KR101121207B1 - Low-refractive anti-reflection coating composition having excellent corrosion resistance and producing method of the same - Google Patents

Abstract

PURPOSE: An anti-reflective coating composition and a manufacturing method thereof are provided to prevent energy scattering of incident light and protect transparent substrate from scratch. CONSTITUTION: An anti-reflective coating composition comprises silicide binder solution which is obtained by reacting silane coupling agent and water with alcohol solution and colloidal silica complex compound solution which is obtained by sol-gel reaction of colloidal silica nanoparticles, silane coupling agent, water and alcohol solvent. The sol-gel reaction is processed at 50-100deg.C in the presence of catalyst. The silicide binder solution comprises 10-15 parts by weight of the silane coupling agent and 15-25 parts by weight of the water based on 100.0 parts by weight of the silicide binder solution.

Description

Anti-reflective coating composition having excellent anti-corrosion property, and its manufacturing method {LOW-REFRACTIVE ANTI-REFLECTION COATING COMPOSITION HAVING EXCELLENT CORROSION RESISTANCE AND PRODUCING METHOD OF THE SAME}

The present invention relates to an anti-reflective coating composition, and more particularly, using a low refractive material, and adjusting the pore size on a transparent substrate to several hundred nanometers (nm) or less smaller than the wavelength of light, including various solar cell modules. When applied to glass of the art, the present invention relates to an antireflection coating composition having a low refractive index excellent in the initial light transmittance, excellent in durability and corrosion resistance, and a method of manufacturing the same.

In general, a solar cell is a semiconductor device that converts light energy into electrical energy by using a photoelectric effect, and has recently been in the spotlight for being clean, noiseless, and infinitely clean energy. In particular, the Tokyo Protocol, which regulates greenhouse gas emissions such as carbon dioxide and methane, came into force on February 16, 2005 to prevent global warming, and solar energy is an important alternative for Korea, which relies on imports for more than 80% of its energy sources. It is one of the energy sources.

Such a solar cell module generates power required by a user by a plurality of solar cell cells connected in parallel and in parallel through a conductive ribbon, and the user can use this power as a commercial power source. The use of the battery module is installed on a roof of a building, a building wall, a mountainous area, an island, a park, a traffic light, a road guide board, and the like, to supply power to a building, or as a power source such as a road guide board, the range of application is widened.

The efficiency of the solar cell can be traced back to the reduction of the loss factor, and the maximum conversion efficiency is obtained when the total loss factor is the smallest. The solar cell loss factors are: ① loss due to surface reflection ② loss due to incomplete absorption (transmission) of long wavelength ③ incomplete use of optical energy ④ recombination in surface and surface layers ⑤ recombination in back and substrate ⑥ opening The effect of the voltage being smaller than the banned signal. ⑦ Loss when forward current flows in the junction. It can be divided into loss of series resistance or parallel resistance. The loss caused by ①, ②, ③ is usually over 50%. have.

The loss due to surface reflection includes loss occurring in the anti-reflection film and the transparent substrate, and the loss due to the incomplete absorption of the long wavelength means that the energy of the solar light contributes to the generation of the electron-electron pair of the solar cell. If the material is smaller than the band width of the material, light does not contribute to the generation of electron-hole pairs, but is transmitted. In the case of silicon solar cells, when light having a wavelength shorter than about 1.13 μm is absorbed by the silicon solar cell, electrical energy is absorbed. Contribute to the occurrence. And, ③ The incomplete use of light energy means that the excess amount exceeding the energy gap among the absorbed light energy is lost by acting as thermal consumption due to the vibration of the lattice. The loss factor of solar cell efficiency can be found from the transparent substrate transparency, which can be seen as the first light transmission in any case. Therefore, the transparent substrate is well protected for a long time with the protection aspect inside the solar cell module. Maintaining a permeable and low refractive index state is a very important factor in terms of solar cell efficiency.

In general, the solar cell module is manufactured by laminating a transparent front substrate, a filler, a solar cell element, a filler, a back protective sheet, and the like sequentially, and vacuum suction and heat pressing them. The solar cell device is generally manufactured using a single crystal silicon substrate or a polycrystalline silicon substrate. Such a silicon substrate is vulnerable to physical impact, and when solar cells are installed outdoors, it is necessary to protect it from the external environment. . In addition, since the electrical output generated by one solar cell element is small, it is necessary to connect a plurality of solar cell materials in a parallel or parallel form to encapsulate a practical electrical output, encapsulate them with transparent substrates and fillers, and manufacture a solar cell module. It is usually done.

