KR20110062566A - Bendable and heat treatable low-emissivity glass and method for preparing the same - Google Patents

Abstract

PURPOSE: Low-emissivity glass and a producing method thereof are provided to secure the high visible light transmission rate greater than 70% after a heat-treating process using dielectric layers and functional reflective-metal protecting layers. CONSTITUTION: Low-emissivity glass capable of bending and tempering includes the following: a first dielectric layer formed with Zn system oxides, and coated on a glass substrate; a first functional reflective-metal protecting layer protecting a functional reflective-metal layer during a heating process; the functional reflective-metal layer reflecting far infrared rays and the solar radiation; a second functional reflective-metal protecting layer; a second dielectric layer formed with either Si system nitrides or oxy-nitrides; and a top protecting layer.

Description

Bendable and heat treatable low-emissivity glass and method for preparing the same}

The present invention relates to a low-radiation glass and a method for manufacturing the same, and more particularly, to a low-radiation glass capable of bending and heat treatment and excellent in durability.

Low-Emissivity (Low-E) glass (commonly referred to as 'Roy glass') is widely used in construction and automotive applications, and it has recently been required to have a visible light transmittance of 70% or more in addition to the basic function of preventing energy loss. Is the trend.

In certain cases, the low-emissive glass also needs to undergo bending or prestressing (often heat treatment) of bending or tempering type. For this purpose, the pane is typically heated to a temperature of about 600 to 700 ° C. prior to the actual treatment of bending or prestressing, during which the functional reflective metal layer (primarily a silver layer) on the glass substrate is often oxidized and diffused. Or, due to the process of agglomeration, it undergoes a structural deformation.

Deformation of the silver metal layer can be confirmed with the naked eye, and this phenomenon appears as a haze phenomenon. This blurring phenomenon can be confirmed by changing the transmittance, surface resistance of the coating surface, and emissivity.

Therefore, the demand for low-emissivity glass that can withstand high thermal stress, low emissivity before thermal (preliminary stress) treatment, high optical properties, and no blur after heat treatment has recently increased. Accordingly, various methods have been proposed for the purpose of improving the multilayer coating film of the low-emissive glass, and examples thereof include the following.

One known method for preventing deterioration of a reflective metal layer such as silver (Ag) at high temperatures is to laminate the silver metal layer in a sandwich (Ti / Ag / Ti) structure between protective films of an oxidizable metal such as titanium.

The thickness of this metal protective film should usually be sufficient to prevent the silver metal layer from deteriorating when the coated glass is heat treated at a high temperature. Such techniques are disclosed in US Pat. No. 4,790,922 and US Pat. No. 4,806,220. However, the heat treatment of such a film structure is more difficult to use commercially because of the blurring phenomenon.

On the other hand, the film structure disclosed in EP 0718250 introduces an oxygen barrier diffusion layer, in particular a layer based on silicon nitride (Si _x N _y ), on top of a functional layer or layers based on silver, and a priming layer. Instead of inserting a priming layer or protective metal layer, it suggests placing a silver layer just above the underlying dielectric coating. By way of example, a multilayer structure of type Si ₃ N ₄ / ZnO / Ag / Nb / ZnO / Si ₃ N ₄ or SiO ₂ / ZnO / Ag / Nb / Si ₃ N ₄ is presented. However, the above structure is not suitable for the naked eye because the visible light transmittance does not satisfy more than 70% after heat treatment, or the silver coating film is agglomerated and diffused, which is not suitable for the naked eye, or the silver coating film reflects the infrared region. Lost and not suitable for commercial use as low-emissive glass.

International Publication No. W097 / 48649 discloses Si ₃ N ₄ / Nb / Ag / Nb which can be toughened (hardened heat treatment) with two thin metal "blocking" layers based on niobium and 0.7 to 2 nm thick. Multilayer structures of the same type as / Si ₃ N ₄ are disclosed. However, such a structure is very difficult to satisfy 70% or more of transmittance after heat treatment.

U. S. Patent No. 6,804, 048 discloses a heat treatable low-emissive glass having a glass / SnO ₂ / ZnO / Ag / Nb / Si ₃ N ₄ layer structure. However, this low-emissive glass has a disadvantage in that scratches occur in the coating during the heat treatment or bending process.

