WO2017122991A1 - Low-emissivity glass - Google Patents

Abstract

The present invention provides a low-emissivity glass comprising: 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 the uppermost protective layer, which are sequentially stacked, beginning from the glass substrate.

Description

Low emission glass

The present invention relates to low-emissivity glass.

Low-emission glass is coated with a low-emission layer that has the function of blocking the sun's heat in summer and preserving indoor heat in the winter, and when used as a building exterior material, energy saving effect of the building can be obtained. Such low-emissive glass can be classified into two types according to the manufacturing method, soft low-E glass by the sputtering process and hard by Atmospheric Pressure Chemical Vapor Deposition. Hard Low-E glass. Hard Roy has the advantage that post coating is possible because it is an oxide film produced at high temperature, and it is free to handle.However, due to the low electrical conductivity of the coating film, it has a decisive disadvantage that insulation and shielding performance is lower than that of soft Roy. There is a limit to large-scale dissemination. On the other hand, the soft Roy manufactured by the sputtering method is relatively excellent in thermal insulation and shielding performance because the coating film is composed of metal Ag having the highest electrical conductivity, and is also composed of a multilayer film including various auxiliary films. By having the advantage that can supply products of various characteristics desired by consumers. However, due to the characteristics of the metal Ag film, which is easily oxidized and deformed even at high temperatures, even at room temperature, post-strengthening is impossible and there are many disadvantages in handling. Among them, the post-reinforcement is impossible because it requires coating after line reinforcement, which can be a fatal drawback in terms of distribution of the product. The proposed to improve this is Roy Glass (Temperable Roy Glass). It is Temperable Roy Glass is sometimes referred to as Heat Treatable Low-E or Heatable Low-E in the industry.Because it is soft glass, it is able to withstand both tempered and curved processing conditions. It has been applied to various fields requiring post heat treatment such as windshield.

For this purpose, Roy glass is usually heated to a temperature of 600-700 ° C. which bends or stresses. During this heat, the functional reflective metal layer (mainly Ag) on the glass substrate is often crystallized due to phenomena such as oxidation and diffusion or aggregation. There is a structural transformation. One of the methods for preventing such deformation, that is, deterioration at high temperature, is to laminate the silver metal layer in a sandwich structure using a metal protective film. However, these methods have also shown limitations in satisfying all desired thermal resistance while maintaining high visible light transmittance.

U. S. Patent No. 6,804, 048 describes heat treatable low-emissive glass having a structure of glass / first dielectric layer / low emissive metal layer / protective layer / second dielectric layer. However, this low-emissive glass has a disadvantage in that a blur occurs in the coating film during the heat treatment or the bending process, and scratches occur due to foreign matters.

The present invention provides a low-emissive glass which is excellent in transmittance and exhibits desired heat resistance even after heat treatment, and has improved durability.

The low-emissivity glass of this invention is a glass base material; 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 stacked from the glass substrate.

The low-emissivity glass of the present invention is excellent in transmittance and heat resistance even after heat treatment, and also excellent in durability, such as reduction of scratches caused by cloudiness and foreign matter.

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

The low-emissivity glass of this invention is a glass substrate and the 1st dielectric layer, the 1st sub dielectric layer, the reflective metal layer, the 1st metal protective layer, the 2nd sub dielectric layer, the 2nd dielectric layer, and the top protection which were laminated | stacked sequentially from the said glass substrate. It may comprise a layer. The low emission glass may have an emissivity of about 0.02 to 0.04, and a visible light transmittance of about 50% or more, but may not be limited thereto.

As the glass substrate, conventional glass which can be used in the art, such as for construction or automobile, may be used, for example, soda lime glass may be used, but the present invention may not be limited thereto. The thickness of the glass substrate may be appropriately selected by those skilled in the art according to the purpose of use, and may have a thickness of about 2 to 12 mm, but may not be limited thereto.