In this case, the characteristics required for the transparent substrate generally used in solar cell modules are mainly required to protect the solar cell module (module), excellent mechanical strength and durability of weather resistance, hydrolysis resistance, etc. This requirement is 90% or more.

That is, since the solar cell module is often used outdoors due to its nature, high durability is required for the members constituting the solar cell module. Low iron tempered glass, which is a substrate used in the solar cell module, mainly needs to have excellent mechanical strength and durability such as weather resistance and hydrolysis resistance for protecting the back surface of the solar cell module. At present, such low iron tempered glass for solar cell modules generally use tempered glass having an iron content of 150 ppm or less imported from China.

In addition to the durability for protecting the inside of the module described above, such a transparent substrate requires not only corrosion resistance or durability to the external environment that can be exposed to rain, wind, or corrosiveness, but also maximizes light transmittance and low refractive index for light. Technical elements are very necessary. In general, in order to improve the transmittance by applying to low iron glass, research is being conducted to improve the transmittance by maximizing transparency to increase light transmittance, adjusting the pattern of low iron glass, or forming a pattern. It is insufficient to present a transparent substrate or a coating composition thereof that can improve light transmittance and increase light refractive index while having durability and corrosion resistance.

The present application is to provide an anti-reflective coating composition that can be coated on a transparent substrate to prevent energy scattering of incident light and improve light transmittance including an initial light transmittance. In addition, the present invention provides a high hardness, high corrosion resistance anti-reflective coating composition which is coated on a transparent substrate to protect the transparent substrate from scratches or a natural external environment, and a manufacturing method thereof, and applied to the transparent substrate to provide a solar cell and other display devices. It is intended to be widely applied to transparent materials.

However, the problem to be solved by the present application is not limited to the above-mentioned problem, and other problems not mentioned will be clearly understood by those skilled in the art from the following description.

In order to achieve the above object, the first aspect of the present application, a silicon compound binder solution obtained by reacting a silane coupling agent and water in an alcohol solvent; And a colloidal silica composite compound solution obtained through a sol-gel reaction through colloidal silica nanoparticles, a silane coupling agent, water, and an alcohol solvent.

In one embodiment, the sol-gel reaction, including the catalyst may be reacted at 50 ~ 100 ℃, but is not limited thereto.

In one embodiment, the silane coupling agent is methyltrimethoxysilane, tetraethoxysilane, methyltrichlorosilane, methyltrimethoxysilane, methyltriethoxysilane, methyltributoxysilane, ethyltrimethoxy Silane, ethyltriisopropoxysilane, ethyltributoxysilane, butyltrimethoxysilane, nonafluorobutylethyltrimethoxysilane, trifluoromethyltrimethoxysilane, dimethyldiaminosilane, dimethyldichlorosilane, dimethyl Diacetoxysilane, dimethyldimethoxysilane, dibutyldimethoxysilane, trimethylchlorosilane, (meth) acryloxypropyltrimethoxysilane, 3- (3-methyl-3-oxetanemethoxy) propyltrimethoxysilane , Methyltri (meth) acryloxysilane, methyl [2- (meth) acryloxyethoxy] silane, and methyltris (3-methyl-3-oxetanemethoxy) silane may be one or more selected from the group consisting of However, It is not.

In one embodiment, the silicon compound binder solution may include 10 to 15 parts by weight of the silane coupling agent and 15 to 25 parts by weight of water based on 100 parts by weight of the silicon compound binder solution, but is not limited thereto. no.

In one embodiment, the colloidal silica nanoparticles may be a spherical diameter of 10 ~ 100 nm, but is not limited thereto.

In one embodiment, the colloidal silica composite compound solution, 10 to 20 parts by weight of the silane coupling agent, 3 to 10 parts by weight of the colloidal silica with respect to 100 parts by weight of the colloidal silica composite compound solution, and the alcohol It may be to include 30 to 50 parts by weight, but is not limited thereto.

In one embodiment, the ratio of the silicon compound binder solution and the colloidal silica composite compound solution may be 60 to 90 parts by weight of the colloidal silica composite compound solution to 10 to 40 parts by weight of the silicon compound binder solution, It is not limited.

In one embodiment, the silicon compound binder solution and the water used in the preparation of the colloidal silica composite compound solution may have a pH of 2 to 6 by the addition of an acid stabilizer, but is not limited thereto.

