WO2018199598A2 - Low-emissivity glass - Google Patents

Abstract

The present invention relates to a low-emissivity glass which performs a function of preventing radiant heat that is generated outdoors from solar heat from coming indoors in the summer season, and a function of reflecting infrared light that is generated indoors so as to return indoors in the winter season.

Description

Low emission glass

The present invention relates to low emissivity glass that blocks radiant heat and increases the transmittance of visible light.

Glass (window), which has the most heat loss in buildings, has recently become more prominent in area and is expected to increase energy loss in buildings. Therefore, in order to minimize energy loss of buildings, it is required to secure technology for low-emission glass.

The low-emissive glass is largely made of soft low-e glass produced by the sputtering process, and hard low-e glass made of atmospheric pressure chemical vapor deposition. Can be classified as

Since the hard low-emissivity glass is subjected to a process of forming a coating film by heat treatment at a high temperature during manufacturing, it is possible to strengthen after-treatment and free handling. However, the electrical conductivity of the coating film included in the hard low-emissive glass has a disadvantage that the heat insulating and shielding performance is lower than the soft low-emissive glass.

Since the soft low-emission glass includes a coating film made of silver (Ag) having high electrical conductivity, the soft low-emissive glass has excellent thermal insulation and shielding performance, and has a low emission property having a physical property required by the consumer because it includes an auxiliary film that performs various functions. There is an advantage that the provision of glass is easy. However, due to the coating film made of silver (Ag) has a disadvantage that does not exhibit a transparent color (neutral color), there is a limit in obtaining a high transmittance and low emissivity.

The present invention is to provide a low-emission glass that exhibits a transparent color and has a high transmittance and a low emissivity.

According to the present invention, a first dielectric layer, a first sub dielectric layer, a first metal layer, a second sub dielectric layer, a second dielectric layer, a third sub dielectric layer, a second metal layer, a fourth sub dielectric layer, and a third dielectric layer are sequentially formed on a glass substrate. The coated glass, wherein the first to fourth sub-dielectric layers each comprise a Zn-based oxide containing at least one element selected from the group consisting of Sn, Nb, Al, Sb, Mo, Cr, Ti, and Ni. under,

The sum of the thickness of the first metal layer and the thickness of the second metal layer provides a low-emissivity glass that is 18 to 25 nm.

The ratio of the thickness of the first metal layer and the thickness of the second metal layer may be 1: 1.5 to 4.

The metal contained in each of the first metal layer and the second metal layer may be at least one selected from the group consisting of Ag, Cu, Au, Al, and Pt.

On the other hand, the low-emissivity glass of this invention is the 1st metal protective layer provided between the said 1st sub dielectric layer and the said 1st metal layer, and the 2nd metal protective layer provided between the said 1st metal layer and the said 2nd sub dielectric layer. The semiconductor device may further include a third metal protective layer provided between the third sub dielectric layer and the second metal layer, and a fourth metal protective layer provided between the second metal layer and the fourth sub dielectric layer.

In addition, the low-emissivity glass of the present invention may further include a protective layer provided on the third dielectric layer, the protective layer is TiO _x N _y (y / x <1, x: y = 100 mol%: 0 mol% to 75 mol%: 25 mol%).

The protective layer may have a thickness of 2 to 15 nm.

The low-emissivity glass of the present invention has a transmittance of 58% or more, a shielding coefficient of 0.36 or less, and an emissivity of 0.025 to 0.035.

In addition, the low-emission glass of the present invention, the a * and b * value of the glass surface reflection color at the observation angle of 0 ° to 55 ° may be -7 to 1.

The low-emissivity glass of the present invention can exhibit high transmittance and low emissivity while showing a transparent color because the thickness ratio of the first metal layer and the second metal layer having a high influence on the optical properties is optimally designed.

1 is a cross-sectional view for explaining the low-emissive glass of the present invention.

Hereinafter, the present invention will be described.

The low-emissivity glass of the present invention has a specific layer structure and the thickness ratio of the first metal layer and the second metal layer is optimized to show a transparent color, and have a high transmittance and a low emissivity. Specifically, it is as follows.

Referring to FIG. 1, the low-emission glass of the present invention may include a glass substrate 11, a first dielectric layer 12, a first sub dielectric layer 13, a first metal layer 14, a second sub dielectric layer 15, and a first substrate. The second dielectric layer 16, the third sub dielectric layer 17, the second metal layer 18, the fourth sub dielectric layer 19, and the third dielectric layer 20 are included. Specifically, the low-emissivity glass of the present invention is sequentially on the glass substrate 11, the first dielectric layer 12, the first sub dielectric layer 13, the first metal layer 14, the second sub dielectric layer 15, The second dielectric layer 16, the third sub dielectric layer 17, the second metal layer 18, the fourth sub dielectric layer 19, and the third dielectric layer 20 are coated glass.