Therefore, the present invention has been invented to solve the above problems, preferably after the heat treatment has a high visible light transmittance of 70% or more, and also possible to post-process heat treatment (bending, strengthening) and there is no cloudy phenomenon or significantly reduced after heat treatment And the purpose is to provide a low-radiation glass and excellent manufacturing method excellent in durability.

In order to achieve the above object, the present invention is made of a Zn-based oxide containing at least one element selected from Sn, Nb, Al, Sb, Mo, Cr, Ti and Ni, sequentially coated on a glass substrate 1 dielectric layer; A first functional reflective metal protective layer that protects the following functional reflective metal layer upon thermal treatment and assists fusion of the following functional reflective metal layer; A functional reflective metal layer that reflects infrared or solar radiation; A second functional reflective metal protective layer protecting the functional reflective metal layer during heat treatment; A second dielectric layer made of Si-based nitride or nitride oxide containing at least one element selected from Al, B, Ti, Nb, Sn and Mo; It provides a low-radiation glass capable of bending and heat treatment, including; and the uppermost protective layer.

In addition, the present invention, the first dielectric layer consisting of a Zn-based oxide containing at least one element selected from Sn, Nb, Al, Sb, Mo, Cr, Ti and Ni on a glass substrate, protects the following functional reflective metal layer during heat treatment And a first functional reflective metal protective layer which helps fusion of the following functional reflective metal layer, a functional reflective metal layer that reflects infrared rays or solar radiation, a second functional reflective metal protective layer which protects the functional reflective metal layer during heat treatment, Al, B, Ti Sequentially coating a second dielectric layer made of Si-based nitride or nitride oxide containing at least one element selected from Nb, Sn and Mo; And coating a top protective layer; provides a method for producing a low-radiation glass capable of bending and heat treatment comprising a.

Accordingly, according to the low-emissivity glass of the present invention and the manufacturing method thereof, visible light transmittance is 70% or more, there is no cloudy phenomenon after heat treatment, it is possible to easily manufacture low-emission glass excellent in durability and excellent heat treatment and bending processing do.

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those skilled in the art may easily implement the present invention.

1 is a view schematically showing the layer structure of the heat-resistant low-radiation glass of the present invention, Figure 2 is a view schematically showing an example of the configuration of the coating apparatus for producing a low-emissivity glass according to the present invention .

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to low radiation glass capable of heat treatment and bending and excellent durability, which is a function of reflecting a first dielectric layer, a first functional reflective metal protective layer, infrared rays or solar radiation sequentially coated on a glass substrate. And a reflective metal layer, a second functional reflective metal protective layer, a second dielectric layer, and an uppermost protective layer. Here, an organic film may be bonded to the uppermost protective layer.

First, as the glass substrate, conventional glass such as soda-lime glass, which is used for construction or automobiles, may be used, and other glass such as plastic or iron plate may be used without limitation. In addition, depending on the purpose of use, glass having a thickness of 2 to 12 mm can be freely used.

The first dielectric layer and the second dielectric layer serve to block oxygen or ions transferred to the functional reflective metal layer during heat treatment such as reinforcement and bending. In the present invention, the first dielectric layer is a Zn-based oxide containing at least one element selected from Sn, Nb, Al, Sb, Mo, Cr, Ti and Ni, more preferably Zn-based oxide containing Sn Can be done. For example, it may have a composition of Zn ₂ SnO ₄ , but the composition range may be variously applied depending on the atmosphere gas content during coating, and suppresses agglomeration or haze due to high heat of the functional reflective metal layer during heat treatment. Do it. When the functional reflective metal protective layer is present, O ₂ of the dielectric layer diffuses into the functional reflective protective layer, which is a metal film or a partial oxide film, at a high temperature of 600 ° C. or higher, thereby increasing the visible light transmittance to, for example, 70% or more after heat treatment. To make it possible.

The diffraction pattern that appears on the crystalline material through X-rays is unique to the material, and it is like a kind of fingerprint, and the crystal structure, lattice constant, etc., which are important information about the structure of the material by XRD (X-Ray Diffractometer) analysis of unknown material I can figure it out. Accordingly, according to the XRD analysis results, peaks of the Zn-based dielectric layer 002 plane and the Ag (111) layer plane appear, indicating the lattice parameters of the Zn-based dielectric layer and the Ag layer. The crystallinity of the Zn-based dielectric layer induces the Ag layer to crystallize well when the Ag layer is deposited on the Zn-based dielectric layer. Accordingly, the Zn-based dielectric layer helps stabilize the Ag film, thereby preventing the Ag film from diffusing into the upper and lower dielectric films during heat treatment and preventing optical defects such as agglomeration from occurring, thereby preventing cloudy coating.