A second aspect of the present application is to prepare a silicon compound binder solution through a sol-gel reaction by adding a silane coupling agent and water to the S1) alcohol solvent; S2) preparing a colloidal silica composite compound solution through a sol-gel reaction by adding a silane coupling agent, water, and colloidal silica nanoparticles to an alcohol solvent; S3) mixing the silicon compound binder solution and the colloidal silica composite compound solution: may provide a method for producing an anti-reflective coating composition comprising:

In one embodiment, the sol-gel reaction in the manufacturing step of the S2) colloidal silica composite compound solution, including the catalyst may be reacted at 50 ~ 100 ℃, but is not limited thereto.

In one embodiment, the preparation of the silicon compound binder solution may include 10 to 15 parts by weight of the silane coupling agent and 15 to 25 parts by weight of water based on 100 parts by weight of the silicon compound binder solution, but is not limited thereto. It doesn't happen.

In one embodiment, the preparation of the colloidal silica composite compound solution, 10 to 20 parts by weight of the silane coupling agent, 3 to 10 parts by weight of the colloidal silica, and 100 parts by weight of the colloidal silica composite compound solution, and It may be to include 30 to 50 parts by weight of the alcohol, but is not limited thereto.

In one embodiment, the mixing of the silicon compound binder solution and the colloidal silica composite compound solution is to mix 60 to 90 parts by weight of the colloidal silica composite compound solution to 10 to 40 parts by weight of the silicon compound binder solution May be, but is not limited thereto.

The third aspect of the present application may provide a transparent substrate comprising the anti-reflective coating composition.

The fourth aspect of the present application may provide a solar cell module including the transparent substrate.

According to the present application, the antireflective coating composition may improve light transmittance through preventing energy scattering of incident light, effect of low refractive index, and preventing light reflection on a transparent substrate. In addition, the antireflective coating composition according to the present application enables long-term bonding to a transparent substrate, and provides high hardness and excellent scratch resistance. In addition, it provides a high corrosion resistance that can prevent surface damage caused by the external environment such as rain, wind, etc. can be used in a transparent transparent substrate in various technical fields.

1 is a graph showing a light transmittance measurement result for each wavelength in one embodiment of the present application;
2 is a graph comparing light transmittance with a transparent substrate including a conventional coating composition in one embodiment of the present application.
Figure 3 according to one embodiment of the present application, the pencil hardness test results photograph.
Figure 4 is a surface photograph of the accelerated weathering resistance evaluation in one embodiment of the present application.
5 is, in one embodiment of the present application, acid resistance, base resistance, base resistance evaluation graph.
6 is a graph of the change in the maximum output value of the solar cell module in one embodiment of the present application.

Hereinafter, embodiments and examples of the present invention will be described in detail with reference to the accompanying drawings so that those skilled in the art can easily carry out the present invention.

It should be understood, however, that the present invention may be embodied in many different forms and is not limited to the embodiments and examples described herein. In the drawings, parts irrelevant to the description are omitted for simplicity of explanation, and like reference numerals designate like parts throughout the specification.

Throughout this specification, when an element is referred to as " including " an element, it is understood that the element may include other elements as well, without departing from the other elements unless specifically stated otherwise.

Throughout this specification, when a layer or member is located “on” with another layer or member, it is not only when one layer or member is in contact with another layer or member, but also between two layers or another member between the two members. Or when another member is present.

As used throughout this specification, the terms “about”, “substantially”, and the like, are used at, or in the vicinity of, numerical values when manufacturing and material tolerances inherent in the meanings indicated are given, and an understanding of the invention Accurate or absolute figures are used to help prevent unfair use by unscrupulous infringers. As used throughout this specification, the term “step of” or “step of” does not mean “step for”.

A first aspect of the present application is a silicon compound binder solution obtained by reacting a silane coupling agent and water in an alcohol solvent; And a colloidal silica composite compound solution obtained through a sol-gel reaction through colloidal silica nanoparticles, a silane coupling agent, water, and an alcohol solvent.

The silane coupling agent has a hydrolyzable group that reacts with an inorganic material in the molecule and an organic functional group that chemically bonds with the organic material, thereby serving to bond the organic material and the inorganic material, and used as an organic-inorganic composite system to provide mechanical strength, water resistance, And to improve the adhesion and the like. In the aspect of the present application, mechanical properties such as tear strength, flexural strength, impact strength, and elongation may be improved to improve adhesiveness to be suitable for application to a transparent substrate, and play a role of surface modification as a filler. The compatibility improvement of resin and the dispersibility to the resin of a filler can be improved.

