KR101756581B1 - Low-emissivity GLASS - Google Patents

Abstract

The present invention relates to a glass substrate comprising a glass substrate and a first dielectric layer sequentially stacked from the glass substrate, a first sub-dielectric layer, a reflective metal layer, a first metal protective layer, a second sub- Emitting glass.

Description

{Low-emissivity GLASS}

The present invention relates to a glass substrate comprising a glass substrate and a first dielectric layer sequentially stacked from the glass substrate, a first sub-dielectric layer, a reflective metal layer, a first metal protective layer, a second sub- Emitting glass.

A lot of heat loss in a building takes place through glass and windows. In recent years, the tendency of the glass to become large in the building has become prominent, and the energy loss of the building is expected to increase accordingly. However, domestic use of low-E glass, which is superior in energy saving effect compared with ordinary glass, is insufficient, and high-performance Roy glass production technology has not been secured. With the recent introduction of institutional devices related to energy conservation, Roy Glass is expected to have explosive demand, and it is urgent to acquire domestic high-performance glass production technology to replace foreign technologies.

 In addition, according to the recent architectural trends, the aesthetic role of the exterior facade of the building is highlighted, and the glass is attracting attention as the part that can freely express the visual aspect of the building freely. The reason why the glass is used as the exterior of the building is that the transparency which is the fundamental characteristic of the glass is ensured and the color, the saturation, and the brightness of the glass can be variously expressed by composition change or coating, This is because of the advantages that can be created. For this reason, the proportion of glass in exterior members is gradually increasing in modern buildings, and in the case of commercial high-rise buildings, the exterior surface is made of glass. As such, glass has the advantage of being able to express its appearance freely while securing transparency compared to other building materials.

Low-emission glass is a low-radiation layer coated on glass that has the function of blocking solar heat in summer and preserving heat in winter. It can save energy of building when used as building exterior material. Such a low-emission glass can be roughly classified into two types according to the manufacturing method. The soft low-E glass by the sputtering process and the hard glass by the atmospheric pressure chemical vapor deposition There is Hard (Low-E) glass. Since the coating film is an oxide film formed at a high temperature, it can be post-strengthened and has a merit of being freely handled. On the other hand, there is a decisive disadvantage that insulation and shielding performance are lowered by soft conductive material due to low electric conductivity of the coating film There is a limit to large-scale supply. On the other hand, since the coating film is composed of metal Ag having the best electrical conductivity, it is relatively soft and has excellent insulation and shielding performance, and is composed of a multilayer film including various auxiliary films. Therefore, And thus it is possible to supply products having various characteristics desired by consumers. However, due to the characteristics of the metal Ag film, which is easily oxidized and deformed even at a high temperature and even at a room temperature, post-strengthening is impossible. In order to improve the quality of the product, it is suggested that a glass which can be reinforced immediately after it is tempered can be used. . Such temperable low-glass is sometimes called "Heat Treatable Low-E" or "Heatable Low-E" in the industry because it can withstand hardening and curving conditions even though it is soft. and has been applied to various fields requiring post-heat treatment such as windshield. For this purpose, the glass rods are usually heated to a temperature of 600 to 700 DEG C, which is bending or stressing. During this application of heat, the functional reflective metal layer (mainly Ag) on the glass substrate is often crystallized due to oxidation and diffusion, It undergoes a structural transformation. One of the methods for preventing such deformation, that is, deterioration at high temperature, is to laminate a silver metal layer with a sandwich structure using a metal protective film. The thickness of the metal protective film should be such that the transmittance can be maintained without deteriorating the Ag metal layer when the coated glass is heat-treated at a high temperature. However, these methods have also shown limitations in satisfying all desired thermal resistances while maintaining a high visible light transmittance.

Korean Patent Registration No. 1015072 discloses a low-emission glass which is free from blurring after heat treatment, has an increased visible light transmittance and improved low-emission properties, but it is not only damaged by external scratches or foreign matter , It is difficult to satisfy the high permeability of 85% or more.

The present invention can improve the transmittance of a low-emission glass by sequentially laminating a first dielectric layer, a first sub-dielectric layer, a reflective metal layer, a first metal protection layer, a second sub-dielectric layer, a second dielectric layer, The present invention also provides a low-emission glass having improved durability and thermal performance.