The glass substrate 11 included in the low emission glass of the present invention serves as a base substrate of the low emission glass. As the glass substrate 11, soda-lime glass used for building or automobile may be used.

The thickness of the glass substrate 11 may be appropriately adjusted according to the purpose of use, and specifically, may be adjusted within the range of 2 to 12 mm.

The first dielectric layer 12 included in the low-emissivity glass of the present invention is provided on the glass substrate 11, and Na ⁺ diffused from the glass substrate 11 during heat treatment of the low-emissivity glass for reinforcement and bending. Blocks the movement of and to block the transfer of oxygen and / or ions to the first metal layer (14). The first dielectric layer 12 may be formed of a Si-based nitride containing at least one element selected from the group consisting of Sn, Nb, Al, Sb, Mo, Cr, Ti, and Ni. Si-based nitride (eg, SiAlN _x , 1.32 ≦ _x ≦ 1.35).

The thickness of the first dielectric layer 12 may be appropriately adjusted according to the purpose of use of the low-emissivity glass, and specifically, may be adjusted within the range of 25 to 35 nm.

The first sub-dielectric layer 13 included in the low-emissivity glass of the present invention is provided on the first dielectric layer 12, and serves to induce crystallization of the first metal layer 14 well, and the first heat treatment during the heat treatment. The dielectric layer 12 serves to suppress the occurrence of optical defects such as diffusion or aggregation of oxygen. The first sub dielectric layer 13 may be formed of a Zn-based oxide containing at least one element selected from the group consisting of Sn, Nb, Al, Sb, Mo, Cr, Ti, and Ni, and specifically, Al is contained. Zn-based oxide (eg, ZnAlO).

The thickness of the first sub dielectric layer 13 may be appropriately adjusted according to the purpose of use of the low-emissivity glass, and specifically, may be adjusted within the range of 5 to 10 nm.

The first metal layer 14 included in the low emission glass of the present invention is provided on the first sub dielectric layer 13 and serves to selectively transmit and reflect solar radiation. The first metal layer 14 may be made of at least one metal selected from the group consisting of Ag, Cu, Au, Al, and Pt. Specifically, the first metal layer 14 has a high transmittance in the visible light region among the solar radiation regions, and has excellent durability. It can be made of Ag which can be represented.

The thickness of the first metal layer 14 may be adjusted according to the thickness of the second metal layer 18, specifically, within the range of 5 to 10 nm. If the thickness of the first metal layer 14 is less than 5 nm, the emissivity may increase, resulting in energy loss. If the thickness of the first metal layer 14 is greater than 10 nm, the transmittance in the visible light region may be lowered, resulting in a transparent color. It is difficult.

The second sub-dielectric layer 15 included in the low-emissivity glass of the present invention is provided on the first metal layer 14, and serves to induce crystallization of the first metal layer 14 well, and at the second heat treatment. The dielectric layer 16 serves to suppress the occurrence of optical defects such as oxygen diffusion or aggregation. The second sub dielectric layer 15 may be formed of a Zn-based oxide containing at least one element selected from the group consisting of Sn, Nb, Al, Sb, Mo, Cr, Ti, and Ni, and specifically, Al is contained. Zn-based oxide (eg, ZnAlO).

The thickness of the second sub dielectric layer 15 may be appropriately adjusted according to the purpose of use of the low-emissivity glass, and specifically, may be adjusted within the range of 5 to 10 nm.

The second dielectric layer 16 included in the low-emissivity glass of the present invention is provided on the second sub dielectric layer 15, and oxygen and / or ions are transferred to the first metal layer 14 or the second metal layer 18 during heat treatment. It blocks the transmission. The second dielectric layer 16 may be formed of a Si-based nitride containing at least one element selected from the group consisting of Sn, Nb, Al, Sb, Mo, Cr, Ti, and Ni. Si-based nitride (eg, SiAlN _x , 1.32 ≦ _x ≦ 1.35).

The thickness of the second dielectric layer 16 may be appropriately adjusted according to the purpose of use of the low-emissivity glass, and specifically, may be adjusted within the range of 70 to 80 nm.