The silane coupling agent may be a lower alkyl group-containing silane coupling agent, but is not limited thereto. In one embodiment, the silane coupling agent may be methyl silicate or ethyl silicate, but is not limited thereto. In an exemplary embodiment, the silane coupling agent is methyltrimethoxysilane, tetraethoxysilane, methyltrichlorosilane, methyltrimethoxysilane, methyltriethoxysilane, methyltributoxysilane, ethyltrimeth Methoxysilane, ethyltriisopropoxysilane, ethyltributoxysilane, butyltrimethoxysilane, nonafluorobutylethyltrimethoxysilane, trifluoromethyltrimethoxysilane, dimethyldiaminosilane, dimethyldichlorosilane, Dimethyl diacetoxysilane, dimethyldimethoxysilane, dibutyldimethoxysilane, trimethylchlorosilane, (meth) acryloxypropyltrimethoxysilane, 3- (3-methyl-3-oxetanemethoxy) propyltrimethoxy One or more selected from the group consisting of silane, methyltri (meth) acryloxysilane, methyl [2- (meth) acryloxyethoxy] silane, and methyltris (3-methyl-3-oxetanemethoxy) silane. You can, but It is not limited.

The silicon compound binder solution is formed by a sol-gel reaction with the silane coupling agent and water in an alcohol solvent, and the silane coupling agent may include 10 to 15 parts by weight based on 100 parts by weight of the silicon compound binder solution. However, the present invention is not limited thereto. If the silane coupling agent is less than 10 parts by weight, hardness and adhesion may be lowered. If the silane coupling agent is more than 15 parts by weight, the gel may be gled after synthesis, which may result in storage stability.

The alcohol solvent of the silicon compound binder solution and the alcohol solvent of the colloidal silica composite compound act as a solvent of the sol-gel reaction and at the same time prevent gelation and enhance the binding force between components in the composition to reflect The prevention composition serves to better coat the transparent substrate. The alcohol may be one or more selected from the group consisting of ethyl alcohol, methyl alcohol, and alkoxy alcohol, but is not limited thereto. In an exemplary embodiment, the alcohol may include, but is not limited to, 2-butoxyethanol, 2-butoxymethanol, 2-butoxybutanol, or a mixture thereof.

The alcohol solvent of the silicon compound binder solution and water in the colloidal silica composite compound participate in the hydrolysis reaction. In the preparation of the silicon compound binder solution, the silane coupling agent is hydrolyzed by reacting with water, especially an excess of water, wherein the water is preferably added with an acid, and partially hydrolyzed when the acid is not added. For example, even when partial hydrolysis of the silane coupling agent occurs, there may be a problem that a silicon compound binder can not be substantially obtained because gelation occurs due to very unstable at room temperature. At this time, the acid serves as a peptizing agent to prevent gelation of the silicon compound binder synthesized with the silane coupling agent, the same principle is the same as when the acid is added to the colloidal silica composite compound.

In one embodiment, the silicon compound binder solution and the water used in the preparation of the colloidal silica composite compound solution may have a pH of 2 to 6 by the addition of an acid stabilizer, but is not limited thereto. Preferably it may have a pH of 3 to 5, but is not limited thereto. In an exemplary embodiment the acid stabilizer may be an inorganic acid, preferably the acid stabilizer is selected from organic acids such as nitric acid, hydrochloric acid, formic acid, acetic acid, propionic acid, butyric acid, lactic acid, citric acid and fumaric acid; It may be at least one selected from the group consisting of phosphoric acid, sulfuric acid, hydrochloric acid, nitric acid, hydrofluoric acid, chlorosulfonic acid, para-toluenesulfonic acid, trichloroacetic acid, polyphosphoric acid, iodic acid, iodic anhydride and perchloric acid, more preferably Inorganic acids such as nitric acid, hydrochloric acid, and the like.

The silicon compound binder solution is formed by a sol-gel reaction with the silane coupling agent and water in an alcohol solvent, and the water may include 15 to 25 parts by weight based on 100 parts by weight of the silicon compound binder solution. It is not limited.

The colloidal silica nanoparticles are spherical silica particles dispersed in water or an organic solvent as amorphous silica nanoparticles, and OH ions are present on the surface of the nanoparticles formed of an electric double layer by alkali ions.