The first dielectric layer included in the low-emissivity glass of the present invention may have a thickness of about 20 to 50 nm, and at least one element selected from the group consisting of Sn, Nb, Al, Sb, Mo, Cr, Ti, and Ni. Si-based nitride or Si-based oxynitride containing may be included, but may not be limited thereto. For example, the first dielectric layer may include a SiAlN _x (x = 1.3 to 1.5) based structure, but may not be limited thereto.

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

The first sub-dielectric layer included in the low-emissivity glass of the present invention may have a thickness of about 5 to 10 nm, at least one selected from the group consisting of Sn, Nb, Al, Sb, Mo, Cr, Ti, and Ni. It may include a Zn-based oxide or Zn-based oxynitride containing an element, but may not be limited thereto. The first sub-dielectric layer may affect the crystallinity of the reflective metal layer to improve thermal performance of the low-emissive glass.

The first sub-dielectric layer may induce crystallization of the reflective metal layer well, and prevent oxygen gas from diffusing into the upper and lower dielectric layers during heat treatment of the reflective metal layer, and may suppress the occurrence of optical defects such as aggregation. have. Preferably, the first sub-dielectric layer may be Zn-based oxide containing Al, but may not be limited thereto.

The reflective metal layer included in the low-emissivity glass of the present invention may have a thickness of about 5 to 20 nm, and may include one or more metals selected from the group consisting of Ag, Cu, Au, Al, and Pt, but It may not be limited. The reflective metal layer may serve to selectively transmit and reflect light (solar ray) in the infrared region.

The first metal protective layer included in the low-emissivity glass of the present invention may have a thickness of about 0.5 to 2 nm, a group consisting of Ni, Cr, Ni-Cr alloy, and NiCrN _x (x = 0.8 to 1). It may include one or more selected from, but may not be limited thereto. Due to the metal protective layer, the durability of the low-emissivity glass of the present invention may be enhanced, and the metal protective layer may function to protect the reflective metal layer during heat treatment.

The first metal protective layer acts as a barrier to prevent the movement of O ₂ in the air during heat treatment for reinforcement and / or bending, and helps the reflective metal layer to perform stable behavior even under high heat treatment conditions. Can be.

The second sub-dielectric layer included in the low-emissivity glass of the present invention may have a thickness of about 5 to 10 nm, and at least one selected from the group consisting of Sn, Nb, Al, Sb, Mo, Cr, Ti, and Ni. It may include a Zn-based oxide or Zn-based oxynitride containing an element, but may not be limited thereto. The second sub-dielectric layer may affect the crystallinity of the reflective metal layer to improve thermal performance of the low-emissive glass.

The second sub-dielectric layer may induce crystallization of the reflective metal layer well, and prevent oxygen gas from diffusing into the upper and lower dielectric layers during heat treatment of the reflective metal layer, and may suppress the occurrence of optical defects such as aggregation. have. Preferably, the second sub-dielectric layer may be a Zn-based oxide containing Al, but may not be limited thereto.

The second dielectric layer included in the low-emissivity glass of the present invention may have a thickness of about 20 to 50 nm, and at least one element selected from the group consisting of Sn, Nb, Al, Sb, Mo, Cr, Ti, and Ni. Si-based nitride, Si-based oxide, or Si-based oxynitride containing may be included, but may not be limited thereto.

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

The uppermost protective layer included in the low-emissivity glass of the present invention may have a thickness of about 2 to 15 nm, TiO _x N _y (x = 0.9 ~ 0.98, y = 0.02 ~ 0.1, y / x <1) Ti-based oxynitride may include, but may not be limited thereto. Due to the uppermost protective layer, the durability of the low-emission glass of the present invention can be enhanced. The uppermost protective layer may serve to reduce the roughness of the surface of the low-emissive glass, increase scratch resistance, and increase mechanical and chemical durability of the coating film. If the thickness of the uppermost protective layer is less than about 2nm, there is a fear that the durability is lowered, and if the thickness of the uppermost protective layer exceeds about 15nm, the transmittance of the low-emissive glass may be reduced or cause clouding. Preferably, the thickness of the uppermost protective layer may be about 2 to 7 nm.

