KR20220065108A - Manufacturing method of multi-layered glass with anti-reflection and insulating air layer - Google Patents

Abstract

The present invention relates to a method for manufacturing a double-glazed glass having an anti-reflection function and insulating air layer. The method for manufacturing a double-glazed glass, which allows an anti-reflection coating process to proceed at room temperature and atmospheric pressure, does not require expensive vacuum equipment. Furthermore, the present invention is configured such that an anti-reflection coating is formed with only one single-layer coating, and thus can reduce production time and costs.

Description

Manufacturing method of multi-layered glass with anti-reflection and insulating air layer

The present invention relates to a method for manufacturing a multilayer glass having an anti-reflection and insulating air layer.

Glass is widely used in various buildings to provide light and visibility. Wider and more transparent glass is being installed to promote and sell products not only in apartment houses such as apartments, but also in commercial facilities that display and sell products, such as department stores and large shopping malls. However, such a glass window has a problem in that the insulation effect is not high compared to the wall surface including various insulation materials. In particular, the rate of heat loss through glass windows outside the building is as high as 40%, and to solve this problem, the demand for double-glazed glass with a double structure is increasing.

This double-glazed glass is effective in reducing the rate of heat loss through the windows in the building, but multiple reflections occur on each of the four surfaces according to the two glass structures. In this case, the shape of the products displayed indoors is not clearly visible, and messy afterimages are generated around them. There is this. Therefore, most commercial facilities use single-layer glass to prevent afterimages or light reflections on the glass windows, leading to an increase in heating costs and building maintenance costs due to excessive heat loss, or to reduce the deterioration of accurate visual information delivery due to multiple reflections. and double glazing is used.

The present inventors have completed the present invention by making earnest efforts to solve the above problems under this background.

Korean Patent Publication No. 10-2020-0071291 Korean Patent Publication No. 10-2013-0045497

One object of the present invention, a glass cleaning step of cleaning the glass with cerium oxide and a rinse solvent; After the glass cleaning step, Ar/O ₂ , N ₂ /O ₂ Surface treatment step of surface-treating the cleaned glass through atmospheric plasma method or strong basic solution under gas conditions; After the surface treatment step, a coating step of coating one side of the surface-treated glass with a solution containing hollow silica solids; And after the coating step, it is to provide a method of manufacturing a multi-layer glass with improved anti-reflection and heat insulation function, comprising an overlapping step of overlapping the two coated glasses so that the side surfaces on which the coating layer is formed face each other.

One aspect of the present invention for achieving the above object is a glass cleaning step of cleaning the glass with cerium oxide and a rinse solvent; After the glass cleaning step, Ar/O ₂ , N ₂ /O ₂ Surface treatment step of surface-treating the cleaned glass through atmospheric plasma method or strong basic solution under gas conditions; After the surface treatment step, a coating step of coating one side of the surface-treated glass with a solution containing hollow silica solids; And after the coating step, it provides a method of manufacturing a multi-layer glass with improved anti-reflection and heat insulation function, comprising an overlapping step of overlapping the coated two glasses so that the side surfaces on which the coating layer is formed face each other.

According to the present invention, since an anti-reflection coating is applied to the inner surfaces of the multilayer glass facing each other, it is possible to manufacture a multilayer glass having an improved visible light transmittance by 4.77%.

In addition, since all processes in forming the anti-reflection film are carried out at atmospheric pressure, it is possible to manufacture a multi-layer glass to which the anti-reflection film is applied with a lower cost and high productivity compared to the vacuum method such as conventional vacuum multi-layer thin film coating and moth-eye structure processing.

In addition, since a coating film having an antireflection function and an insulating air layer is formed with only one single layer coating, production time and production cost can be shortened.

1 to 3 are diagrams illustrating a glass cleaning process.
4 to 6 show the glass surface treatment process before coating the anti-reflection film.
7 and 8 show the coating process of the anti-reflection solution.
9 shows the thermal curing process of the coating film.
10 shows a cross-section and surface SEM of the coating film.
11 to 13 show the optical properties and thermal insulation properties of the multi-layer glass on which the coating film is formed.

