KR20210033847A - Low-emissivity glass - Google Patents

Abstract

The present invention relates to a low-emissivity glass comprising: a glass substrate; and a stacking unit including an infrared reflective metal layer and an upper metal protective layer and lower metal protective layer respectively disposed on upper and lower portions of the infrared reflective metal layer, wherein the upper metal protective layer and the lower metal protective layer each independently include one or more metal oxides selected from the group consisting of nickel, chromium and nickel-chromium alloy. In addition, the low-emissivity glass has excellent solar shielding performance and thermal insulation performance.

Description

Low-emission glass {LOW-EMISSIVITY GLASS}

The present invention relates to a low-emission glass having high visible light transmittance, excellent solar shielding performance, and excellent thermal insulation performance.

Around 2000, the need for energy savings in residential buildings increased. To this end, hard-loy glass products produced overseas were mainly used, but since the reinforcement of the insulation standards for residential buildings, the use of soft-loy glass has been increasing instead of hard-loy glass products with low insulation performance.

At this time, the hard-loy glass and the soft-roy glass have different coating methods during manufacture. Specifically, the hard-loy glass is manufactured by depositing a conductive oxide film on a high temperature disk of 600°C or higher on-line on a float line using a CVD deposition method (chemical vapor deposition method), A coating film having excellent durability can be laminated through the reaction of the glass surface and the conductive oxide. However, hard-loy glass has excellent durability, but physical properties such as thermal insulation performance are relatively lower than that of soft-loy glass. The soft-roy glass is manufactured by forming a reactive gas in a vacuum chamber and forming a plasma in a target material to which a voltage is applied, and the ionized gas collides with the material of the target material and physically bonds to the surface of the glass. Compared to the hard-loy glass, it is advantageous in laminating various materials because there is no restriction on the temperature range, and high-performance coating films having various colors can be manufactured.

On the other hand, low-emission glass installed in residential buildings requires a high sense of view and does not require increased surface strength through heat strengthening, so the required mechanical performance is lower than that for non-residential buildings, so non-reinforced single-loy glass with high visible light transmittance is applied. Has been. The non-reinforced single low-e glass is a low-emission glass having a metal layer containing one silver, and is inexpensive among low-e-coated glass and meets current building insulation standards. However, in recent years, energy saving in buildings has emerged as an important issue, and the application of high-insulation low-E glass is required in accordance with the zero-energy enforcement policy.

As described above, in order to reduce heating heat loss by increasing the heat insulation performance of the glass, the thickness of the metal layer must be increased. However, when the thickness of the metal layer is increased, the infrared reflectance increases due to the properties of the metal, which lowers the visible light transmittance, thereby reducing the sense of view. Due to this problem, low-emission glass having a thick metal layer has a limitation that is difficult to apply to residential buildings requiring high visible light transmittance.

As an alternative to this, Korean Patent No. 1,386,806 (Patent Document 1) discloses a low emissivity coating having improved chemical and mechanical properties, including one or more absorbing layers. However, the low emissivity coating of Patent Document 1 has a disadvantage of having a low transmittance so that it is difficult to adapt to a residential building by simultaneously applying a barrier layer and an absorbing layer.

Therefore, there is a need for research and development on low-emission glass having excellent visible light transmittance of 70% or more and solar heat ray transmittance of 40% or less, which has excellent thermal insulation performance and solar shielding performance.

Korean Patent Registration No. 1,386,806 (published on July 15, 2013)

Accordingly, the present invention is to provide a low-emissivity glass having an excellent visible light transmittance of 70% or more, a solar heat ray transmittance of 40% or less, excellent insulation performance and solar shielding performance, and a low emissivity of 0.03 or less.

The present invention is a glass substrate; And

A lamination unit including an infrared reflecting metal layer and an upper metal protective layer and a lower metal protective layer respectively disposed above and below the infrared reflecting metal layer,

The upper metal protection layer and the lower metal protection layer each independently contain an oxide of at least one metal selected from the group consisting of nickel, chromium, and nickel-chromium alloy, providing a low-emission glass.

