KR102532523B1 - 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 double-glazed glass having an anti-reflection and insulating air layer. The method for manufacturing double-glazed glass of the present invention does not require expensive vacuum equipment because the anti-reflection film coating process is performed at room temperature and atmospheric pressure. Since an antireflection coating film is formed by single-layer coating, production time and production cost can be reduced.

Description

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

The present invention relates to a method for manufacturing a double-glazed glass having an anti-reflective and insulating air layer.

Glass is widely used in various buildings for light and visibility. In addition to multi-unit dwellings such as apartments, commercial facilities displaying and selling products such as department stores and large shopping malls are installing wider and more transparent glass to promote and sell products. However, such glass windows have a problem in that the thermal insulation effect is not high compared to walls containing various insulators. In particular, the heat loss rate through the glass window outside the building is high enough to reach 40%, and to solve this problem, the demand for double-glazed glass in which glass plates are installed in a double structure is increasing.

This double-glazed glass is effective in reducing heat loss through windows in a building, but multiple reflections occur on each of the four surfaces according to the structure of two sheets of glass. In this case, the shape of the products displayed indoors is not clearly visible, and messy afterimages are generated around the area. there is Accordingly, most commercial facilities use single-layer glass to prevent afterimages or light reflection on glass windows, which leads to an increase in heating and building maintenance costs due to excessive heat loss, or to reduce the deterioration of accurate visual information transmission due to multiple reflections. I am using double glazing.

Under this background, the present inventors have made an earnest effort to solve the above problems and have completed the present invention.

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

One object of the present invention is a glass cleaning step of cleaning the glass with cerium oxide and a rinse solvent; After the glass cleaning step, a surface treatment step of surface treating the cleaned glass through an atmospheric plasma method under Ar/O ₂ , N ₂ /O ₂ gas conditions or a strong basic solution; 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, to provide a method for manufacturing double-glazed glass with improved anti-reflection and heat insulation functions, comprising an overlapping step of overlapping the two coated glasses such that the sides on which the coating layers are 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, a surface treatment step of surface treating the cleaned glass through an atmospheric plasma method under Ar/O ₂ , N ₂ /O ₂ gas conditions or a strong basic solution; 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 an overlapping step of overlapping the two coated glasses such that the sides on which the coating layers are formed face each other after the coating step.

According to the present invention, since the antireflection coating is applied to the inner surface of the double-glazed glass facing each other, double-glazed glass with improved visible light transmittance by 4.77% can be manufactured.

In addition, since all processes in forming the anti-reflection film are performed at atmospheric pressure, it is possible to manufacture double-glazed glass with an anti-reflection film with low cost and high productivity compared to conventional vacuum methods such as 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 reduced.

1 to 3 are diagrams showing a glass cleaning process.
4 to 6 show a glass surface treatment process before coating the antireflection 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 cross-section and surface SEM of the coating film.
11 to 13 show optical properties and heat insulation properties of double-glazed glass on which a coating film is formed.

A detailed description of this is as follows. Meanwhile, each description and embodiment disclosed in the present invention may also 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 seen that the scope of the present invention is limited by the specific descriptions described below.

In the prior art, in order to prevent reflection ^of double-glazed glass, a multilayer film of three or more layers is formed using sputtering, a chemical vapor deposition (CVD) method, and the like. High vacuum conditions are required, and the same number of multilayer films as three or more layers requires repeated film formation processes. That is, there is a problem in that repetitive coating of high refractive index and low refractive index materials is involved, resulting in increased production cost and production time.

In order to solve the problems of the prior art, the present invention is a glass cleaning step of cleaning the glass with cerium oxide and a rinse solvent; After the glass cleaning step, a surface treatment step of surface treating the cleaned glass through an atmospheric plasma method or a strong basic solution under Ar/O ₂ , N ₂ /O ₂ 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 an overlapping step of overlapping the two coated glasses such that the sides on which the coating layers are formed face each other after the coating step.

The present invention also provides a double-glazed glass manufactured by the above manufacturing method.

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

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 at 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, each of 3 It may be included in a concentration of 30% to 30%.

In the present invention, the coating step may be performed by dip coating, flow coating, roll coating or slot die coating among 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 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 performed by dip coating, it may be performed under 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 antireflection 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 capable of causing destructive interference of the refractive index of 1.5 of glass, and exhibits a characteristic of effectively preventing reflection.

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

In the present invention, the antireflection 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 manufacturing method of the double-glazed glass may include a thermal curing step after the coating step. The thermal curing step may be to use an inline conveyor-type strengthening furnace heated to 600 to 750 ° C. When such a thermal curing step is added, it not only shortens the curing time of the anti-reflection film, but also inevitably proceeds in the manufacture of double-glazed glass, so that the heat-strengthening process proceeds to the anti-reflection film curing, so a separate thermal curing process is additionally invested, It is possible to reduce costs as there is no need for expansion.

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

Hereinafter, the present invention will be described in more detail through examples. However, these examples are intended to illustrate the present invention by way of example, and the scope of the present invention is not limited to these examples.