In one embodiment, the colloidal silica nanoparticles, spherical may be 1 ~ 500 nm in diameter, but is not limited thereto. In an exemplary embodiment, preferably, the colloidal silica nanoparticles may have a spherical diameter of 10 to 100 nm. When the diameter of the colloidal silica nanoparticles is less than 1 nm, the porosity due to the coating on the transparent substrate is low to prevent the decrease in refractive index, and when the diameter exceeds 500 nm, it is difficult to have characteristics due to surface modification. There may be a problem, the size of the pore within the numerical range can be adjusted to a range smaller than the wavelength of light, when applied to a transparent substrate, in particular when applied to a transparent substrate of the solar cell module anti-reflective coating composition according to the present application Compared with the transparent base material not included, the initial light transmittance may be greatly improved. The colloidal silica nanoparticles may be used as a more specific example, such as SNOWTEX series of Nissan chemical or Ludox series of Dupont, but is not limited thereto.

In the preparation of the colloidal silica composite compound solution, the sol-gel reaction may include a catalyst, and the catalyst may be preferably an inorganic acid such as nitric acid or hydrochloric acid, but is not limited thereto. The sol-gel reaction in the preparation of the colloidal silica composite compound solution may be reacted at 50 ~ 100 ℃ under a nitrogen stream or under normal air, preferably at 70 ~ 90 ℃, but is not limited thereto It is not. The numerical range is to consider the boiling point of the alcohol used as the solvent, the reaction can be made smoothly at the temperature of the numerical range.

The colloidal silica composite compound solution includes 10 to 20 parts by weight of the silane coupling agent, 3 to 10 parts by weight of the colloidal silica, and 30 to 50 parts by weight of the alcohol based on 100 parts by weight of the colloidal silica composite compound solution. Preferably, but not limited thereto. If the silane coupling agent is less than 10 parts by weight may have problems of hardness and adhesion, and if it exceeds 20 parts by weight may have a problem of gelation. In addition to preventing the gelation of the obtained product within the numerical range of 30 to 50 parts by weight of the alcohol, it is possible to improve the coating of the transparent substrate by strengthening the binding force between the components of the composition.

In one embodiment of the present application, the ratio of the silicon compound binder solution and the colloidal silica composite compound solution is preferably 60 to 90 parts by weight of the colloidal silica composite compound solution relative to 10 to 40 parts by weight of the silicon compound binder solution However, the present invention is not limited thereto. It is excellent in light transmittance and refractive index in the numerical range of the silicon compound binder solution.

A second aspect of the present application is to prepare a silicon compound binder solution through a sol-gel reaction by adding a silane coupling agent and water to the S1) alcohol solvent; S2) preparing a colloidal silica composite compound solution through a sol-gel reaction by adding a silane coupling agent, water, and colloidal silica nanoparticles to an alcohol solvent; S3) mixing the silicon compound binder solution and the colloidal silica composite compound solution: may provide a method for producing an anti-reflective coating composition comprising:

In the method for preparing an antireflective coating composition of the present application, the contents and repeated descriptions of the antireflective coating composition described in detail above are omitted, and hereinafter, those skilled in the art to which the present invention pertains easily antireflective coating composition of the present application. It will be described in detail so as to manufacture.

The step S1) of preparing a silicon compound binder solution through a sol-gel reaction by adding a silane coupling agent and water to the alcohol solvent may include adding a silane coupling agent, preferably a lower alkyl group-containing silane coupling agent to the alcohol solvent. After stirring at room temperature, a silicon compound binder solution may be prepared by performing a sol-gel reaction by adding water for hydrolysis.

In one embodiment, the preparation of the silicon compound binder solution may include 10 to 15 parts by weight of the silane coupling agent and 15 to 25 parts by weight of water based on 100 parts by weight of the silicon compound binder solution, but is not limited thereto. It doesn't happen. If necessary, after adjusting the concentration of the silicon compound binder solution so that the solid content is 70 to 80% by weight, an additional alcohol is added immediately to stabilize the produced silicon compound binder so that the concentration of the silicon compound binder solution is increased. It may be diluted so that the solid content is 30% by weight or less relative to the total solution. If the silane coupling agent is less than 10 parts by weight, hardness and adhesion may be lowered. If the silane coupling agent is more than 15 parts by weight, the gel may be gled after synthesis, which may cause storage stability. In one embodiment, the sol-gel reaction in the step of preparing the S2) colloidal silica composite compound solution, it may be reacted at 50 ~ 100 ℃ including a catalyst, in an exemplary embodiment nitrogen at room temperature It is preferred to perform for about 24 hours under air flow or in an atmosphere, but is not limited thereto. The catalyst may be an inorganic acid such as nitric acid or hydrochloric acid, but is not limited thereto.