The Ti-based oxynitride included in the uppermost protective layer of the present invention may further contain one or more elements selected from W, Zr, and Si, but may not be limited thereto.

The low-emissivity glass of the present invention may further include 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, but may not be limited thereto. The second metal protective layer acts as a barrier to prevent the movement of O ₂ in the air during heat treatment for reinforcement and / or bending, and also helps the reflective metal layer to perform stable behavior even under high heat treatment conditions. Can be.

The second metal protective layer included in the low-emissivity glass of the present invention may include one or more selected from the group consisting of Ni, Cr, Ni-Cr alloy, and NiCrN _x (x = 0.8 to 1), but It may not be limited.

Hereinafter, the present invention will be described in more detail with reference to Examples. However, these examples are only for the understanding of the present invention, and the scope of the present invention in any sense is not limited to these examples.

EXAMPLE

Low radiation  Manufacture of glass 1- Example  One

A 6 mm thick transparent glass was first coated with a SiAlN _x (x = 1.3-1.5) layer with a thickness of 25 nm under a nitrogen / argon atmosphere as the first dielectric layer. The ZnAlO layer was then coated at 10 nm under argon / oxygen atmosphere as the first sub-dielectric layer. Ag was then coated with a reflective metal layer at about 10 nm under an argon atmosphere. The NiCr layer was coated 0.8 nm thick with a first metal protective layer, followed by a 10 nm thick ZnAlO layer with a second sub-dielectric layer under an argon / oxygen atmosphere, and a SiAlN _x (x = 1.3-1.5) layer with a second dielectric layer. Was coated to a thickness of 25 nm under nitrogen / argon atmosphere. Finally, the TiO _x N _y (x = 0.9 to 0.98, y = 0.02 to 0.1, y / x <1) layer was coated with a thickness of about 5 nm under an argon nitrogen atmosphere as the uppermost protective layer. Prepared. The film structure of the low-emissivity glass of Example 1 prepared 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 / top protective layer .

Preparation of Low Emissive Glass 1-Comparative Example 1

The low-emissive glass was manufactured under the same conditions as in Example 1 except that the second metal protective layer was further included before the coating of the reflective metal layer and the top protective layer was not included. 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 prepared was as follows: first dielectric layer / first sub-dielectric layer / second metal protective layer / reflective metal layer (Ag) / first metal protective layer / second sub-dielectric layer / agent 2 dielectric layers.

Preparation of Low Emissive Glass 1-Comparative Example 2

The low-emissive glass was manufactured 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-emissive glass of Comparative Example 2 prepared was as follows: first dielectric layer / reflective metal layer (Ag) / first metal protective layer / second dielectric layer.

Preparation of Low Emissive Glass 1-Comparative Example 3

A low-emissive glass was manufactured 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 prepared 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 radiation  Preparation of Glass 1-Property Evaluation

The low-emissive glass samples of Examples 1 and Comparative Examples 1 to 3 prepared above, the low-emissive glass sample while maintaining the temperature of the bottom of the phase at a temperature of about 600 ~ 700 ℃ in a general strengthening furnace used for producing tempered glass Heated for about 5 minutes to pass through and then quenching conditions.

Before and after the heat treatment, visible light transmittance was measured according to the KS L 2514 standard at 10 degrees of D65 standard light source in the wavelength range of 380 to 780 nm, and the sheet resistance was measured by a surface resistance measuring instrument (non-contact sheet resistance measuring instrument). Emissivity was measured according to KS L 2525 standard using an infrared spectrometer (FTIR). Emissivity is a value measured by Ag, which is a reflective metal layer, and is one of physical properties that can be used as a low-emissivity glass. The scratches were measured using an Elcometer 1720 instrument. Specifically, the glass specimen was placed on the measuring instrument, sprinkled with water, and matched with the cleaning conditions. Was confirmed and evaluated as level (Lv). Haze is a method of evaluating the degree of clouding of the coating film after heat treatment of the low-emission glass, and the level (Lv) was evaluated by visual observation.