In the present invention, the material of the second dielectric layer formed on the second functional reflective metal protective layer to be described later includes Si-based nitride or nitride oxide containing at least one element selected from Al, B, Ti, Nb, Sn and Mo. Can be used. For example, it is preferable to use Si _x N _y (x / y <0.75), Si _x O _y N _z (x / y <2, x / z <0.75) and the like. Among them, the refractive index of the Si _x O _y N _z film can be changed from about 1.46 to 2.3 depending on the composition of x, y, and z, and among these, 1.5 ≦ n (refractive index) ≦ 1.9 is preferable.

As the second dielectric layer, the Si _x O _y N _z coating layer has a refractive index n of about 1.46 to 2.3, as mentioned on page 72, "Sputterered Silicon Oxynitride for Microphotomics: A Materals Study by Jessica Gene Sandlad". Among them, preferably, a dielectric layer having a refractive index n of about 1.5 to 1.9 may be used, and more preferably, a dielectric layer having a refractive index of 1.5 to 1.7 may be used. At this time, in order to obtain a desired refractive index, it is necessary to adjust the sputtering conditions such as the partial pressure of argon / oxygen / nitrogen (eg, argon / oxygen / nitrogen = 360sccm / 120sccm / 320sccm) and power / voltage. Stoichiometry can be observed and controlled through a plasma emission monitor (PEM).

The thickness of the first dielectric layer and the second dielectric layer is preferably in the range of 10 to 55 nm, more preferably the thickness of the first dielectric layer is 20 to 45 nm, and the thickness of the second dielectric layer is 30 to 55 nm. It is good to have. If the thickness of each of the first dielectric material and the second dielectric layer is less than 10 nm or more than 55 nm, there may be a problem that the durability of the coating film is degraded or the optical properties are degraded.

In the low-emissivity glass of the present invention, the first functional reflective metal protective layer formed on the first dielectric layer is a barrier preventing the movement of Na and O _{2 in} the air diffused in the glass during heat treatment such as strengthening and bending. Role and Ag layer (functional reflective metal layer) helps the fusion of Ag to enable stable behavior even under high heat treatment conditions, and finally plays an important function of absorbing O ₂ penetrating into the functional reflective metal layer. The first functional reflective metal protective layer may be made of Ni, Cr or Ni-Cr alloy, and the thickness thereof is preferably in the range of 0.5 to 5 nm, more preferably in the thickness of 0.5 to 1.5 nm. . If the thickness of the first functional metal protective layer is less than 0.5 nm, there may be a problem that the cloudyness of the coating film is increased after the heat treatment and the bending process. When the thickness of the first functional metal protective layer is greater than 5 nm, the transmittance is lowered or the cloudyness of the coating film is also increased after the heat treatment and the bending process. There may be a problem.

In addition, the functional reflective metal layer formed on the first functional reflective metal layer serves to selectively transmit and reflect solar radiation. In the present invention, Ag, Au, Cu, or the like may be used as the material of the functional reflective metal layer, and Ag (silver) is most preferred. The functional reflective metal layer of low radiation glass requires high electrical conductivity, low absorption in the visible region, and excellent durability. Ag is most suitable for this. When silver is used as the material of the functional reflective metal layer, some elements may be added to improve durability, but if the input amount is excessively high, the low radiation performance may be deteriorated. According to one embodiment of the present invention, as a material of the functional reflective metal layer, silver (Ag) doped with 0.5 to 5% by weight of an element selected from Ni, Pd, Pt, Cu, and Au may be used. When the content of the element doped in silver (Ag) is less than 0.5% by weight, it may be difficult to improve the desired level of durability, and when it exceeds 5% by weight, the performance of reflecting the infrared region may deteriorate or clouding may occur after heat treatment. have. In addition, the thickness of the functional reflective metal layer is preferably 4 to 14 nm, more preferably 6 to 10 nm. If the thickness is less than 4 nm, the low radiation performance may not be sufficient. If the thickness exceeds 14 nm, the reflectance may be excessively high, which may lower the open feeling.