Preparation Example 1: Preparation of anti-reflection glass

First, in the antireflection film forming step, 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 20% water and a rinsing solvent. A polishing pad in the form of a sponge or brush was used, and the rotational speed was 500 to 1800 rpm in a multi-plane rotation method. (Figures 1 to 3)

Next, surface treatment was performed before coating so that the antireflection film could be uniformly formed. Specifically, an atmospheric pressure plasma method using Ar/O ₂ and N ₂ /O ₂ Gas was used, and in another manufacturing example, surface treatment was performed using a KOH strong basic solution. In the atmospheric plasma process, the ratio of Ar (argon gas): O ₂ (oxygen) was set to 15:5 lpm. (FIGS. 4 to 6)

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

The coating of the antireflection solution was performed using a coating method, and in other manufacturing examples, a dip coating method, a roll coating method, and a slot die coating method were used, respectively. Coating conditions were carried out by changing the moving speed of the glass from 10 mm / s to 100 mm / s according to the amount of solids. (FIG. 7 and 8) In the case of slot die coating, as conditions for optimizing the light transmittance improvement, the liquid discharge amount was 500 μl, the waiting time after liquid contact was 3 seconds, the coating gap was 0.2 mm, and the coating speed was 20 mm/sec. 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 while passing through a thermal tempering furnace. In this case, an inline conveyor type strengthening furnace heated to 600 ~ 750 ° C was used so that the coating film could be efficiently thermally cured while maintaining durability (FIG. 9). Thereafter, the glass was cut and overlapped so that the surfaces coated with the anti-reflection film faced each other, and support means were applied to the top and bottom to manufacture double-glazed glass so that a space between the anti-reflection film was 10 mm.

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

It was prepared in the same manner as in Preparation Example 1, but the double-glazed glass was prepared using a solution containing 35% hollow silica solids as the antireflection solution.

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

It is prepared in the same manner as in Preparation Example 1, but in the process of coating the antireflection solution by slot die coating, the liquid discharge amount is 500 μl, the waiting time after liquid contact is 3 seconds, the coating gap is 0.2 mm, and the coating speed is 40 mm / second. glass was made.

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

It was manufactured in the same manner as in Preparation Example 1, but the anti-reflection film-coated surfaces were overlapped so that the anti-reflection film faces each other, and then the double-glazed glass was manufactured such that a space between the anti-reflection film was secured at 30 mm.

Experimental Example 1: Measurement of optical properties and insulation effect of double glazing

First, in order to check whether the anti-reflection film was evenly coated on the surface of the glass prepared in the above preparation example, an anti-reflection film formation image was taken with an electron microscope. As a result, as shown in FIG. 10, 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, 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 Intins' refractive index meter (UNECS-1500m), it was confirmed that the antireflection monolayer film had a refractive index of 1.25, which would cause destructive interference with respect to the refractive index of 1.5 of the glass. It can be seen that the refractive index can be

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

As a result, as shown in Table 1 and FIGS. 11 and 12, it was confirmed that the transmittance was improved in the double-glazed glass product coated with the anti-reflection film compared to the double-glazed glass not coated with the anti-reflection film solution. Specifically, when considering the wavelength of light, it showed an average improvement of 4.7%, and it was confirmed that the transmittance improved up to 5.5% in the visible light wavelength recognized by humans. This is because the double-glazed glass coated with the antireflection film has a remarkably high degree of transmission of light as it is without being reflected, and it can be seen that the chronic light reflection problem in the glass windows of commercial facilities can be further improved through such double-glazed glass.

2009 03 conventional
Double layer 10mm gap bare 200903 Anti-reflection coating double-layer spacing 10mm AR Transmittance improvement value Transmittance average (300nm to 800nm) 84.66203576% 89.43806895% 4.776033187%
Transmittance 550 nm (central wavelength of visible light) 85.314974% 90.824711% 5.509737%

Next, the heat insulating function of the double-glazed glass coated with the antireflection film was examined. The thermal conductivity of each of the existing double-glazed glass and the double-glazed glass of Preparation Example 1 not coated with the antireflection film was measured using a thermal conductivity meter from Sweden Hotdisk. As a result, as shown in Table 2 below, it was confirmed that the thermal conductivity of the double-glazed glass of Preparation Example 1 was significantly reduced compared to the thermal conductivity of the pure glass, thereby improving the thermal insulation performance. 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 increase the insulation performance, but the light transmittance may be lowered accordingly and the light reflection may become 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 antireflection films are also necessary to secure the function of the double-glazed glass.

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

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

Claims (6)

A glass cleaning step of cleaning the glass with cerium oxide and a rinse solvent;
After the glass cleaning step, a surface treatment step of surface treating the cleaned glass through an atmospheric plasma method or a strong basic solution under a gas condition in which the volume ratio of Ar:O ₂ is 14:6 to 16:4;
After the surface treatment step, a coating step of coating one side of the surface-treated glass with a solution containing 35% by weight of hollow silica solids; and
After the coating step, the coating layer has a refractive index of 1.25 and the coating step comprises an overlapping step of overlapping the two coated glasses so that the side surfaces on which the coating layers are formed face each other with a distance between the coating layers of 6 to 12 mm. A method for manufacturing double-glazed glass in which light transmittance is improved compared to double-glazed glass that is not coated to prevent light reflection, and thermal conductivity is reduced compared to double-glazed glass without the coating step, thereby improving heat insulation function,
The coating step is made of dip coating, flow coating, roll coating or slot die coating among coating methods,
When the coating step is performed by slot die coating, the contact liquid discharge amount is 400 to 600 μl, the waiting time after 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.
When the coating step is performed by dip coating, it is made under conditions of a glass discharge time of 55 to 65 mm/sec and a drying temperature of 75 to 85 ° C.
delete delete delete delete The method of claim 1, comprising the step of thermally curing the coating film using an inline conveyor-type strengthening furnace heated to 600 to 750 ° C as a thermal curing step after the coating step.

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