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

Sample	Remarks	Visible light	Sheet resistance	Emissivity	scratch	Haze
		Transmittance (%)	(Ω / sq)		Lv.	Lv.
Example 1	Before heat treatment	81.7	6.8	0.06	2	X
	After heat treatment	86.8	4.8	0.04	2	2
Comparative Example 1	Before heat treatment	74.6	6.82	0.06	3	X
	After heat treatment	81.4	4.35	0.04	3	2
Comparative Example 2	Before heat treatment	82.3	7.5	0.07	2	X
	After heat treatment	87.1	5.5	0.05	4	4
Comparative Example 3	Before heat treatment	80.4	6.81	0.06	3	X
	After heat treatment	85.8	4.8	0.04	3	2

X: no blur

As can be seen in Table 1, the low-emissive glass according to the embodiment of the present invention has excellent visible light transmittance before and after heat treatment, and also excellent in sheet resistance, scratch performance and haze performance, suitable for use in building glass, etc. Do. On the other hand, the low-emission glass according to Comparative Examples 1 to 3 was found to be somewhat insufficient to maintain high permeability and at the same time durability and heat resistance performance.

Low radiation  Manufacture of glass 2- Example  2

The 6 mm thick transparent glass was first coated with a SiAlN _x (x = 1.3-1.5) layer with a thickness of 25 nm under nitrogen / argon atmosphere as the first dielectric layer. The ZnAlO layer was then coated at 10 nm under an argon / oxygen atmosphere as the first sub-dielectric layer. The NiCr layer was then coated 3 nm thick with a second metal protective layer, and the reflective metal layer Ag was coated at about 10 nm under an argon atmosphere. The NiCr layer was then coated with a first metal protective layer 1.5 nm thick, followed by a 10 nm thick ZnAlO layer with a second sub-dielectric layer under an argon / oxygen atmosphere and SiAlN _x (x = 1.3-1.5) as a second dielectric layer. The layer was coated to 25 nm thick under nitrogen / argon atmosphere. Finally, the TiO _x N _y (x = 0.9-0.98, y = 0.02-0. 1, y / x <1) layer was coated with a thickness of about 5 nm under an argon / nitrogen atmosphere as the uppermost protective layer. Was prepared. The film structure of the low-emissivity glass of Example 2 prepared was as follows: first dielectric layer / first sub-dielectric layer / second metal protective layer / reflective metal layer (Ag) / first metal protective layer / second sub-dielectric layer / first 2 dielectric layer / top protection layer.

Low radiation  Manufacture of glass 2- Comparative example  4

A low-emissive glass was prepared under the same conditions as in Example 2 except that the first and second sub-dielectric layers were not included. The film structure of the low-emissivity glass of Comparative Example 4 prepared was as follows: first dielectric layer / second metal protective layer / reflective metal layer (Ag) / first metal protective layer / second dielectric layer / top protective layer.

Low radiation  Manufacture of glass 2- Comparative example  5

A low-emissive glass was produced under the same conditions as in Example 2 except that the first and second sub-dielectric layers and the uppermost protective layer were not included. The film structure of the low-emissive glass of Comparative Example 5 prepared was as follows: first dielectric layer / second metal protective layer / reflective metal layer (Ag) / first metal protective layer / second dielectric layer.

Low radiation  Preparation of Glass 2-Evaluation of Properties

The low-emissive glass samples of Examples 2 and Comparative Examples 4 to 5 prepared above, the low-emissive glass sample while maintaining the temperature of the bottom of the phase at a temperature of about 600 ~ 700 ℃ in a general strengthening furnace used for producing tempered glass Heated for about 5 minutes to pass through and then quenching conditions.