The low emissivity glass of the present invention comprises a glass substrate; And a first dielectric layer, a first sub-dielectric layer, a reflective metal layer, a first metal protective layer, a second sub-dielectric layer, a second dielectric layer, and a top protective layer sequentially laminated from the glass substrate.

The low-emission glass of the present invention is obtained by sequentially laminating a dielectric layer, a sub-dielectric layer, a reflective metal layer, a metal protective layer, and the like on a glass substrate, which can be improved in chemical and mechanical durability and bendable, And has advantages of being heat-treated.

Hereinafter, the present invention will be described in more detail.

The low-emission glass of the present invention comprises a glass substrate and a first dielectric layer, a first sub-dielectric layer, a reflective metal layer, a first metal protective layer, a second sub-dielectric layer, a second dielectric layer, Layer. The low emissivity glass may have an emissivity of about 0.02 to 0.04, and a visible light transmittance of at least about 50%, but may not be limited thereto.

As the glass base material, ordinary glass which can be used in the art such as building or automobile can be used. For example, soda lime glass may be used, but the present invention is not limited thereto. The thickness of the glass base material may be appropriately selected by a person skilled in the art depending on the purpose of use, and may have a thickness of about 2 to 12 mm, but may not be limited thereto.

The thickness of the first dielectric layer included in the low-emission glass of the present invention may be about 20 to 50 nm and may be at least one element selected from the group consisting of Sn, Nb, Al, Sb, Mo, Cr, Based oxynitride, Si-based nitride containing Si, or Si-based oxynitride. For example, the first dielectric layer may include, but is not limited to, a SiAlN _x based structure.

The first dielectric layer serves to block Na ⁺ diffused from the lower glass substrate, for example soda lime glass, during heat treatment such as strengthening or bending, and / or to block oxygen and / or ions transferred to the reflective metal layer can do.

The thickness of the first sub-dielectric layer included in the low-emission glass of the present invention may be about 5 to 10 nm, and may be at least one element selected from the group consisting of Sn, Nb, Al, Sb, Mo, Cr, Zn-based oxides or Zn-based oxynitrides, but the present invention is not limited thereto. The first sub-dielectric layer affects the degree of crystallization of the reflective metal layer, thereby improving the thermal performance of the low-emission glass.

The first sub-dielectric layer induces crystallization of the reflective metal layer to be well performed, prevents oxygen gas from diffusing into the upper and lower dielectric films during the heat treatment of the reflective metal layer, and suppresses the occurrence of optical defects such as lumps have. Preferably, the first sub-dielectric layer may be a Zn-based oxide containing Al, but may not be limited thereto.

The thickness of the reflective metal layer included in the low-emission glass of the present invention may be about 5 to 20 nm and may include one or more metals selected from the group consisting of Ag, Cu, Au, Al, and Pt, . The reflective metal layer may selectively transmit and reflect light (solar radiation) in the infrared region.

The thickness of the first metal protective layer included in the low-emission glass of the present invention may be about 0.5 to 2 nm, and may include at least one selected from the group consisting of Ni, Cr, Ni-Cr alloy, and NiCrN _x But may not be limited thereto. The durability of the low-emission glass of the present invention can be enhanced due to the metal protective layer, and the metal protective layer can function to protect the reflective metal layer during the heat treatment.

The first metal protective layer serves as a barrier to prevent the movement of O ₂ in the air during the heat treatment for strengthening and / or bending, and also helps the reflective metal layer to stably behave even under high heat treatment conditions .

The thickness of the second sub-dielectric layer included in the low-emission glass of the present invention may be about 5 nm to 10 nm and may be at least one selected from the group consisting of Sn, Nb, Al, Sb, Mo, Cr, Zn-containing oxides or Zn-based oxynitrides containing an element, but the present invention is not limited thereto. The second sub-dielectric layer affects the degree of crystallization of the reflective metal layer to improve the thermal performance of the low-emission glass.

The second sub-dielectric layer induces crystallization of the reflective metal layer to be well performed, prevents oxygen gas from diffusing into the upper and lower dielectric films during the heat treatment of the reflective metal layer, and suppresses the occurrence of optical defects such as lumps have. Preferably, the second sub-dielectric layer may be a Zn-based oxide containing Al, but may not be limited thereto.

The thickness of the second dielectric layer included in the low-emission glass of the present invention may be about 20 to 50 nm, and at least one element selected from the group consisting of Sn, Nb, Al, Sb, Mo, Cr, But not limited to, Si-based nitrides, Si-based oxides, or Si-based oxynitrides.