The third sub-dielectric layer 17 included in the low-emissivity glass of the present invention is provided on the second dielectric layer 16, and serves to induce crystallization of the second metal layer 18 well, and during the heat treatment, the second sub-dielectric layer 17 is provided. The dielectric layer 16 serves to suppress the occurrence of optical defects such as oxygen diffusion or aggregation. The third sub dielectric layer 17 may be formed of a Zn-based oxide containing at least one element selected from the group consisting of Sn, Nb, Al, Sb, Mo, Cr, Ti, and Ni, and specifically, Al is contained. Zn-based oxide (eg, ZnAlO).

The thickness of the third sub dielectric layer 17 may be appropriately adjusted according to the purpose of use of the low-emissivity glass, and specifically, may be adjusted within the range of 5 to 10 nm.

The second metal layer 18 included in the low emission glass of the present invention is provided on the third sub dielectric layer 17 and serves to selectively transmit and reflect solar radiation. The second metal layer 18 may be made of at least one metal selected from the group consisting of Ag, Cu, Au, Al, and Pt. Specifically, the second metal layer 18 has a high transmittance in the visible light region of the solar radiation region, and has excellent durability. It can be made of Ag which can be represented.

The thickness of the second metal layer 18 may be adjusted according to the thickness of the first metal layer 14, and specifically, may be adjusted within the range of 15 to 20 nm. If the thickness of the second metal layer 18 is less than 15 nm, the emissivity may increase, resulting in energy loss. If the thickness of the second metal layer 18 is greater than 20 nm, the transmittance in the visible light region may be low, and thus the final manufactured glass may not exhibit a transparent color. .

The low emission glass of the present invention may be a sum (T ₁ + T ₂₎ is 18 to 25 ㎚ a thickness (T ₁₎ to the thickness (T ₂₎ of the second metal layer 18 of the first metal layer 14 . In addition, the ratio of the first metal layer (14) thickness (T ₁₎ to the thickness (T ₂₎ of the second metal layer 18 may be of 1.5 to _{4: (T 1: T 2} ) is 1.

Thus, low emission glass of the present invention has a thickness (T ₁₎ and the second thickness of the metal layer (18) (T ₂₎ is high because it is adjusted to have a specific percentage transmittance and low emissivity in the first metal layer 14 At the same time, a transparent color may be indicated.

The fourth sub-dielectric layer 19 included in the low-emissivity glass of the present invention is provided on the second metal layer 18, and serves to induce crystallization of the second metal layer 18 well, and at the second heat treatment. The diffusion of oxygen into the dielectric layer 16 or the third dielectric layer 20 serves to suppress the occurrence of optical defects such as agglomeration. The fourth sub dielectric layer 19 may be formed of a Zn-based oxide containing one or more elements selected from the group consisting of Sn, Nb, Al, Sb, Mo, Cr, Ti, and Ni, and specifically, Al is contained. Zn-based oxide (eg, ZnAlO).

The thickness of the fourth sub dielectric layer 19 may be appropriately adjusted according to the purpose of use of the low-emissivity glass, and specifically, may be adjusted within the range of 5 to 10 nm.

The third dielectric layer 20 included in the low-emissivity glass of the present invention is provided on the fourth sub dielectric layer 19, and serves to block oxygen and / or ions from being transferred to the second metal layer 18 during heat treatment. do. The third dielectric layer 20 may be made of Si-based nitride containing at least one element selected from the group consisting of Sn, Nb, Al, Sb, Mo, Cr, Ti, and Ni, and specifically, Al may be contained. Si-based nitride (eg, SiAlN _x , 1.32 ≦ _x ≦ 1.35).

The thickness of the third dielectric layer 20 may be appropriately adjusted according to the purpose of use of the low-emissivity glass, and specifically, may be adjusted within the range of 15 to 25 nm.

Meanwhile, the low-emissive glass of the present invention may further include a metal protective layer that protects the first metal layer 14 and the second metal layer 18 to allow stable behavior during heat treatment, and blocks the movement of oxygen. .

Specifically, the low-emissivity glass of the present invention includes the first metal protective layer 21, the first metal layer 14, and the second sub dielectric layer 15 provided between the first sub dielectric layer 13 and the first metal layer 14. ) Between the second metal protective layer 22, the third sub dielectric layer 17 and the second metal layer 18, the third metal protective layer 23, and the second metal layer 18. And a fourth metal protective layer 24 provided between the fourth sub dielectric layer 19 and the fourth sub dielectric layer 19. The first metal protective layer 21, the second metal protective layer 22, the third metal protective layer 23, and the fourth metal protective layer 24 may be made of oxides containing Ni and Cr, respectively.