Meanwhile, the second functional reflective metal protective layer formed on the functional reflective metal layer may include Ni, Cr, or Ni-Cr alloy which is not nitrided or oxidized or oxidized at a rate of 50 mol% or less. In the case of Ni-Cr alloy, the weight ratio of Ni and Cr may be 90:10 to 70:30, more preferably 80:20. When Ni, Cr, or Ni-Cr alloy coats the oxide film (ie, the first dielectric layer in the present invention), the ratio of argon and oxygen should be about 80/20 (eg Ar 664sccm / O ₂ 136sccm). . If the ratio of oxygen is too high, Ag may be oxidized during the coating process. If the ratio of oxygen is too low, it may be coated with a metal film instead of a partial oxide film. Therefore, when coating a NiCrO _x film in the process, it is important to properly control its oxidation rate, and the coating for this can be determined by the hysteresis curve of the metal. In addition, when the argon / oxygen partial pressure is 80/20, the absorption coefficient (Extinction Coefficient) value of the single layer is the lowest, and Ag can be prevented from being oxidized during coating, and the cloudy state is excellent after the heat treatment. In addition, the thickness is in the range of 2 to 20 nm, preferably in terms of visible light transmittance without blur after heat treatment, and more preferably 4 to 10 nm.

In the low-emissivity glass of the present invention, the material of the uppermost protective layer formed on the second functional reflective metal protective layer includes Ti-based nitride containing at least one element selected from W, Ti, Si, Ta, Al, and Zr. It can be an oxide. Here, the top protective layer using TiO _x N _y reduces surface roughness as mentioned in "Characterization of TiOxNy films grown by PECVD Method: Structural and optical properties_Solid State Phenomena Vol. 111 (April 2009) pp.151-154". It serves to increase scratch resistance and to increase mechanical / chemical durability of the coating film. For example, TiO _x N _y (1.37 ≦ _x + _y ≦ 1.95, 0.15 ≦ _y ≦ 0.92) is preferable. Bending and heat treatment in that it will tend to "Nitrogen effects on crystallization kinetics of amorphous TiOxNy thin film_Lawrence Berkeley National Laboratory_2001" mentioned was nitrogen inside as TiO _x N _y on by reducing the stress, reducing the coating fracture which can occur during heat treatment It is advantageous in the case of coating, and proper oxidizing and nitriding atmosphere control is required for coating. This stoichiometry can be monitored via PEM. It is preferable that the thickness of an uppermost protective layer is 2-15 nm, More preferably, it is 5-10 nm. If the thickness is less than 2 nm, the color may appear red, resulting in poor aesthetics and poor durability. If the thickness is more than 15 nm, the transmittance may be reduced or cause blurring.

On the other hand, the low-emissive glass of the present invention, in addition to the functional layers as described above, may further include functional layers commonly employed in the low-emissive glass within the scope that can achieve the object of the present invention. In addition, the low-emissivity glass of the present invention may be configured by repeating two or more multilayer structures including a series of functional layers sequentially stacked on a glass substrate as shown in FIGS. 3 and 4.

That is, a first functional reflection including a first dielectric layer containing a Zn-based oxide containing at least one element selected from Sn, Nb, Al, Sb, Mo, Cr, Ti, and Ni, Ni, Cr, or Ni-Cr alloy A metal protective layer, a functional reflective metal layer that reflects infrared or solar radiation, a second functional reflective metal protective layer comprising Ni, Cr, or Ni-Cr alloy oxidized to 50 mol% or less, and Al, B, Ti, Nb, W, Ti, Si, Ta, at the top of the multilayer structure formed by sequentially stacking a second dielectric layer including a Si-based oxide or nitride oxide containing at least one element selected from Sn and Mo is repeatedly stacked on a glass substrate The uppermost protective layer including a nitride oxide containing at least one element selected from Al and Zr may be laminated.

Thus, the low-emissivity glass according to the present invention is a functional reflective metal protective layer comprising Ni, Cr or Ni-Cr alloy which is not nitrided or oxidized or nitrided or oxidized to 50 mol% or less as a layer in contact with the functional reflective metal layer. It may further comprise one or more, the functional reflective metal protective layer may be present between the first dielectric layer and the functional reflective metal protective layer or between the first dielectric layer and the top protective layer.