The low-emission glass according to the present invention has a high visible light transmittance of 70% or more and a low sheet resistance, has a strong blue color of reflection on the glass surface, has excellent mechanical properties such as scratch resistance and moisture resistance, and is less than 40% solar rays. As it has transmittance, it has excellent solar shielding performance and thermal insulation performance. For this reason, the low-emission glass is suitable as a building material for residential buildings.

Hereinafter, the present invention will be described in detail.

In the present specification, when a part "includes" a certain component, it means that other components may be further included rather than excluding other components unless otherwise stated.

Further, in the present specification, when a member is positioned "on" another member, this includes not only a case where a member is in contact with another member, but also a case where another member exists between the two members.

Further, in the present specification, "refractive index" is a refractive index value measured for a wavelength of 550 nm using a spectroscopic ellipsometer.

In addition, in this specification, "a* value" and "b* value" of glass are measured according to KS L 2514 standard using a D65 standard light source in a wavelength range of 380 to 780 nm based on an average thickness of a glass substrate of 6 mm. It means the a* value and b* value of the glass surface.

Low-emission glass according to the present invention is a glass substrate; And a lamination unit including an infrared reflecting metal layer and an upper metal protective layer and a lower metal protective layer respectively disposed above and below the infrared reflecting metal layer.

Specifically, the low-emission glass is a repeating unit in which a first dielectric layer, a first auxiliary dielectric layer, a first lower metal protective layer, a first infrared reflective metal layer, a first upper metal protective layer, and a second auxiliary dielectric layer are sequentially stacked. It may include. In this case, the low-emission glass may include 1 or more, 1 to 5, 1 to 4, or 1 to 3 repeating units.

For example, the low-emission glass includes a glass substrate, a first dielectric layer, a first auxiliary dielectric layer, a first lower metal protective layer, a first infrared reflective metal layer, a first upper metal protective layer, a second auxiliary dielectric layer, a second dielectric layer, and It may include a form in which the overcoat layer is sequentially stacked. That is, the low-emission glass may include one lamination unit including an infrared reflecting metal layer and an upper metal protective layer and a lower metal protective layer respectively disposed above and below the infrared reflecting metal layer.

For example, the low-emission glass is a glass substrate, a first dielectric layer, a first auxiliary dielectric layer, a first lower metal protective layer, a first infrared reflective metal layer, a first upper metal protective layer, a second auxiliary dielectric layer, a second dielectric layer, A third auxiliary dielectric layer, a second lower metal protective layer, a second infrared reflective metal layer, a second upper metal protective layer, a fourth auxiliary dielectric layer, a third dielectric layer, and an overcoat layer may be sequentially stacked. That is, the low-emission glass may include two lamination units including an infrared reflecting metal layer and an upper metal protective layer and a lower metal protective layer respectively disposed above and below the infrared reflecting metal layer.

As described above, the low-emission glass according to the present invention includes a lamination unit including an upper metal protective layer and a lower metal protective layer respectively disposed above and below the infrared reflective metal layer, thereby preventing damage to the infrared reflective metal layer. There is an effect of improving the durability to be able to. Specifically, the lower metal protective layer increases the adhesion between the dielectric layer and the infrared reflective metal layer to increase the scratch prevention effect, and the upper metal protective layer protects the infrared reflective metal layer from humidity and chemical substances.

Glass substrate

The glass substrate serves as a base substrate for low-emission glass.

In this case, as the glass substrate, conventional glass such as soda lime glass, low iron glass, green original glass, or blue original glass may be used as the glass substrate.

In addition, glass having an appropriate thickness may be used as the glass substrate according to the purpose of use. For example, as the glass substrate, a transparent soda lime glass having an average thickness of 2 to 12 mm, or 5 to 6 mm may be used.

First to third dielectric layers

Each of the first to third dielectric layers serves to control the optical properties of the manufactured glass by blocking ions or oxygen transmitted to the infrared reflecting metal layer during heat treatment.

The first dielectric layer and the second dielectric layer may each independently include at least one selected from the group consisting of nitride and nitride oxide. Specifically, the first dielectric layer and the second dielectric layer may each independently include a silicon-containing nitride. More specifically, the first dielectric layer and the second dielectric layer may each independently include SiAlNx, where x may be 1.0 to 1.8, or 1.3 to 1.5.