In one embodiment, the preparation of the colloidal silica composite compound solution, 10 to 20 parts by weight of the silane coupling agent, 3 to 10 parts by weight of the colloidal silica, and 100 parts by weight of the colloidal silica composite compound solution, and It may be to include 30 to 50 parts by weight of the alcohol, it is preferable to perform the reaction for about 24 hours, but is not limited thereto. There may be a problem of hardness and adhesion, and if it exceeds 20 parts by weight there may be a problem of gelation. In addition to preventing the gelation of the obtained product within the numerical range of 30 to 50 parts by weight of the alcohol, it is possible to improve the coating of the transparent substrate by strengthening the binding force between the components of the composition.

In one embodiment, the mixing of the silicon compound binder solution and the colloidal silica composite compound solution is to mix 60 to 90 parts by weight of the colloidal silica composite compound solution to 10 to 40 parts by weight of the silicon compound binder solution May be, but is not limited thereto. It is excellent in light transmittance and refractive index in the numerical range of the silicon compound binder solution.

The third aspect of the present application may provide a transparent substrate comprising the anti-reflective coating composition. The transparent substrate may be a glass substrate, a transparent plastic substrate, and the like, and preferably, low iron tempered glass, but is not limited thereto. In an exemplary embodiment, the low iron tempered glass is selected as the transparent substrate, and ultrasonic cleaning is performed using cerium oxide, which is used as an abrasive of the glass, to remove foreign substances on the surface of the low iron tempered glass. After mixing the surfactant and water in a predetermined ratio to remove the remaining cerium oxide by ultrasonic cleaning, the anti-reflective coating composition is coated on the low iron tempered glass by spin coating, spray coating, or the like to dry the coating film 100 ~. The coating process can be carried out by coating to a thickness of 150 nm and heat curing at a temperature of 200 ° C. or higher for about 15 minutes.

The fourth aspect of the present application may provide a solar cell module including the transparent substrate. The manufacturing of the solar cell module can be manufactured by the manufacture of various types of modules in a self-selectable method having an average knowledge in the art to which the present application belongs, typically a transparent substrate, a filler, a solar cell device, a filler and the back It can be produced by sequentially laminating a protective sheet and the like.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

(1) Preparation of Silicon Compound Binder Solution

A 2-liter four-necked flask equipped with a thermometer, a condenser, and a stirrer was installed inside a heating mantle, and then tetraethyl silane (Si (OC ₂ H ₅ ) ₄ , Dow Corning was added as a silane coupling agent to 1 liter of ethyl alcohol. Co., Ltd., Z-6697) was added and stirred for 30 minutes at room temperature. Thereafter, 200 g of water adjusted to pH 4 by nitric acid was added thereto, and then a silicon compound binder solution was prepared while stirring at 500 rpm for 24 hours at room temperature.

(2) Colloidal  Preparation of Silica Composite Compound

After installing a 1 L four-necked flask equipped with a thermometer, a condenser and a stirrer, nitrogen was supplied and methyltrimethoxysilane (CH ₃ Si (OCH ₃ ) ₃ , Dow Corning, Z-6070) as a silane coupling agent. 100 g and 500 ml of ethyl alcohol were added thereto, followed by stirring for 30 minutes. Thereafter, 50 g of water adjusted to pH 4 by nitric acid was added thereto, and stirring was further performed for 30 minutes. Thereafter, after adding 90 g of spherical colloidal silica (Nissan Chemical, Snowtex-O), the colloidal silica composite compound solution was prepared while stirring at 500 rpm for 24 hours at 80 ° C.

(3) Preparation of Antireflective Coating Composition

The silicon compound binder solution and the colloidal silica composite compound thus prepared were mixed and stirred at a ratio of 20:80 to prepare an antireflective coating composition.

Preparation of Transparent Substrate Including Anti-Reflective Coating Composition

In order to coat the anti-reflective coating composition obtained in Example 1 on the low iron tempered glass which is a solar cell module protective substrate, an automatic spray device equipped with a 1.3 mm multi-hole vortex type nozzle, a compressor of ³ kg / cm ² Under pressure, sprayed two or three times at a distance of 15 cm from the low iron tempered glass to form an antireflection layer on the surface thereof, and then dried at room temperature for about 5 minutes and thermoset at 200 ℃ for at least 15 minutes.