The second dielectric layer acts to block Na ⁺ which is diffused from the lower glass substrate, for example soda lime glass, during heat treatment such as strengthening or bending, and / or to block oxygen and / or ions transferred to the reflective metal layer can do.

The thickness of the top protective layer included in the low-emission glass of the present invention is about 2 to 15 nm and may include, but not be limited to, Ti-based oxynitride with TiO _x N _y (y / x <1) have. The top protective layer can enhance the durability of the low emissivity glass of the present invention. For example, x: y can be 100 mol%: 0 mol% to 75 mol%: 25 mol% based on 100 mol% of the sum of x and y. The uppermost protective layer may reduce the roughness of the low-emission glass surface, increase the scratch resistance, and increase the mechanical and chemical durability of the coating film. If the thickness of the uppermost protective layer is less than about 2 nm, the durability may deteriorate. If the thickness of the uppermost protective layer is more than about 15 nm, the transmittance of the low-emission glass may be decreased or cloudy. Preferably, the thickness of the top protective layer may be about 2 to 7 nm.

The Ti-based oxynitride contained in the uppermost protective layer of the present invention may further contain at least one element selected from W, Zr, and Si, but may not be limited thereto.

The low emissivity glass of the present invention may further include, but is not limited to, a second metal protective layer having a thickness of 1.5 to 5 nm between the first sub-dielectric layer and the reflective metal layer. The second metal protective layer serves as a barrier to prevent the movement of O ₂ in the air during the heat treatment for strengthening and / or bending, and also helps the reflective metal layer to stably behave even under high heat treatment conditions .

The second metal protective layer included in the low-emission glass of the present invention may include, but is not limited to, at least one selected from the group consisting of Ni, Cr, Ni-Cr alloy, and NiCrN _x .

Hereinafter, the present invention will be described more specifically by way of examples. However, these examples are provided only for the understanding of the present invention, and the scope of the present invention is not limited to these examples in any sense.

[Example]

Low emission  Preparation of glass 1 - Example  One

A 6 mm thick transparent glass was first coated with a first dielectric layer of SiAlN _x layer with a thickness of 25 nm under a nitrogen / argon atmosphere. The ZnAlO layer as the first sub-dielectric layer was then coated with 10 nm under an argon / oxygen atmosphere. The reflective metal layer Ag was then coated to about 10 nm under an argon atmosphere. A NiCr layer was coated to a thickness of 0.8 nm as a first metal protective layer and then a ZnAlO layer was deposited to a thickness of 10 nm as a second sub-dielectric layer in an argon / oxygen atmosphere and a SiAlN _x layer was deposited as a second dielectric layer in a nitrogen / nm. &lt; / RTI &gt; Finally, the low-emission glass of Example 1 was prepared by coating the TiO _x N _y layer with a top protective layer to a thickness of about 5 nm under an argon nitrogen atmosphere. The film structure of the low emissivity glass of Example 1 was as follows: First dielectric layer / first sub-dielectric layer / reflective metal layer (Ag) / first metal protective layer / second sub-dielectric layer / second dielectric layer / .

Low emission  Preparation of glass 1 - Comparative Example  One

The low-emission glass was produced under the same conditions as in Example 1, except that it included one second metal protective layer before coating the reflective metal layer and no uppermost protective layer. The second metal protective layer was formed by coating NiCr in an argon atmosphere. The film structure of the low emissivity glass of Comparative Example 1 was as follows: First dielectric layer / first sub-dielectric layer / second metal protective layer / reflective metal layer (Ag) / first metal protective layer / second sub- 2 dielectric layer.

Low emission  Preparation of glass 1 - Comparative Example  2

Low-emission glass was produced under the same conditions as in Example 1, except that the first and second sub-dielectric layers and the uppermost protective layer were not included. The film structure of the low emissivity glass of Comparative Example 2 manufactured as follows: First dielectric layer / reflective metal layer (Ag) / first metal protective layer / second dielectric layer.

Low emission  Preparation of glass 1 - Comparative Example  3

Low-emission glass was produced under the same conditions as in Example 1, except that the uppermost protective layer was not included. The film structure of the low emissivity glass of Comparative Example 3 manufactured as follows: First dielectric layer / first sub-dielectric layer / reflective metal layer (Ag) / first metal protective layer / second sub-dielectric layer / second dielectric layer.