In addition, the third dielectric layer may include at least one selected from the group consisting of nitride and nitride oxide. Specifically, the third dielectric layer may include silicon-containing nitride. More specifically, the third dielectric layer may include SiAlNx, where x may be 1.0 to 1.8, or 1.3 to 1.5.

Each of the first and second dielectric layers may independently have a refractive index of 1.8 to 2.5, or 1.8 to 2.2, and an absorption coefficient of 0.1 or less, or 0 to 0.1. When the refractive index and absorption coefficient of each of the first dielectric layer and the second dielectric layer are within the above ranges, it is possible to prevent a problem in that the visible light transmittance of the manufactured glass is decreased.

The third dielectric layer may have a refractive index of 1.8 to 2.5, or 1.8 to 2.2, and an absorption coefficient of 0.1 or less, or 0 to 0.1. When the refractive index and absorption coefficient of the third dielectric layer are within the above ranges, a problem in that the visible light transmittance of the manufactured glass is decreased can be prevented.

In addition, the first dielectric layer and the third dielectric layer may each independently have an average thickness of 25 to 50 nm, or 30 to 40 nm. When the average thickness of each of the first dielectric layer and the third dielectric layer is within the above range, it is possible to prevent a problem that the durability of the manufactured glass is deteriorated and a problem that the blue color of the surface is decreased.

The second dielectric layer may have an average thickness of 60 to 80 nm, or 60 to 70 nm. When the average thickness of the second dielectric layer is within the above range, it is possible to prevent a problem in which durability of the manufactured glass is deteriorated and a problem in which blue color of the surface is decreased.

First auxiliary dielectric layer, second auxiliary dielectric layer, third auxiliary dielectric layer, and fourth auxiliary dielectric layer

Each of the first auxiliary dielectric layer, the second auxiliary dielectric layer, the third auxiliary dielectric layer, and the fourth auxiliary dielectric layer blocks ions or oxygen transmitted to the infrared reflecting metal layer during heat treatment, and increases the crystallinity of the infrared reflecting metal layer to increase the optical properties of the manufactured glass. It plays a role of improving insulation performance while controlling.

Each of the first auxiliary dielectric layer and the second auxiliary dielectric layer may independently include an oxide. Specifically, the first auxiliary dielectric layer and the second auxiliary dielectric layer may each independently include zinc and aluminum-containing oxides. More specifically, the first auxiliary dielectric layer and the second auxiliary dielectric layer may each independently include ZnAlOy, and in this case, y may be 0.5 to 1.5, or 0.8 to 1.2. If y is out of the above range, a deposition rate may decrease due to an excess of oxygen or an increase in a visible ray absorption rate due to lack of oxygen may occur.

In addition, the third auxiliary dielectric layer and the fourth auxiliary dielectric layer may each independently include an oxide. Specifically, the third auxiliary dielectric layer and the fourth auxiliary dielectric layer may each independently include zinc and aluminum-containing oxides. More specifically, the third auxiliary dielectric layer and the fourth auxiliary dielectric layer may each independently include ZnAlOy, and in this case, y may be 0.5 to 1.5, or 0.8 to 1.2. If y is out of the above range, a deposition rate may decrease due to an excess of oxygen or an increase in a visible ray absorption rate due to lack of oxygen may occur.

The first auxiliary dielectric layer and the second auxiliary dielectric layer may each independently have a refractive index of 1.6 to 2.3, or 1.6 to 2.0, and an absorption coefficient of 0.1 or less, or 0 to 0.1. When the refractive index and absorption coefficient of each of the first and second auxiliary dielectric layers are within the above ranges, it is possible to improve transmittance and thermal insulation performance. When the refractive index and absorption coefficient are out of the above ranges, the function of improving the crystallinity of the infrared reflecting metal layer is lost, and thus, it has a metallic property other than a dielectric.