Before and after the heat treatment, visible light transmittance was measured according to the KS L 2514 standard at 10 degrees of D65 standard light source in the wavelength range of 380 to 780 nm, and the sheet resistance was measured by a surface resistance measuring instrument (non-contact sheet resistance measuring instrument). Emissivity was measured according to KS L 2525 standard using an infrared spectrometer (FTIR). Emissivity is a value measured by Ag, which is a reflective metal layer, and is one of physical properties that can be used as a low-emissivity glass. The scratches were measured using an Elcometer 1720 instrument. Specifically, the glass specimen was placed on the measuring instrument, sprinkled with water, and matched with the cleaning conditions. Was confirmed and evaluated as level (Lv). Haze is a method of evaluating the degree of clouding of the coating film after heat treatment of the low-emission glass, and the level (Lv) was evaluated by visual observation.

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

Sample	Remarks	Visible light	Sheet resistance	Emissivity	scratch	Haze
		Transmittance (%)	(Ω / sq)		Lv.	Lv.
Example 2	Before heat treatment	52.0	4.2	0.04	One	X
	After heat treatment	59.0	2.6	0.02	One	One
Comparative Example 4	Before heat treatment	53.0	5.0	0.04	2	X
	After heat treatment	56.0	3.8	0.03	3	3
Comparative Example 5	Before heat treatment	52.4	5.02	0.05	2	X
	After heat treatment	55.8	3.85	0.03	3	2

X: no blur

As can be seen in Table 2, the low-emissivity glass according to the embodiment of the present invention is excellent in visible light transmittance before and after heat treatment, and also excellent in sheet resistance, scratch performance and haze performance suitable for use in building glass, etc. Do. On the other hand, the low-emissivity glass according to Comparative Examples 4 to 5 was found to be somewhat insufficient to maintain high transmission performance and durability and heat resistance performance.

Claims (11)

1. Glass substrates; And sequentially laminated from the glass substrate,

   A first dielectric layer;

   A first subdielectric layer;

   Reflective metal layer;

   A first metal protective layer;

   A second subdielectric layer;

   A second dielectric layer; And

   Top protective layer

   Including, low-emissivity glass.
2. The method of 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, Ti and Ni. It is to contain, low radiation glass.
3. The method of claim 1,

   The first sub-dielectric layer has a thickness of 5 to 10 nm and contains Zn-based oxides or Zn-based oxynitrides containing at least one element selected from the group consisting of Sn, Nb, Al, Sb, Mo, Cr, Ti, and Ni. To include, low-emissivity glass.
4. The method of claim 1,

   The reflective metal layer has a thickness of 5 to 20 nm, and comprises one or more metals selected from the group consisting of Ag, Cu, Au, Al, and Pt, low radiation glass.
5. The method of claim 1,

   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 NiCrN _x (x = 0.8 to 1), Spinning glass.
6. The method of claim 1,

   The second subdielectric layer has a thickness of 5 to 10 nm and contains Zn-based oxide or Zn-based oxynitride containing at least one element selected from the group consisting of Sn, Nb, Al, Sb, Mo, Cr, Ti and Ni. To include, low-emissivity glass.
7. The method of claim 1,

   The second dielectric layer has a thickness of 20 to 50 nm, and contains Si-based nitride, Si-based oxide, or at least one element selected from the group consisting of Sn, Nb, Al, Sb, Mo, Cr, Ti, and Ni; or A low radiation glass containing Si type oxynitride.
8. The top protective layer of claim 1, wherein the uppermost protective layer has a thickness of 2 to 15 nm and includes Ti-based oxynitride having TiO _x N _y (x = 0.9-0.98, y = 0.02-0.1, y / x <1). Low emission glass which is to.
9. The method of claim 8,

   The Ti-based oxynitride further comprises one or more elements selected from W, Zr, and Si, low-emissivity glass.
10. The method of claim 1,

    And a second metal protective layer 1.5 to 5 nm thick between the first sub-dielectric layer and the reflective metal layer.
11. The method of claim 10,

    The second metal protective layer is Ni, Cr, Ni-Cr alloy, and NiCrN _x (x = 0.8 ~ 1), wherein the low-emissive glass containing at least one selected from the group consisting of.