This will be described in detail as follows. Meanwhile, each description and embodiment disclosed in the present invention may be applied to each other description and embodiment. That is, all combinations of the various elements disclosed herein fall within the scope of the present invention. In addition, it cannot be considered that the scope of the present invention is limited by the specific descriptions described below.

In the prior art, a multilayer film of three or more layers is formed by using sputtering, CVD (Chemical Vapor ^Deposition ), etc. to prevent reflection of the multilayer glass. High vacuum conditions are required, and repeated film formation processes are required in the same way as the number of multilayer films of three or more layers. That is, there is a problem in that repeated coating of the high refractive index and the low refractive index material is involved, resulting in increased production cost and production time.

In order to solve the problems of the prior art, the present invention provides a glass cleaning step of cleaning the glass with a cerium oxide and a rinse solvent; After the glass cleaning step, Ar/O ₂ , N ₂ /O ₂ Surface treatment step of surface-treating the cleaned glass through atmospheric plasma method or strong basic solution under gas conditions; After the surface treatment step, a coating step of coating one side of the surface-treated glass with a solution containing hollow silica solids; And after the coating step, it provides a method of manufacturing a multi-layer glass with improved anti-reflection and heat insulation function, comprising an overlapping step of overlapping the coated two glasses so that the side surfaces on which the coating layer is formed face each other.

The present invention also provides a multilayer glass manufactured by the above manufacturing method.

In the present invention, the surface treatment step may be surface treatment through an atmospheric plasma method or 0.1 to 1 mol% of KOH aqueous solution under the condition that the ratio of Ar:O ₂ is 14:6 to 16:4.

In the present invention, the coating step may be to coat one side of the surface-treated glass with a solution containing hollow silica solids in a concentration of 3 to 30%. Specifically, the solution to be coated in the coating step may further include a dispersing agent and a thickening agent, and more specifically, the dispersing agent and the thickening agent may be PVP (Polyvinylpyrrolidone) and ethylene glycol (Ethylen Glycol), respectively, 3 It may be included in a concentration of 30% to 30%.

In the present invention, the coating step may be made by dip coating, flow coating, roll coating or slot die coating method among the coating methods.

In the present invention, when the coating step is performed by slot die coating, the liquid discharge amount is 400 to 600 μl, the waiting time after the liquid contact is 2.5 to 3.5 seconds, the coating gap is 0.1 to 0.3 mm, and the coating speed is 15 to 25 mm/sec. it could be

In the present invention, when the coating step is made of dip coating, it may be made under the conditions of a glass discharge time of 55 to 65 mm / sec, and a drying temperature of 75 to 85 °C.

In the present invention, the refractive index of the anti-reflection film formed on one side of the glass through the coating step may be 1.20 to 1.30, or 1.25. This is a refractive index that can cause destructive interference of the refractive index of 1.5 of glass, and exhibits a property of effectively preventing reflection.

In the present invention, the washing step may be washing with a CeO ₂ (cerium oxide) solution having a particle size of 0.1 to 20 μm dispersed in water 10 to 30% and a rinse solvent, specifically, a 20% dispersed particle size It may be used with a cerium oxide solution of 5 to 15 μm and a rinse solvent.

In the present invention, the anti-reflection solution coated on one side of the glass in the coating step may be a solution containing 3 to 30%, 10 to 20%, or 15% of hollow silica solids.

In the present invention, the method for manufacturing the multilayer glass may include a thermal curing step after the coating step. The thermosetting step may be to use an inline conveyor type strengthening furnace heated to 600 ~ 750 ℃. If such a thermal curing step is added, not only will the curing time of the anti-reflection film be shortened, but it must be unavoidably proceeded during the manufacture of multilayer glass to proceed from the thermal strengthening process to the anti-reflective film curing, so additional investment in a separate thermal curing process, There is no need to expand, so it is possible to reduce costs.

In the present invention, the overlapping step is a step of overlapping two glass plates so that the anti-reflection film faces each other, applying a support means to the upper and lower portions, and overlapping so that the space between the anti-reflection film is formed to be 3 to 20 mm or 6 to 12 mm may be doing

Hereinafter, the present invention will be described in more detail through examples. However, these examples are for illustrative purposes only, and the scope of the present invention is not limited to these examples.