< Comparative example  1>

Example 2 was followed, except that the transparent substrate was coated using a commercially available anti-reflection (AR) coating material (PV-100, Chemwelltech) containing high refractive index TiO ₂ and WO _3. .

< Test Example  1>: Light transmittance  Test

The light transmittance test was carried out on the transparent base substrate obtained in Example 2 and the transparent base substrate obtained in Comparative Example 1, and the experiment was commissioned by the Korea Testing Institute.

1 shows a graph of a result of measuring transmittance for each wavelength of the transparent substrate obtained through Example 2. FIG. As can be seen through Figure 1, compared to using only the conventional low iron tempered glass, it was confirmed that the average visible light region of 380 ~ 780 nm is increased by 2.8%.

On the other hand, Figure 2 is a graph comparing the transmittance of the transparent substrate of Example 2 and Comparative Example 1 as an embodiment of the present application. As can be seen through Figure 2, the glass of the antireflection coating composition of the low refractive index of the present application can be seen that the light transmittance is increased by more than 0.5% on average compared to the glass of the high refractive index of the antireflection coating.

< Test Example  2>: pencil hardness test

The pencil hardness test was carried out on the transparent substrate obtained in Example 2, and the experiment was commissioned by the Korea Institute of Industrial Technology.

3 is a photograph of the pencil hardness test results of the transparent substrate of Example 2 in one embodiment of the present application. As can be seen through Figure 3, the pencil hardness of the transparent substrate including the anti-reflective coating composition according to the present application can be confirmed that the surface strength is very excellent at 9H.

< Test Example  3>: Promote weather resistance test

After manufacturing the Taeang battery module comprising the transparent substrate obtained in Example 2, the accelerated test for 4000 hours using an outdoor weathering test using an accelerated weathering meter (Q-Panel, USA) in the room Before and after the evaluation, the surface was observed using an scanning electron microscope (Scanning Electron Microscopy, SEM).

4 is a surface photograph of the film using FE-SEM before and after the accelerated weather resistance 000 hours evaluation of the transparent substrate of the solar cell module including the transparent substrate of Example 2 according to an embodiment of the present application. As can be seen through Figure 4, even after 4000 hours peeling or swelling of the coating film surface of the present application did not appear.

< Test Example  4>: chemical resistance test

Evaluation of acid resistance, base resistance, and saline resistance, which were chemical resistance tests, was performed on the transparent base substrate obtained through Example 2. The acid resistance was 5% aqueous HCl solution, the basic resistance was NaOH 5% aqueous solution, and the salt resistance was NaCl 5% aqueous solution. The specimens coated with the antireflective composition were immersed in each aqueous solution for 96 hours, and the change of transmittance was observed. The results are shown in FIG.

As can be seen through Figure 5, it can be seen that the excellent acid resistance, base resistance, saline resistance of the transparent substrate of the present application.

< Test Example  5>: Field test

After manufacturing the Taeang battery module including the transparent substrate obtained in Example 2, the analysis of the electro-optical characteristics according to the environmental change of the solar cell module. The solar cell module was exposed to the outside, and the change of the maximum output value according to the environmental change was measured. Measuring once a week during exposure to the outside for 12 months, the maximum power of the module was measured over a total of 52 results. For the module coated with the anti-reflective coating composition according to an embodiment of the present application, On average, the output increased by 4.12%. The results are shown in FIG.

From the above physical and field tests, it was confirmed that the anti-reflective coating composition of the present application can be effectively coated on the substrate, thereby meeting the object of the present invention.

Although the present invention has been described in detail with reference to embodiments and examples, the present invention is not limited to the above embodiments and embodiments, and may be modified in various forms, and within the technical spirit of the present invention. It is obvious that many modifications are possible to those skilled in the art.