In addition, the third auxiliary dielectric layer and the fourth auxiliary dielectric layer may each independently have a refractive index of 1.6 to 2.3, or 1.6 to 2.0, and an absorption coefficient of 0.1 or less, or 0 to 0.1. When the refractive index and absorption coefficient of each of the third auxiliary dielectric layer and the fourth auxiliary dielectric layer are within the above ranges, it is possible to improve transmittance and thermal insulation performance. When the refractive index and absorption coefficient are out of the above ranges, the function of improving the crystallinity of the infrared reflecting metal layer is lost, and thus, it has a metallic property other than a dielectric.

The first auxiliary dielectric layer and the second auxiliary dielectric layer may each independently have an average thickness of 6 to 12 nm, or 8 to 10 nm. When the average thickness of each of the first auxiliary dielectric layer and the second auxiliary dielectric layer is within the above range, the degree of crystallinity of the infrared reflecting metal layer can be further increased, thereby preventing a decrease in thermal insulation performance.

In addition, the third auxiliary dielectric layer and the fourth auxiliary dielectric layer may each independently have an average thickness of 6 to 12 nm, or 8 to 10 nm. When the average thickness of each of the third auxiliary dielectric layer and the fourth auxiliary dielectric layer is within the above range, the degree of crystallinity of the infrared reflecting metal layer can be further increased, thereby preventing a decrease in thermal insulation performance.

First lower metal protective layer, first upper metal protective layer, second lower metal protective layer, and second upper metal protective layer

Each of the first lower metal protective layer, the first upper metal protective layer, the second lower metal protective layer, and the second upper metal protective layer serves to protect the infrared reflective metal layer from external impact and contamination.

In this case, the first lower metal protective layer, the first upper metal protective layer, the second lower metal protective layer, and the second upper metal protective layer may each independently include a metal, a metal nitride, or a metal oxide. When the metal protective layer contains metal, the durability of the manufactured glass is excellent, but a problem of high absorption of visible light may occur. When it contains a nitride, the durability of the manufactured glass may be deteriorated and contain oxides. In this case, since the manufactured glass has a low absorption rate of visible light, it is preferable that the metal protective layer includes a metal oxide.

Specifically, the first lower metal protective layer, the first upper metal protective layer, the second lower metal protective layer, and the second upper metal protective layer are each independently selected from the group consisting of nickel, chromium, and nickel-chromium alloys. It may contain an oxide of a metal. More specifically, the first lower metal protective layer, the first upper metal protective layer, the second lower metal protective layer, and the second upper metal protective layer may each independently include NiCrOz, wherein z is 0.05 to 0.2, Or 0.05 to 0.1. If z is out of the above range, the infrared reflecting metal layer may be oxidized due to an excess of oxygen to reduce the performance and visible light transmittance of the glass, and the visible light absorption rate may be improved due to lack of oxygen.

In addition, the first lower metal protective layer, the first upper metal protective layer, the second lower metal protective layer, and the second upper metal protective layer may each independently have an average thickness of 0.5 to 2 nm, or 0.5 to 1 nm. . When the average thickness of each of the first lower metal protective layer, the first upper metal protective layer, the second lower metal protective layer, and the second upper metal protective layer is within the above range, durability and/or visible light transmittance of the manufactured glass decreases. It is possible to prevent the problem and the problem that the cloudiness of the coating film increases after the heat treatment and bending process.

The first infrared reflecting metal layer and the second infrared reflecting metal layer

The first infrared reflecting metal layer and the second infrared reflecting metal layer each selectively reflect the radiation of the sun to improve the solar heat ray shielding performance of the manufactured glass and at the same time implement low radiation.

The first infrared reflecting metal layer and the second infrared reflecting metal layer may each independently include a metal having excellent conductivity, and include at least one metal selected from the group consisting of gold, silver, platinum, aluminum, and copper. I can. Specifically, the first infrared reflecting metal layer and the second infrared reflecting metal layer may contain silver (Ag). More specifically, the first infrared reflecting metal layer and the second infrared reflecting metal layer may be made of silver.

In addition, the average thickness of the first infrared reflecting metal layer and the second infrared reflecting metal layer may each independently be 5 to 15 nm, or 8 to 13 nm. When the thickness of the first infrared reflecting metal layer and the second infrared reflecting metal layer is within the above range, the formation of the infrared reflecting metal layer is not normally performed, resulting in insufficient low-emissivity performance of the manufactured glass, and the glass surface due to the high reflectance of the manufactured glass. It can prevent the problem of deteriorating the blue color of the product.