According to another embodiment of the present invention, on the glass substrate, the first dielectric layer, the first functional reflective metal protective layer, the functional reflective metal layer, the second functional reflective metal protective layer, the second dielectric layer, and the top protective layer described above The coating may be repeated two or more times to produce a low radiation glass.

Typically, the low-emissive glass of the present invention may be manufactured by the following procedure using a vacuum sputtering method as a thin film forming method for laminating each coating film. First, the glass substrate is placed in a vacuum chamber and evacuated until the degree of vacuum becomes 5 × 10 ⁻⁷ to 9 × 10 ⁻⁵ torr to form a vacuum. Then, as discharge occurs and gas plasma is generated, argon (Ar), oxygen (O ₂ ), nitrogen (N ₂ ) gas, etc. are introduced into the vacuum chamber, and a direct current or alternating voltage is applied between the two electrodes. As gas ions collide with a cathode provided with a metal target to be stacked, atoms are released from the metal target to be stacked on a substrate. An appropriate gas is introduced according to the type of coating film to be laminated, and the thickness of the coating film to be formed is appropriately controlled by appropriately adjusting the deposition rate of each coating film and the time exposed to the sputtering process. At this time, there is no particular limitation on the temperature of the substrate.

The low emissive glass of the present invention can be produced by sequentially coating functional layers onto a glass substrate using a Magnettron sputter coater as shown in FIG. 2. In the sputter coater of FIG. 2, t1 to t12 are both silicon and titanium tubular targets used to coat targets for forming the first and second dielectric layers, such as Si _x N _y (Si _x O _y N _z ) and TiOxNy films. P1 is a target for forming a first dielectric layer, for example, a Zn target containing Sn, P2 and P4 are targets for forming a functional reflective metal protective layer, such as a NiCr target (Ni: Cr = 80: 20), and P3 is a functional Targets for forming reflective metal layers, such as Ag targets. According to one example of the present invention, a glass substrate is introduced into the sputter coater of FIG. 2, and the respective functional layers are sequentially coated while moving from the zones ZONE1 to 7. The thickness of each layer can be easily adjusted by adjusting the moving speed of a glass substrate or the sputtering speed by voltage regulation of each target.

The visible light transmittance of the low-emissivity glass according to the present invention is preferably 40% or more, more preferably 50% or more when measured before heat treatment with a D65 standard light source of 380 to 780 nm when the thickness of the transparent glass substrate is 6 mm. When measuring after heat treatment, it is preferably 70% or more, and more preferably 74% or more.

Further, the low-emissivity glass of the present invention preferably has a sheet resistance of 13 GPa / sq or less and an emissivity of 0.15 or less.

Hereinafter, the present invention will be described in more detail with reference to Examples. However, the scope of protection of the present invention is not limited by these examples.

[ Example ]

Using a Magnettron sputter coater as shown in Figure 2, a low-emissive glass with a film having a composition and thickness as shown in the following Examples and Comparative Examples was prepared.

Example  1 to Example  5

The first dielectric layer (ZnSnO) was first coated with a thickness of 25 nm under oxygen / argon (80% oxygen / 20% argon partial pressure) atmosphere to 6 mm thick transparent glass as a glass substrate. Subsequently, the NiCr films were each 0.5 nm (Example 1), 1 nm (Example 2), 1.5 nm (Example 3), 2 nm (Example 4), 2.5 nm (Example) under an argon atmosphere as the first functional reflective metal protective layer. 5) and each Ag metal layer was coated with a thickness of 8.5 nm under an argon 100% atmosphere as a functional reflective metal layer. The film was then coated 6 nm thick under an oxygen / argon (oxygen 20% / argon 80% partial pressure) atmosphere with a second functional reflective metal protective layer (NiCrO _x , x = 1.67). The second dielectric layer (Si _x O _y N _z , x = 1, y = 0.08, z = 0.63) was then 30 nm thick under oxygen / nitrogen / argon (oxygen 15% / nitrogen 40% / argon 45% partial pressure) atmosphere. The TiO _x N _y (x = 1.14, y = 0.23) layer was coated with a thickness of 5 nm under an oxygen / nitrogen / argon (16% oxygen / 68% nitrogen / argon 16% partial pressure) atmosphere as a top protective layer. Then, after each sample was heat-treated, the cloudiness was measured. (The blur is considered good within 3.2 and the bad is above 8)