Low emission  Preparation of glass 1 - Comparative Example  4

Low-emission glass was produced under the same conditions as in Example 1, except that the thickness of the first metal protective layer was 3.0 nm. The film structure of the low emissivity glass of Comparative Example 4 was as follows: First dielectric layer / First sub-dielectric layer / Reflective metal layer (Ag) / First metal protective layer / Second sub-dielectric layer / Second dielectric layer / .

Low emission  Preparation of glass 1 - Property evaluation

The low-emissivity glass samples of Example 1 and Comparative Examples 1 to 4 were prepared in the same manner as in Example 1 and Comparative Examples 1 to 4 except that in the general tempering furnace used in the production of tempered glass, Followed by heating for about 5 minutes, followed by quenching.

The visible light transmittance was measured according to the KS L 2514 standard, and the sheet resistance was measured using a surface resistivity meter (non-contact sheet resistance meter) at a wavelength of 380 to 780 nm before and after the heat treatment. The sheet resistance is a value measured by Ag, which is a solar radiation reflective metal layer, and shows one of the evaluation properties that can be used to measure performance as a low-emission glass even after heat treatment. Scratches were measured using an Elcometer 1720 instrument. Specifically, glass specimens were placed on a measuring instrument and sprayed with water (in accordance with the washing conditions), and the width and number of scratches And evaluated by the level (Lv). Haze evaluated the degree of clouding of the coating film after heat-treating the low-emission glass, and evaluated the level (Lv) by visual observation.

The measurement results for the above items are shown in Table 1 below.

As can be seen from the above Table 1, the low-emission glass according to the embodiment of the present invention is excellent in the visible light transmittance before and after the heat treatment, and has excellent sheet resistance, scratch performance and haze performance, Do. On the other hand, it has been confirmed that the low-emission glass according to Comparative Examples 1 to 4 is somewhat insufficient to maintain high transmission performance and durability and heat resistance performance.

Low emission  Preparation of glass 2 - Example  2

A 6 mm thick transparent glass was first coated with a 25 nm thick SiAlN _x layer as the first dielectric layer under a nitrogen / argon atmosphere. The ZnAlO layer as the first sub-dielectric layer was then coated with 10 nm under an argon / oxygen atmosphere. Next, a NiCr layer was coated to a thickness of 3 nm as a second metal protective layer, and a reflective metal layer Ag was coated to a thickness of about 10 nm under an argon atmosphere. Thereafter, a NiCr layer was coated to a thickness of 1.5 nm as a first metal protective layer, a ZnAlO layer was formed to a thickness of 10 nm as a second sub-dielectric layer in an argon / oxygen atmosphere, and a SiAlN _x layer was formed as a second dielectric layer in a nitrogen / argon atmosphere 25 nm thick. Finally, the low-emission glass of Example 2 was prepared by coating the TiO _x N _y layer as the top protective layer to a thickness of about 5 nm under an argon / nitrogen atmosphere. The film structure of the produced low emission glass of Example 2 is as follows: First dielectric layer / first sub-dielectric layer / second metal protective layer / reflective metal layer (Ag) / first metal protective layer / second sub- 2 Dielectric layer / top protective layer.

Low emission  Preparation of glass 2 - Comparative Example  5

Low-emission glass was produced under the same conditions as in Example 2, except that the sub-dielectric layer was not included. The film structure of the low emissivity glass of Comparative Example 5 manufactured as follows: First dielectric layer / second metal protective layer / reflective metal layer (Ag) / first metal protective layer / second dielectric layer / top protective layer.

Low emission  Preparation of glass 2 - Comparative Example  6

Low-emission glass was produced under the same conditions as in Comparative Example 5, except that the sub-dielectric layer and the uppermost protective layer were not included. The film structure of the low emissivity glass of Comparative Example 6 manufactured as follows: First dielectric layer / second metal protective layer / reflective metal layer (Ag) / first metal protective layer / second dielectric layer.

Low emission  Preparation of glass 2 - Comparative Example  7

Low-emission glass was produced under the same conditions as in Example 2, except that the thickness of the second metal protective layer was about 1.0 nm. The film structure of the low emissivity glass of Comparative Example 7 was as follows: First dielectric layer / first sub-dielectric layer / second metal protective layer / reflective metal layer (Ag) / first metal protective layer / second sub- 2 Dielectric layer / top protective layer.