Each thickness of the first metal protective layer 21, the second metal protective layer 22, the third metal protective layer 23, and the fourth metal protective layer 24 is appropriately adjusted according to the purpose of use of the low-emissivity glass. And specifically may be adjusted within the range of 0.1 to 1 nm, respectively.

In addition, the low-emission glass of the present invention may further include a protective layer 25 provided on the third dielectric layer 20 to reduce the surface roughness of the low-emission glass, and to increase durability and scratch resistance. The protective layer 25 may be formed of an oxide represented by TiO _x N _y (y / x <1 and x: y = 100 mol%: 0 mol% to 75 mol%: 25 mol%).

The thickness of the protective layer 25 may be appropriately adjusted according to the purpose of use of the low-emissivity glass, specifically, may be adjusted within the range of 2 to 15 nm. When the thickness of the protective layer 25 is less than 2 nm, the durability of the low-emissive glass may be lowered, and when the thickness of the protective layer 25 is greater than 15 nm, the transmittance of the low-emissive glass may be lowered or may cause blur.

The low-emission glass of the present invention according to the present invention has a high transmittance and low emissivity, and because of the transparent color (neutral color) can not only obtain a large energy saving effect when applied to the building, but also enhance the aesthetics of the building.

Specifically, the low-emissivity glass of the present invention may have a transmittance of 58% or more, a shielding coefficient of 0.36 or less, and an emissivity of 0.025 to 0.035. In addition, the low-emission glass of the present invention may have a * and b * values of the glass surface reflection color at -7 to 1, respectively, at an observation angle of 0 ° to 55 °.

Hereinafter, the present invention will be described in detail with reference to the following Examples. However, the following Examples are merely to illustrate the present invention, the present invention is not limited by the following Examples.

Example 1

Each layer was formed by using a magnetron (C-Mag) sputter coating machine through the following process.

First, a first dielectric layer (SiAlN _x , 1.32 ≦ _x ≦ 1.35) was coated on a 6 mm thick transparent glass substrate at a thickness of 30 nm under an atmosphere of nitrogen / argon (nitrogen ratio: 45-60 vol%). Subsequently, the first sub-dielectric layer ZnAlO was coated with a thickness of 7 nm under an oxygen / argon (oxygen ratio: 5 to 20% by volume) atmosphere. Subsequently, the first metal protective layer (NiCr) was coated with a thickness of 0.5 nm under argon atmosphere, and the first metal layer (Ag) was coated with 7 nm under argon atmosphere. The second metal protective layer (NiCr) was then coated with a thickness of 0.5 nm under argon atmosphere. Subsequently, the second sub-dielectric layer ZnAlO was coated with a thickness of 7 nm under an oxygen / argon (oxygen ratio: 5 to 20% by volume) atmosphere. Subsequently, a second dielectric layer (SiAlN _x , 1.32 ≦ _x ≦ 1.35) was coated to a thickness of 75 nm under an atmosphere of nitrogen / argon (nitrogen ratio: 45 to 60% by volume). Subsequently, the third sub-dielectric layer (ZnAlO) was coated to a thickness of 7 nm under an oxygen / argon (oxygen ratio: 5 to 20% by volume) atmosphere. Subsequently, a third metal protective layer (NiCr) was coated with a thickness of 0.5 nm under an argon atmosphere. Subsequently, the second metal layer Ag was coated with a thickness of 18 nm under an argon atmosphere, and then the fourth metal protective layer (NiCr) was coated with a thickness of 0.5 nm under an argon atmosphere. Subsequently, the fourth sub-dielectric layer ZnAlO was coated with a thickness of 7 nm under an oxygen / argon (oxygen ratio: 5 to 20% by volume) atmosphere. Subsequently, a third dielectric layer (SiAlN _x , 1.32 ≦ _x ≦ 1.35) was coated with a thickness of 20 nm under an atmosphere of nitrogen / argon (nitrogen ratio: 45 to 60% by volume), and finally, a top protective layer (TiO _x N _y). , x: y = 19 mol%: 1 mol%) was subjected to a process of coating a 5 nm thick under a nitrogen / argon atmosphere (nitrogen ratio: 45 ~ 60% by volume) to prepare a low-emissive glass.

The low-emission glass was passed through a tempered furnace (600-700 ° C., respectively, upper and lower temperatures) used in the production process of tempered glass, heat-treated for about 5 minutes, and then subjected to post-treatment under conditions of rapid cooling.

Example 2

The low-emissive glass was manufactured and post-treated through the same process as in Example 1 except that the first metal layer was coated with a thickness of 4 nm and the second metal layer was coated with a thickness of 14 nm.