In Example 2, the sample of Example 2 having the best cloudiness was heat-treated at 685 ° C. for 2 minutes to 20 minutes at an electric furnace, and then visible light transmittance and solar ray transmittance were measured according to each heat treatment time. As a result, it was confirmed that both visible light transmittance and heat transmittance change were good (within 3% change rate) according to the heat treatment time from the 2-minute heat treatment. 5 is a graph showing a change in transmittance according to heat treatment time.

In addition, the parameters of the sputtering process performed in preparing the sample of Example 2 having the highest haze among the above examples are shown in the form of the table below.

Example  6 to 8

Samples were further prepared as shown in Table 4 below to check durability, and the scratch and moisture resistance were evaluated together with the samples prepared above.

(Scratches should not be visible to the naked eye and ΔEnbs is considered to be good when the number of pinholes within 1.5 is less than or equal to three in a prepared 100 × 100 mm specimen)

Comparative example  1, 2

For the comparative example of the first functional reflective metal protective layer, the first dielectric layer (ZnSnO) was first coated with a thickness of 25 nm under an oxygen / argon (80% oxygen / 20% partial pressure) atmosphere in a 6 mm thick transparent glass as a glass substrate. . Subsequently, the NiCr films were first coated with a first functional reflective metal protective layer under an argon atmosphere at 0 nm (no coating in Comparative Example 1) and 8 nm thick (Comparative Example 2), respectively. coating with nm. Next, the film was coated with a second functional reflective metal protective layer (NiCrO _x , x = 1.67) in an oxygen / argon (oxygen 80% / argon 20% partial pressure) atmosphere to a thickness of 6 nm. Then, the second dielectric layer (Si _x O _y N _z , x = 1, y = 0.08, z = 0.63) was made to have a thickness of 30 nm under oxygen / nitrogen / argon (oxygen 15% / nitrogen 40% / argon 45% partial pressure) atmosphere. After coating, the TiO _x N _y (x = 1.14, y = 0.23) layer as a top protective layer was coated to a thickness of 5 nm under an oxygen / nitrogen / argon (16% oxygen / 68% nitrogen / argon 16% partial pressure) atmosphere, Each sample was measured for haze after heat treatment.

(The cloudiness is considered to be good within 3.2 and the quality is above 8. The transmittance should be 70% or more after heat treatment.)

In Comparative Example 1, the cloudiness was not satisfied, and in Comparative Example 2, the NiCr thickness was

The coating was too thick to satisfy the transmittance.

Comparative example  3

The sample of Comparative Example 3 was compared with the sample of Example 2 to compare the second functional reflective metal protective layer. In the sample of Comparative Example 3, the first dielectric layer (ZnSnO) was first coated on a 6 mm thick transparent glass at 25 nm in an oxygen / argon (80% oxygen / 20% argon) atmosphere. Subsequently, the NiCr films were each coated with a thickness of 1 nm under an argon atmosphere as the first functional reflective metal protective layer, and the Ag metal layer was coated with a thickness of 8.5 nm under an argon 100% atmosphere. Next, the film was coated with a second functional reflective metal protective layer (NiCrO _x , x = 1.95) in an oxygen / argon (oxygen 80% / argon 20% partial pressure) atmosphere to a thickness of 6 nm. Then, the second dielectric layer (Si _x O _y N _z , x = 1, y = 0.08, z = 0.63) was made to have a thickness of 30 nm under oxygen / nitrogen / argon (oxygen 15% / nitrogen 40% / argon 45% partial pressure) atmosphere. The TiO _x N _y (x = 1.14, y = 0.23) layer was coated to a thickness of 5 nm under an oxygen / nitrogen / argon (16% oxygen / 68% nitrogen / argon 16% partial pressure) atmosphere as a top protective layer. Thus, compared with Comparative Example 2 For Example, a comparative example for the difference, i.e. the difference between the gas partial pressure of the NiCrO _x coating film of gas conditions when coating NiCrO _x film.

After each sample was heat treated, the cloudiness was measured.