Preparation Example 1: Preparation of anti-reflection glass

First, in the step of forming the anti-reflection film, glass cleaning was performed to prevent defects caused by foreign substances. Specifically, it was washed with a CeO ₂ (cerium oxide) solution having a particle size of 0.1 to 20 μm dispersed in water 20% and a rinse solvent. As the polishing pad, a sponge or brush-type polishing pad was used, and the rotation speed was set to 500 to 1800 rpm in a multiple plane rotation method. (FIGS. 1 to 3)

Next, surface treatment was performed before coating so that the anti-reflection film could be uniformly formed. Specifically, an atmospheric pressure plasma method using Ar/O ₂ , N ₂ /O ₂ Gas together was used, and in other preparation examples, surface treatment was performed using a KOH strong basic solution. In the atmospheric plasma process, Ar (argon gas): O ₂ (oxygen) ratio was set to 15:5 lpm was carried out under conditions. (FIGS. 4 to 6)

Next, an anti-reflection solution was coated on one side of the glass plate. The antireflection solution coated on the glass plate was used as a thickener, a dispersant, and a solution containing 15% of hollow silica solids.

The coating method of the anti-reflection solution was used, and in other manufacturing examples, dip coating, roll coating, and slot die coating method were used, respectively. Coating conditions were performed by varying the moving speed of glass from 10 mm/s to 100 mm/s depending on the amount of solid content. (FIGS. 7 and 8) In the case of proceeding to slot die coating, as conditions for optimizing the improvement of light transmittance, the liquid discharge amount was 500 μl, the waiting time after the liquid contact was 3 seconds, the coating gap was 0.2 mm, and the coating speed was 20 mm/second. In the case of the dip coating method, the glass discharge time was 60 mm/sec, and the drying temperature was 80°C.

Next, as part of the tempered glass manufacturing process, the thermal curing of the coating film was allowed to proceed naturally as it went through a heat-hardening furnace. In this case, an inline conveyor type reinforcement furnace heated to 600 ~ 750 ° C was used so that the coating film could be efficiently thermally cured while maintaining durability ( FIG. 9 ). After the glass was cut, the surfaces coated with the anti-reflection film were overlapped to face each other, and a support means was applied to the upper and lower portions to prepare a double-layer glass so that the space between the anti-reflection film was secured to 10 mm.

Preparation Example 2: Preparation of Comparative Example of Anti-Reflection Glass

It was prepared in the same manner as in Preparation Example 1, but a multilayer glass was prepared using a solution containing 35% of hollow silica solids as an anti-reflection solution.

Preparation Example 3: Preparation of Comparative Example of Anti-Reflection Glass

Prepared in the same manner as in Preparation Example 1, except that in the process of coating the anti-reflection solution with slot die coating, 500 μl of liquid discharge, 3 seconds of waiting time after contact, 0.2 mm of coating gap, and 40 mm/second of coating speed. Glass was made.

Preparation Example 4: Preparation of Comparative Example of Anti-Reflection Glass

It was prepared in the same manner as in Preparation Example 1, but after overlapping the surfaces coated with the anti-reflection film to face each other, a double-layer glass was prepared so that the space between the anti-reflection films was secured to 30 mm.

Experimental Example 1: Measurement of optical properties and thermal insulation effect of multi-layer glass

First, in order to check whether the antireflection film was evenly coated on the surface of the glass prepared in Preparation Example, an image of the antireflection film formation was taken with an electron microscope. As a result, it was confirmed that the coating composition was uniformly coated on one side of the glass plate in both the cross section and the surface as shown in FIG. 10, and was formed to a thickness of about 450 nm.

Additionally, as a result of measuring the refractive index of the antireflection film formed on the side of the glass plate using an Intins refractive index meter (UNECS-1500m), it was confirmed that the antireflection monolayer had a refractive index of 1.25, which would cause destructive interference with respect to the 1.5 refractive index of the glass. It can be seen that the refractive index can be

Next, in order to measure the optical properties (transmittance) of the multilayer glass prepared in Preparation Example, the light transmittance was measured using an Evolution 300 UV-Vis Spectrophotometer manufactured by Thermo Scientific.