Example 3

The low-emissive glass was manufactured and post-treated through the same process as in Example 1 except that the first metal layer was coated with a thickness of 7 nm and the second metal layer was coated with a thickness of 15 nm.

Example 4

The low-emissive glass was manufactured and post-treated through the same process as in Example 1 except that the first metal layer was coated with a thickness of 7 nm and the second metal layer was coated with a thickness of 13 nm.

Comparative Example 1

The low-emissive glass was manufactured and post-treated through the same process as in Example 1 except that the first metal layer was coated with a thickness of 6 nm and the second metal layer was coated with a thickness of 8 nm.

Comparative Example 2

A low-emissive glass was manufactured and post-treated through the same process as in Example 1 except that the first metal layer was coated with a thickness of 13 nm and the second metal layer was coated with a thickness of 15 nm.

Comparative Example 3

The low-emissive glass was manufactured and post-treated through the same process as in Example 1 except that the first metal layer was coated with a thickness of 7 nm and the second metal layer was coated with a thickness of 21 nm.

Experimental Example 1

The physical properties of the low-emissive glass obtained in Examples 1 to 4 and Comparative Examples 1 to 3 were evaluated by the following method, and the results are shown in Table 1 below.

1. Visible light transmittance and reflected color: Visible light transmittance and reflected color were measured according to the D65 standard light source 10 degrees KS L 2514 in the wavelength range of 380 ~ 780 nm, respectively.

2. Emissivity: Emissivity was measured using Fourier transform infrared spectroscopy (FT-IR).

division Visible light transmittance Reflection color Emissivity 0 °° 55 °° a * b * a * b * Example 1 65.5 0.77 -5.8 -2.1 -2.8 0.025 Example 2 68.4 -0.46 -3.24 -1.2 -2.4 0.035 Example 3 66.4 0.89 -6.2 -2.8 -3.1 0.029 Example 4 67.7 1.52 -6.7 -3.1 -4.5 0.032 Comparative Example 1 72.0 -0.62 -7.4 4.5 -8.7 0.043 Comparative Example 2 56.9 2.72 -14.61 8.76 -17.91 0.020 Comparative Example 3 56.1 -1.54 -7.2 5.6 -8.2 0.021

Referring to Table 1, it can be seen that the low-emissivity glass according to the present invention is low in emissivity while high visible light transmittance. In addition, the low-emissivity glass according to the present invention can also confirm that the transparent color (neutral color) because the result of the evaluation of the reflection color on the front and side shows the vicinity of 0 to -7 to 1.

Claims (8)

Sequentially on the glass substrate, A glass coated with a first dielectric layer, a first sub dielectric layer, a first metal layer, a second sub dielectric layer, a second dielectric layer, a third sub dielectric layer, a second metal layer, a fourth sub dielectric layer, and a third dielectric layer, The first to fourth sub-dielectric layers are each composed of a Zn-based oxide containing at least one element selected from the group consisting of Sn, Nb, Al, Sb, Mo, Cr, Ti, and Ni, The sum of the thickness of the first metal layer and the thickness of the second metal layer is 18 to 25 nm. The method according to claim 1, The ratio of the thickness of the first metal layer and the thickness of the second metal layer is 1: 1.5 to 4 low-emissivity glass. The method according to claim 1, The low-emissive glass whose a * and b * value of a glass surface reflection color is -7-1 in observation angle 0 degrees-55 degrees. The method according to claim 1, Low-emissive glass, wherein the metal contained in each of the first metal layer and the second metal layer is at least one selected from the group consisting of Ag, Cu, Au, Al, and Pt. The method according to claim 1, A first metal protective layer provided between the first sub dielectric layer and the first metal layer; A second metal protective layer provided between the first metal layer and the second sub dielectric layer; A third metal protective layer provided between the third sub dielectric layer and the second metal layer; And The low emission glass further comprises a fourth metal protective layer provided between the second metal layer and the fourth sub-dielectric layer. The method according to claim 1, Further comprising a protective layer provided on the third dielectric layer, A low-emissive glass, wherein the protective layer is made of an oxide represented by TiO _x N _y (y / x <1 and x: y = 100 mol%: 0 mol% to 75 mol%: 25 mol%). The method according to claim 6, The low-emissive glass whose thickness of the said protective layer is 2-15 nm. The method according to claim 1, A low emissive glass having a transmittance of 58% or more, a shielding coefficient of 0.36 or less, and an emissivity of 0.025 to 0.035.

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