not necessary for any product implementing the present application to achieve all the advantages described above at the same time. BRIEF DESCRIPTION OF DRAWINGS

[0032] In order to more clearly illustrate the technical solutions of the embodiments of the present application, the following will briefly introduce the drawings needed for the embodiment description. Obviously, the drawings in the following description are only some embodiments of the present application, and other drawings can also be obtained by those skilled in the art without any creative labor.

[0033] Figure 1 The infrared spectrum of the functional silica sol in Example 1 of the present application is shown in the following figure.

[0034] Figure 2 The infrared spectrum of the doped silica sol in Example 2 of the present application is shown in the following figure. DETAILED DESCRIPTION

[0035] The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.

[0036] The preparation methods of the functional silica sol and the doped silica sol in the following examples and comparative examples of the present application are shown as follows:

[0037] I. Preparation of the functional silica sol

[0038] S1: 60 ml of ethanol, 1 ml of ammonia water with a concentration of 2 mol / L, and 0.8 ml of deionized water were fully mixed and uniformly mixed, 5 ml of tetraethyl orthosilicate was added, and the reaction was stirred at room temperature for 3 h, and then aged for 72 h, and then the reaction was refluxed for 10 h, and then the product was collected after standing for 12 h, and the product was collected after repeating the reflux reaction for 3 times, to obtain a silica sol;

[0039] S2: 3.5 ml of methyl hydrogen-containing silicone oil with a hydrogen content of 1.55% and 2 g of allyltrimethoxysilane were placed in 50 ml of propyl alcohol, nitrogen was introduced, 0.03 g of chloroplatinic acid was added, and the temperature was raised to 75°C for reaction for 8 h, and then the low-boiling substances were removed by distillation under reduced pressure, and then the product was collected, to obtain a modified silicone oil;

[0040] S3: 1.6 ml of deionized water, 80 ml of ethanol, and 3.5 ml of the modified silicone oil were fully mixed, 1.2 ml of glacial acetic acid with a concentration of 1 mol / L was added, the temperature was raised to 55°C for reaction for 1.5 h, and then the product was obtained after aging for 18 h, to obtain a pre-hydrolysis sol of the modified silicone oil;

[0041] S4: 25 ml of the silica sol and 30 ml of the pre-hydrolysis sol of the modified silicone oil were fully mixed, and then the product was obtained after ultrasonic treatment at room temperature for 1 h and aging for 12 h, to obtain a functional silica sol.

[0042] The functional silica sol was dried in an oven at 120°C for 4 h, and then the product was ground after being mixed with potassium bromide in an agate crucible after cooling, and then the product was pressed into a micro-translucent sheet in a tablet press, and then the infrared spectrum of the product was tested by using a ThermoFisher Nicolet 6700 type Fourier infrared spectrometer. Figure 1 It can be seen that the infrared spectrum of the functional silica sol is shown in the following figure. -1the absorption peak of carbon-hydrogen bond, 2153cm -1 the absorption peak of silicon-hydrogen bond, 1102cm -1 the absorption peak of silicon-oxygen-silicon bond, 1272cm -1 the absorption peak of silicon-methyl bond, 1131cm -1 the absorption peak of silicon-oxygen-carbon single bond, since the silicon-hydrogen bond in the structure of methyl-containing hydrogen silicone oil cannot all participate in the reaction due to steric hindrance effect, the absorption peak of silicon-hydrogen bond appears at 2153cm -1 in the infrared spectrum of the functional silica sol, while the absorption peaks of silicon-methyl and silicon-oxygen-carbon appear at 1272cm -1 and 1131cm -1 respectively, which indicates that the silica sol is successfully modified by the modifying silicone oil.

[0043] II. Preparation of doped silica sol

[0044] SS1: 2g of zinc borate was placed in 80ml of ethanol, and after ultrasonic dispersion for 20min, a mixed solution was formed;

[0045] SS2: 80ml of the mixed solution, 8ml of tetraethyl orthosilicate and 1.2ml of deionized water were fully mixed and uniformly mixed, ammonia water with a concentration of 1.5mol / L was added to adjust the pH to 8, ultrasonic dispersion was performed for 10min, and then reflux reaction was performed for 5h, after which the product was collected to obtain the doped silica sol.