As a result, as shown in Table 1, FIGS. 11 and 12, it was confirmed that the transmittance was improved in the multi-layer glass product coated with the anti-reflection film compared to the multi-layer glass not coated with the anti-reflection film solution. Specifically, when considering the wavelength of light, it was confirmed that, on average, it showed an improvement of 4.7%, and the transmittance was improved to 5.5% in the wavelength of visible light recognized by humans. It can be seen that the multi-layer glass coated with an anti-reflection film does not reflect light but transmits it as it is.

200903 Conventional
double layer 10mm gap bare 200903 Multi-layer thickness 10mm AR with anti-reflection coating Transmittance improvement Transmittance average (300nm~800nm) 84.66203576 % 89.43806895% 4.776033187%
Transmittance 550 nm (visible light center wavelength) 85.314974 % 90.824711 % 5.509737 %

Next, it was attempted to confirm the insulating function of the multi-layer glass coated with the anti-reflection film. The thermal conductivity of each of the conventional multilayer glass not coated with an anti-reflection film and the multilayer glass of Preparation Example 1 was measured using a thermal conductivity meter from Sweden Hotdisk. As a result, as shown in Table 2 below, compared to the thermal conductivity of the pure glass, it was confirmed that the thermal conductivity of the multilayer glass of Preparation Example 1 was significantly reduced, and thus the thermal insulation performance was improved. In this case, the thickness of the coating layer and the concentration of the coating solution may be increased as in Preparation Example 2 in order to further improve the thermal insulation performance, but the light transmittance is lowered accordingly and light reflection may be severe. It can be seen that there is In addition, considering the results of Preparation Examples 3 and 4, it can be seen that appropriate coating conditions and the distance between the anti-reflection film are also necessary to secure the function of the multilayer glass.

pure glass Preparation Example 1 Preparation 2 Preparation 3 Preparation 4 thermal conductivity 895 mW/m K 181 mW/m K 175 W/m K 346 W/m K 287 W/m K

From the above description, those skilled in the art to which the present invention pertains will understand that the present invention may be embodied in other specific forms without changing the technical spirit or essential characteristics thereof. In this regard, it should be understood that the embodiments described above are illustrative in all respects and not restrictive. The scope of the present invention should be construed as being included in the scope of the present invention, rather than the above detailed description, all changes or modifications derived from the meaning and scope of the claims to be described later and their equivalents.

Claims (6)

A glass cleaning step of cleaning the glass with cerium oxide and a rinse solvent;
After the glass cleaning step, Ar/O ₂ , N ₂ /O ₂ Surface treatment step of surface-treating the cleaned glass through atmospheric plasma method or strong basic solution under gas conditions;
After the surface treatment step, a coating step of coating one side of the surface-treated glass with a solution containing hollow silica solids; and
After the coating step, the method of manufacturing a double-layer glass with improved antireflection and heat insulation function, comprising the step of overlapping the two coated glasses so that the side surfaces on which the coating layer is formed face each other.
According to claim 1, wherein the surface treatment step Ar: O ₂ The ratio of 14:6 to 16:4 under normal pressure plasma method or KOH solution under the conditions of the surface treatment, the method for producing a multilayer glass.
The method of claim 1, wherein the coating step is to coat one side of the surface-treated glass with a solution containing hollow silica solids at a concentration of 3 to 30%.
The method of claim 1, wherein the coating step is made by dip coating, flow coating, roll coating or slot die coating method among coating methods.
5. The method of claim 4, wherein when the coating step consists of slot die coating, a liquid discharge amount of 400 to 600 μl, a waiting time after contacting a liquid of 2.5 to 3.5 seconds, a coating gap of 0.1 to 0.3 mm, and a coating speed of 15 to 25 mm / sec. will be done,
When the coating step is made of dip coating, the glass discharge time 55 to 65 mm / sec, the drying temperature of 75 to 85 ℃ will be made under the condition of a manufacturing method of a multilayer glass.
According to claim 1, As a thermal curing step after the coating step, the method of manufacturing a multi-layer glass comprising the step of proceeding the thermal curing of the coating film using an inline conveyor-type strengthening furnace heated to 600 ~ 750 °C.

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