Low emission  Preparation of glass 2 - Comparative Example  8

Low-emission glass was produced under the same conditions as in Example 2, except that the thickness of the second metal protective layer was about 7.0 nm. The film structure of the low emissivity glass of Comparative Example 8 was as follows: First dielectric layer / first sub-dielectric layer / second metal protective layer / reflective metal layer (Ag) / first metal protective layer / second sub- 2 Dielectric layer / top protective layer.

Low emission  Preparation of glass 2 - Comparative Example  9

A low-emission glass was produced under the same conditions as in Example 2, except that the thickness of the first metal protective layer was 3.0 nm and the thickness of the second metal protective layer was 6.0 nm. The film structure of the low emissivity glass of Comparative Example 9 was as follows: First dielectric layer / first sub-dielectric layer / second metal protective layer / reflective metal layer (Ag) / first metal protective layer / second sub- 2 Dielectric layer / top protective layer.

Low emission  Manufacture of glass 2 - Property evaluation

The low emissivity glass samples of Example 2 and Comparative Examples 5 to 9 were prepared in the same manner as in Example 1 except that the low emissivity glass samples Followed by heating for about 5 minutes, followed by quenching.

The visible light transmittance was measured according to the KS L 2514 standard, and the sheet resistance was measured using a surface resistivity meter (non-contact sheet resistance meter) at a wavelength of 380 to 780 nm before and after the heat treatment. The sheet resistance is a value measured by Ag, which is a solar radiation reflective metal layer, and shows one of the evaluation properties that can be used to measure performance as a low-emission glass even after heat treatment. Scratches were measured using an Elcometer 1720 instrument. Specifically, glass specimens were placed on a measuring instrument and sprayed with water (in accordance with the washing conditions), and the width and number of scratches And evaluated by the level (Lv). Haze evaluated the degree of clouding of the coating film after heat-treating the low-emission glass, and evaluated the level (Lv) by visual observation.

The measurement results for the above items are shown in Table 2 below.

As can be seen from the above Table 2, the low-emission glass according to the embodiment of the present invention is excellent in the visible light transmittance before and after the heat treatment, and has excellent sheet resistance, scratch performance and haze performance, Do. On the other hand, the low-emission glass according to Comparative Examples 5 to 9 is found to be somewhat insufficient to maintain high transmission performance and durability and heat resistance performance.

Claims (11)

Glass substrates; And a glass substrate,
A first dielectric layer;
A first sub-dielectric layer;
Reflective metal layer;
A first metal protective layer;
A second sub-dielectric layer;
A second dielectric layer; And
Top protective layer
Lt; / RTI &gt;
Wherein the first metal protective layer has a thickness of 0.5 to 2 nm and comprises at least one selected from the group consisting of Ni, Cr, Ni-Cr alloy, and NiCrNx. The method according to claim 1,
The first dielectric layer has a thickness of 20 to 50 nm and includes Si-based nitride or Si-based oxynitride containing at least one element selected from the group consisting of Sn, Nb, Al, Sb, Mo, Cr, That radiating glass, which is to do. The method according to claim 1,
The first sub-dielectric layer has a thickness of 5 to 10 nm, and a Zn-based oxide or Zn-based oxynitride containing at least one element selected from the group consisting of Sn, Nb, Al, Sb, Mo, Cr, That radiative glass, which is inclusive. The method according to claim 1,
Wherein the reflective metal layer has a thickness of 5 to 20 nm and comprises at least one metal selected from the group consisting of Ag, Cu, Au, Al, and Pt. delete The method according to claim 1,
The second sub-dielectric layer has a thickness of 5 to 10 nm, and a Zn-based oxide or Zn-based oxynitride containing at least one element selected from the group consisting of Sn, Nb, Al, Sb, Mo, Cr, That radiative glass, which is inclusive. The method according to claim 1,
Wherein the second dielectric layer has a thickness of 20 to 50 nm and includes at least one element selected from the group consisting of Si-based nitride, Si-based oxide, or Si-containing nitride containing at least one element selected from the group consisting of Sn, Nb, Al, Sb, Wherein the composition comprises a compound nitride. The method according to claim 1,
Wherein the top protective layer has a thickness of 2 to 15 nm and comprises a Ti-based oxynitride of TiO _x N _y (y / x <1). 9. The method of claim 8,
Wherein the Ti-based oxynitride further contains at least one element selected from W, Zr, and Si. delete delete