[0046] The doped silica sol was dried in an oven at 120℃ for 4h, and after cooling, it was mixed with potassium bromide in an agate crucible and ground, and then placed in a tablet press to press into a micro-translucent sheet. Infrared spectrum test was performed using a ThermoFisher Nicolet 6700 type Fourier infrared spectrum tester, and it can be seen that: Figure 2 the absorption peak of carbon-hydrogen bond in methyl is at 2935cm -1 , the absorption peak of silicon-oxygen-silicon single bond is at 1121cm -1 , the absorption peak of hydroxyl group is at 3461cm -1 , the absorption peak of boron-oxygen single bond is at 1382cm -1 , the absorption peak of zinc-oxygen single bond is at 530cm -1 , the absorption peak of zinc-oxygen single bond is at 1382cm -1 , and the absorption peak of zinc-oxygen single bond is at 530cm -1 , which indicates that zinc borate is successfully doped in the silica sol.

[0047] Example 1

[0048] Preparation of AR coating combined solution

[0049] Step one, 30ml functional silica sol, 50ml 10% isopropyl alcohol aqueous solution are mixed uniformly, and AR coating combination A liquid is obtained after packaging;

[0050] Step two, 20ml doped silica sol, 35ml 10% isopropyl alcohol aqueous solution are mixed uniformly, and AR coating combination B liquid is obtained after packaging;

[0051] Step three, 10ml 1mol / L ammonia water is packaged to obtain AR coating combination C liquid.

[0052] Example 2

[0053] Preparation of AR coating combination liquid

[0054] Step one, 40ml functional silica sol, 60ml 11% isopropyl alcohol aqueous solution are mixed uniformly, and AR coating combination A liquid is obtained after packaging;

[0055] Step two, 25ml doped silica sol, 40ml 11% isopropyl alcohol aqueous solution are mixed uniformly, and AR coating combination B liquid is obtained after packaging;

[0056] Step three, 11ml 1.5mol / L ammonia water is packaged to obtain AR coating combination C liquid.

[0057] Example 3

[0058] Preparation of AR coating combination liquid

[0059] Step one, 50ml functional silica sol, 80ml 10% isopropyl alcohol aqueous solution are mixed uniformly, and AR coating combination A liquid is obtained after packaging;

[0060] Step two, 30ml doped silica sol, 50ml 10% isopropyl alcohol aqueous solution are mixed uniformly, and AR coating combination B liquid is obtained after packaging;

[0061] Step three, 12ml 2mol / L ammonia water is packaged to obtain AR coating combination C liquid.

[0062] Comparative example 1

[0063] Preparation of AR coating combination liquid

[0064] 65ml silica sol and 100ml 11% isopropyl alcohol aqueous solution are mixed uniformly, and AR coating combination liquid is obtained after packaging.

[0065] Performance detection

[0066] The AR coating combination solution prepared in Example 1-Example 3 was coated on the surface of photovoltaic glass with a light transmittance of 94.8±0.02%, AR coating combination A was first coated on the surface of the glass to form a bottom coating layer, and after curing and film forming, AR coating combination B was coated, and after curing, AR coating combination C was coated; the AR coating combination solution prepared in Comparative Example 1 was directly coated on the surface of the photovoltaic glass and cured, and the photovoltaic glass coated in Example 1-Example 3 and Comparative Example 1 was heated to 500°C after being kept at 60°C for 30 min for annealing treatment, and the annealing treatment time was 2 h, and after natural cooling to room temperature, it was used as a sample; the pencil hardness of the sample was detected according to the reference standard GB / T6739-2006; the light transmittance of the sample in the wavelength range of 380 nm-1100 nm was tested using an Agilent cary60 type ultraviolet visible spectrophotometer, and the average value of the light transmittance of three different positions was taken as the result, and the light transmittance gain was calculated according to the formula: light transmittance gain=light transmittance-photovoltaic glass light transmittance, to judge the antireflection effect of the sample; the surface resistivity of the sample was tested using a DRK321B-II surface resistivity tester to judge its antistatic ability, and the specific test results are shown in the following table:

[0067] As can be seen from the above table, the pencil hardness of the AR coating combination solution prepared in Example 1-Example 3 reaches 4H, has good mechanical properties, and the light transmittance gain is as high as 3.7%, has excellent antireflection and antistatic effects, and in actual use, can effectively prevent the accumulation of dust and other pollutants caused by static adsorption, which affects the antireflection effect, while the AR coating combination solution prepared in Comparative Example 1 has low hardness, low light transmittance gain, and no antistatic ability, because the base material is directly used with silica sol and is not modified.