Claims (15)

delete Silicon compound binder solutions obtained by reacting a silane coupling agent and water in an alcohol solvent; And,
A colloidal silica composite solution obtained through a sol-gel reaction through colloidal silica nanoparticles, a silane coupling agent, water and an alcohol solvent, and
The sol-gel reaction, including the catalyst is reacted at 50 ~ 100 ℃,
Antireflective coating composition.
The method of claim 2,
The silane coupling agent is methyltrimethoxysilane, tetraethoxysilane, methyltrichlorosilane, methyltrimethoxysilane, methyltriethoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriisopro Foxysilane, ethyltributoxysilane, butyltrimethoxysilane, nonafluorobutylethyltrimethoxysilane, trifluoromethyltrimethoxysilane, dimethyldiaminosilane, dimethyldichlorosilane, dimethyldiacetoxysilane, dimethyl Dimethoxysilane, Dibutyldimethoxysilane, Trimethylchlorosilane, (meth) acryloxypropyltrimethoxysilane, 3- (3-methyl-3-oxetanemethoxy) propyltrimethoxysilane, methyltri (meth) One or more selected from the group consisting of acryloxysilane, methyl [2- (meth) acryloxyethoxy] silane, and methyltris (3-methyl-3-oxetanemethoxy) silane,
Antireflective coating composition.
Silicon compound binder solutions obtained by reacting a silane coupling agent and water in an alcohol solvent; And,
A colloidal silica composite solution obtained through a sol-gel reaction through colloidal silica nanoparticles, a silane coupling agent, water and an alcohol solvent, and
The silicon compound binder solution, 10 to 15 parts by weight of the silane coupling agent and 15 to 25 parts by weight of water based on 100 parts by weight of the silicon compound binder solution,
Antireflective coating composition.
The method of claim 2,
The colloidal silica nanoparticles are spherical, the diameter of which is 10 to 100 nm,
Antireflective coating composition.
Silicon compound binder solutions obtained by reacting a silane coupling agent and water in an alcohol solvent; And,
A colloidal silica composite solution obtained through a sol-gel reaction through colloidal silica nanoparticles, a silane coupling agent, water and an alcohol solvent, and
The colloidal silica composite compound solution includes 10 to 20 parts by weight of the silane coupling agent, 3 to 10 parts by weight of the colloidal silica, and 30 to 50 parts by weight of the alcohol based on 100 parts by weight of the colloidal silica composite compound solution. That is,
Antireflective coating composition.
Silicon compound binder solutions obtained by reacting a silane coupling agent and water in an alcohol solvent; And,
A colloidal silica composite solution obtained through a sol-gel reaction through colloidal silica nanoparticles, a silane coupling agent, water and an alcohol solvent, and
The ratio of the silicon compound binder solution and the colloidal silica composite compound solution is 60 to 90 parts by weight of the colloidal silica composite compound solution to 10 to 40 parts by weight of the silicon compound binder solution,
Antireflective coating composition.
Silicon compound binder solutions obtained by reacting a silane coupling agent and water in an alcohol solvent; And,
A colloidal silica composite solution obtained through a sol-gel reaction through colloidal silica nanoparticles, a silane coupling agent, water and an alcohol solvent, and
The water used in the preparation of the silicon compound binder solution and the colloidal silica composite compound solution has a pH of 2 to 6 by the addition of an acid stabilizer,
Antireflective coating composition.
S1) preparing a silicon compound binder solution through a sol-gel reaction by adding a silane coupling agent and water to an alcohol solvent;
S2) preparing a colloidal silica composite compound solution through a sol-gel reaction by adding a silane coupling agent, water, and colloidal silica nanoparticles to an alcohol solvent;
S3) mixing the silicon compound binder solution and the colloidal silica composite compound solution:
The sol-gel reaction in the step of preparing the colloidal silica composite solution of S2), including the catalyst, is reacted at 50 ~ 100 ℃,
Process for preparing antireflective coating composition.
delete The method of claim 9,
Preparation of the silicon compound binder solution is to include 10 to 15 parts by weight of the silane coupling agent and 15 to 25 parts by weight of water based on 100 parts by weight of the silicon compound binder solution,
Process for preparing antireflective coating composition.
The method of claim 9,
Preparation of the colloidal silica composite compound solution, 10 to 20 parts by weight of the silane coupling agent, 3 to 10 parts by weight of the colloidal silica with respect to 100 parts by weight of the colloidal silica composite compound solution, and 30 to 50 weight of the alcohol To include wealth,
Process for preparing antireflective coating composition.
The method of claim 9,
The mixing of the silicon compound binder solution and the colloidal silica composite compound solution is to mix 60 to 90 parts by weight of the colloidal silica composite compound solution to 10 to 40 parts by weight of the silicon compound binder solution,
Process for preparing antireflective coating composition.
A composition comprising the antireflective coating composition of any one of claims 2 to 8,
Transparent substrate.
A solar cell module comprising the transparent substrate of claim 14.

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