Overcoat layer

The overcoat layer serves to protect the second dielectric layer or the third dielectric layer from an external environment.

The overcoat layer may include a material having high mechanical strength, low surface roughness, and high visible light transmittance. For example, the overcoat layer may include silicon (Si), niobium (Nb), titanium (Ti), zirconium (Zr), tantalum (Ta), or an alloy, oxide, nitride, or nitride oxide thereof. Specifically, the overcoat layer may include a zirconium-containing oxide or nitride, or a titanium-containing oxide or nitride.

In addition, the average thickness of the overcoat layer may be 2 to 15 nm, or 2 to 7 nm. When the average thickness of the overcoat layer is within the above range, it is possible to prevent a problem in that durability of the manufactured glass is deteriorated, and a problem in which fogging occurs after heat treatment of the manufactured glass.

The low-emission glass according to the present invention may have a transmittance of 70% or more or 73% or more for visible light having a wavelength of 380 to 780 nm, and a solar transmittance of 65% or less, 60% or less, 40% or less, or 35% or less. .

In addition, the low-emission glass may have an a* value of 0 to 10 or 0 to 5, and a b* value of -20 to 0, or -16 to -3, -10 to 0, or -10 to -5.

The low-emission glass may have a sheet resistance of 8Ω/□ or less, 7Ω/□ or less, 3.7Ω/□ or less, or 3.0Ω/□ or less. The sheet resistance is a value measured by the infrared reflecting metal layer, and the sheet resistance is an evaluation property that can measure the performance of the glass even after heat treatment.The lower the sheet resistance is, the better the far-infrared reflecting property, which lowers the emissivity and improves the thermal insulation performance. .

In addition, the low-emissivity glass may have an emissivity of 0.1% or less, 0.09% or less, 0.03% or less, or 0.025% or less. Emissivity refers to the ratio of energy that is partially re-emitted after absorbing external light energy or re-radiated when surface reflection occurs.The maximum value is 1, and the smaller the value, the higher the ratio of energy re-emitted or re-radiated. it means.

The low-emission glass according to the present invention as described above has a strong blue surface, and has excellent chemical and mechanical durability both before and after heat treatment. In addition, the low-emission glass has a high visible light transmittance of 70% or more and a low sheet resistance, has excellent mechanical properties such as scratch resistance and moisture resistance, and has a solar ray transmittance of 60% or less or 40% or less to shield sunlight. Excellent performance and insulation performance. For this reason, the low-emission glass is suitable as a building material for residential buildings.

The low-emission glass according to the present invention may be manufactured using a magnetron sputtering method as a method for forming a thin film for forming each layer. That is, the method of manufacturing a low-emission glass according to the present invention may include forming each layer by a magnetron sputtering deposition method.

Hereinafter, the present invention will be described in more detail through examples. However, these examples are only intended to aid understanding of the present invention, and the scope of the present invention is not limited to these examples in any sense.

[Example]

Example 1. Preparation of low-emission glass

The thickness of each layer is adjusted as described in Table 1, and the glass substrate, the first dielectric layer, the first auxiliary dielectric layer, the first lower metal protective layer, the first infrared reflective metal layer, the first upper metal protective layer, and the second auxiliary dielectric layer , A second dielectric layer, a third auxiliary dielectric layer, a second lower metal protection layer, a second infrared reflective metal layer, a second upper metal protection layer, a fourth auxiliary dielectric layer, a third dielectric layer, and an overcoat layer are sequentially stacked. Glass was made.

Specifically, a first dielectric layer was coated on a 5mm-thick transparent glass substrate using a SiAl target in a nitrogen and argon atmosphere. Thereafter, the first auxiliary dielectric layer was coated on the first dielectric layer using a ZnAl target in an oxygen and argon atmosphere. _{Thereafter, a first lower metal protective layer (composed of NiCrO 0.05} ) was coated on the first auxiliary dielectric layer using a NiCr target in an atmosphere containing oxygen and argon in a volume ratio of 5:95. Thereafter, the first infrared reflective metal layer was coated on the first lower metal protective layer using an Ag target in an argon atmosphere.