[0068] In the description of the present specification, the description of the terms "one embodiment", "some embodiments", "an example", "a specific example", or "some examples" and the like means that the specific features, structures, materials or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present application. In the present specification, the illustrative description of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any appropriate manner in any one or more embodiments or examples. In addition, the different embodiments or examples described in the present specification and the features of the different embodiments or examples can be combined and combined by those skilled in the art without contradiction.

[0069] The above merely illustrates and describes the concept of the present application, and those skilled in the art can make various modifications or supplements to the described specific embodiments or adopt similar ways to replace, as long as the modifications or supplements or replacements do not deviate from the scope defined by the concept of the present application, and should belong to the protection scope of the present application.

Claims

1. A functional AR coating solution, characterized in that, It consists of three parts: AR coating combination solution A, AR coating combination solution B, and AR coating combination solution C. AR coating combination solution A is made from the following raw materials in parts by weight: 30-50 parts functional silica sol and 50-80 parts diluent; AR coating combination solution B is made from the following raw materials in parts by weight: 20-30 parts doped silica sol and 35-50 parts diluent; AR coating combination solution C is made from the following raw materials in parts by weight: 10-12 parts ammonia water. The preparation method of the functional silica sol includes the following steps: S1: Mix ethanol, ammonia and deionized water thoroughly, add tetraethyl orthosilicate, stir at room temperature for 3-5 hours, age for 72-96 hours, reflux for 10-12 hours, stand for 12-24 hours, repeat reflux reaction 3-5 times, collect the product to obtain silica sol. S2: Methyl hydrogen silicone oil and allyltrimethoxysilane are placed in propanol, nitrogen gas is introduced, a catalyst is added, the temperature is raised to 75-85℃ and reacted for 8-10 hours, low-boiling substances are removed by vacuum distillation and the product is collected to obtain modified silicone oil. S3: After thoroughly mixing deionized water, ethanol, and modified silicone oil, add glacial acetic acid, heat to react, and age for 18-24 hours to obtain a pre-hydrolyzed sol of modified silicone oil. S4: Thoroughly mix the silica sol with the pre-hydrolyzed sol of modified silicone oil, sonicate at room temperature for 1-2 hours, and age for 12-18 hours to obtain functional silica sol; The preparation method of the doped silica sol is as follows: SS1: Zinc borate is placed in ethanol and ultrasonically dispersed for 20-30 minutes to form a mixture; SS2: Mix the mixture, tetraethyl orthosilicate, and deionized water thoroughly. Add ammonia water with a concentration of 1.5-3 mol / L to adjust the pH. After ultrasonic dispersion for 10-20 min, reflux the reaction for 5-8 h. After the reaction is completed, collect the product to obtain the doped silica sol.

2. The functional AR coating solution according to claim 1, characterized in that, The diluent is an aqueous solution of isopropanol with a mass fraction of 10-12%; the concentration of the ammonia water is 1-2 mol / L.

3. The functional AR coating solution according to claim 1, characterized in that, In step S2, the hydrogen content of the methyl hydrogen silicone oil is 1.55-2.55%.

4. The functional AR coating solution according to claim 1, characterized in that, In step S2, the catalyst is chloroplatinic acid.

5. The functional AR coating solution according to claim 1, characterized in that, In step S3, the heating reaction temperature is 55-65℃ and the time is 1.5-3h.

6. The functional AR coating solution according to claim 1, characterized in that, In step SS2, the pH adjustment range is 8-10.

7. A functional AR coating solution as described in claim 1, characterized in that, Prepared by the following production methods: Step 1: Mix the functional silica sol and diluent evenly, and then encapsulate to obtain AR coating combination solution A; Step 2: Mix the doped silica sol and diluent evenly, and then encapsulate to obtain AR coating combination solution B; Step 3: After encapsulating the ammonia water, we obtain AR coating combination solution C.

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