(The haze is considered to be good within 3.2 and the bad is above 8. The sheet resistance should be less than 15Ω)

In the case of Comparative Example 3, Ag was oxidized during coating and the sheet resistance appeared as Error, which was evaluated as poor.

Comparative example  4

For comparison of the uppermost protective layer, the first dielectric layer (ZnSnO) was first coated with a thickness of 25 nm in an oxygen / argon (80% oxygen / 20% argon) atmosphere in a 6 mm thick transparent glass. Subsequently, each of the NiCr films was sequentially coated with a first functional reflective metal protective layer under an argon atmosphere to a thickness of 1 nm, and the Ag metal layer was coated with a thickness of 8.5 nm under an argon 100% atmosphere. Next, the film was coated with a second functional reflective metal protective layer (NiCrO _x , x = 1.95) in an oxygen / argon (oxygen 80% / argon 20% partial pressure) atmosphere to a thickness of 6 nm. Then, the second dielectric layer (Si _x O _y N _z , x = 1, y = 0.08, z = 0.63) was made to have a thickness of 30 nm under oxygen / nitrogen / argon (oxygen 15% / nitrogen 40% / argon 45% partial pressure) atmosphere. As a top protective layer, the TiO ₂ layer was coated to a thickness of 5 nm under an oxygen / argon (oxygen 80% / argon 20% partial pressure) atmosphere. The sample was then heat treated and then the haze was measured.

(The blur is considered good within 3.2 and the bad is above 8)

The sample of the comparative example 4 showed a cloudiness of 8 or more, and was evaluated as defective.

Comparative example  5, 6

In order to compare the durability, the durability of the samples in which the first functional reflective metal protective layer and the top protective layer were removed (the first functional reflective metal protective layer removal: Comparative Example 4 and the top protective layer removal: Comparative Example 5) respectively removed in Example 2 Evaluated.

(Scratches should not be visible to the naked eye and ΔEnbs is considered to be good when the number of pinholes within 1.5 is less than or equal to three in a prepared 100 × 100 mm specimen)

In Comparative Examples 5 and 6, scratches were generated, and in Comparative Example 6, the number of pin holes was 3 or more, which was evaluated as poor in ΔEnbs.

The embodiments of the present invention have been described in detail above, but the scope of the present invention is not limited to the above-described embodiments, and various modifications of those skilled in the art using the basic concepts of the present invention defined in the following claims and Improved forms are also included in the scope of the present invention.

1 is a view schematically showing the layer structure of the heat-resistant low-radiation glass of the present invention.

2 is a view schematically showing an example of the configuration of a coating apparatus for manufacturing a low-emissive glass according to the present invention.

3 is a view schematically showing the layer structure of the low-emissive glass obtained by repeating the sequential coating twice in accordance with the present invention.

4 is a view schematically showing the layer structure of the low-emissive glass obtained by repeating the sequential coating three times in accordance with the present invention.

5 is a graph showing a change in transmittance according to heat treatment time in an embodiment of the present invention.

Claims (24)

Sequentially coated on a glass substrate, A first dielectric layer composed of a Zn-based oxide containing at least one element selected from Sn, Nb, Al, Sb, Mo, Cr, Ti, and Ni; A first functional reflective metal protective layer that protects the following functional reflective metal layer upon thermal treatment and assists fusion of the following functional reflective metal layer; A functional reflective metal layer that reflects infrared or solar radiation; A second functional reflective metal protective layer protecting the functional reflective metal layer during heat treatment; A second dielectric layer made of Si-based nitride or nitride oxide containing at least one element selected from Al, B, Ti, Nb, Sn and Mo; And Top protective layer; Low radiation glass capable of bending and heat treatment comprising a. The multi-layered structure of claim 1, wherein a multilayer structure including a first dielectric layer, a first functional reflective metal protective layer, a functional reflective metal layer, a second functional reflective metal protective layer, and a second dielectric layer is repeatedly stacked on the glass substrate. Low radiation glass capable of bending and heat treatment, characterized in that having a structure in which the uppermost protective layer is laminated on the top. The low radiation glass as claimed in claim 1 or 2, wherein the first functional reflective metal protective layer is made of Ni, Cr, or Ni-Cr alloy as a layer in contact with the functional reflective metal layer. The low radiation glass as claimed in claim 3, wherein the first functional reflective metal protective layer has a thickness of 0.5 to 5 nm. The low radiation glass as claimed in claim 4, wherein the first functional reflective metal protective layer has a thickness of 0.5 to 1.5 nm. The method of claim 1 or claim 2, wherein the functional reflective metal layer is bent and heat-treated low radiation, characterized in that made of silver (Ag) doped with 0.5 to 5% by weight of the element selected from Ni, Pd, Pt, Cu and Au Glass. The low-radiation glass according to claim 6, wherein the functional reflective metal layer has a thickness of 4 to 14 nm. The method of claim 7, wherein the thickness of the functional reflective metal layer is 6 ~ 10nm characterized in that the low radiation glass capable of bending and heat treatment. The bending and heat treatment of claim 1 or 2, wherein the second functional reflective metal protective layer is made of Ni, Cr or Ni-Cr alloy nitrided or oxidized to 50 mol% or less as a layer in contact with the functional reflective metal layer. Low emission glass available. The method of claim 9, wherein the thickness of the second functional reflective metal protective layer is 2 to 20 nm, characterized in that the low-emission glass capable of bending and heat treatment. The method of claim 10, wherein the thickness of the second functional reflective metal protective layer is 4 ~ 10 nm characterized in that the low-emission glass capable of bending and heat treatment. The low radiation glass as claimed in claim 1 or 2, wherein the uppermost protective layer is a Ti-based nitride oxide containing at least one element from W, Ti, Si, Ta, Al, and Zr. The method according to claim 12, wherein the uppermost protective layer is made of Ti nitride oxide TiO _x N _y (where 1.37≤x + y≤1.95, 0.15≤y≤0.92) and the thickness is 2 ~ 15 nm Low radiation glass capable of bending and heat treatment. The method of claim 13, wherein the top protective layer has a thickness of 5 ~ 10 nm, the low-radiation glass capable of bending and heat treatment. The visible light transmittance measured by the D65 standard light source of 380-780 nm when the thickness of the said transparent glass substrate is 6 mm is 40% or more in the measurement before heat processing, and 70% or more in the measurement after heat processing. Characterized in that the low-emission glass capable of bending and heat treatment. The low-radiation glass capable of bending and heat treatment according to claim 1, wherein the sheet resistance is 13 GPa / sq or less and emissivity is 0.15 or less. The low radiation glass as claimed in claim 1 or 2, wherein the first dielectric layer has a thickness of 10 to 55 nm. The method of claim 17, wherein the thickness of the first dielectric layer is 20 to 45 nm, low radiation glass capable of bending and heat treatment. The method according to claim 1 or 2, wherein the second dielectric layer is made of Si-based nitride oxide Si _x O _y N _z (where x / y <2, x / z <0.75) and the thickness is 10 ~ 55 nm Low radiation glass capable of bending and heat treatment, characterized in that. The method of claim 19, wherein the thickness of the second dielectric layer is 30 to 55 nm, low radiation glass capable of bending and heat treatment. The low-radiation glass capable of bending and heat treatment according to claim 1, further comprising an organic film bonded to the uppermost protective layer. On a glass substrate, a first dielectric layer made of a Zn-based oxide containing at least one element selected from Sn, Nb, Al, Sb, Mo, Cr, Ti and Ni, protects the following functional reflective metal layer during heat treatment, and the following functional reflective metal layer A first functional reflective metal protective layer which helps fusion of the metal, a functional reflective metal layer that reflects infrared or solar radiation, a second functional reflective metal protective layer which protects the functional reflective metal layer during heat treatment, Al, B, Ti, Nb, Sn and Sequentially coating a second dielectric layer made of Si-based nitride or nitride oxide containing at least one element selected from Mo; And Coating a top protective layer; Method for producing a low-radiation glass capable of bending and heat treatment comprising a. 22. The method of claim 21, wherein the coating of the first dielectric layer, the first functional reflective metal protective layer, the functional reflective metal layer, the second functional reflective metal protective layer, and the second dielectric layer on the glass substrate sequentially , The method of manufacturing a low-radiation glass capable of bending and heat treatment, characterized in that the manufacturing by performing the step of coating the top protective layer. 24. The method of claim 22 or 23, wherein the first dielectric layer and the second dielectric layer are coated using a tubular magnetron sputter coating machine.

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