Thereafter, the first upper metal protective layer, the second lower metal protective layer, and the second upper metal protective layer are coated in the same manner as the first lower metal protective layer as described above, and the second auxiliary dielectric layer, the third auxiliary dielectric layer, and the second upper metal protective layer are coated. 4 The auxiliary dielectric layer was coated in the same manner as the first auxiliary dielectric layer as described above. In addition, the second dielectric layer and the third dielectric layer were coated in the same manner as the first dielectric layer as described above.

Thereafter, the overcoat layer was coated on the third dielectric layer using a zirconium (Zr) target in an argon and nitrogen atmosphere.

Example 2.

When the first lower metal protective layer, the first upper metal protective layer, the second lower metal protective layer, and the second upper metal protective layer are manufactured, coating (composed of NiCrO _0.1 ) in an atmosphere containing oxygen and argon in a volume ratio of 10:90 Except for that, a low-emission glass was prepared in the same manner as in Example 1.

Example 3.

When manufacturing the first lower metal protective layer, the first upper metal protective layer, the second lower metal protective layer, and the second upper metal protective layer, coating (composed of NiCrO _0.2 ) in an atmosphere containing oxygen and argon in a volume ratio of 20:80 Except for that, a low-emission glass was prepared in the same manner as in Example 1.

Comparative Example 1.

When manufacturing the first lower metal protective layer, the first upper metal protective layer, the second lower metal protective layer, and the second upper metal protective layer, coating (composed of NiCrO _0.5 ) in an atmosphere containing oxygen and argon in a volume ratio of 50:50 Except for that, a low-emission glass was prepared in the same manner as in Example 1.

Comparative Example 2.

The same method as in Example 1, except that the first lower metal protective layer, the first upper metal protective layer, the second lower metal protective layer, and the second upper metal protective layer were coated under an argon atmosphere (composed of NiCr). A low-emissivity glass was prepared.

Comparative Example 3.

When the first upper metal protective layer is prepared, it is coated (composed of NiCr) in an argon atmosphere), and when the second upper metal protective layer is prepared, it is coated under an atmosphere containing oxygen and argon in a volume ratio of 5:95 (composed of NiCrO _0.05 ), A low-emission glass was manufactured in the same manner as in Example 1, except that the first lower metal protective layer and the second lower metal protective layer were not formed.

Comparative Example 4.

When manufacturing the first lower metal protective layer and the second lower metal protective layer, coating (composed of NiCr) under an argon atmosphere, and when preparing the first upper metal protective layer and the second upper metal protective layer, oxygen and argon were mixed in a volume ratio of 5:95. A low-emission glass was prepared in the same manner as in Example 1, except that the coating was performed under an atmosphere containing (composed of NiCrO _0.05).

Comparative Example 5.

When manufacturing the first lower metal protective layer, the first upper metal protective layer, the second lower metal protective layer, and the second upper metal protective layer, coating (composed of _0.03 NiCrO) in an atmosphere containing oxygen and argon in a volume ratio of 3:97 Except for that, a low-emission glass was prepared in the same manner as in Example 1.

Comparative Example 6.

When manufacturing the first lower metal protective layer, the first upper metal protective layer, the second lower metal protective layer, and the second upper metal protective layer, coating (composed of NiCrO _0.25 ) in an atmosphere containing oxygen and argon in a volume ratio of 25:75 Except for that, a low-emission glass was prepared in the same manner as in Example 1.

Comparative Examples 7 to 9.

In the same manner as in Example 1, except that the thicknesses of the first lower metal protective layer, the first upper metal protective layer, the second lower metal protective layer, and the second upper metal protective layer were adjusted as described in Table 2. A low-emission glass was prepared.

(Thickness nm) Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 First dielectric layer 33 33 33 33 35 33 First auxiliary dielectric layer 11 11 11 11 11 11 First lower metal protective layer 0.8 0.8 0.8 0.8 0.5 - First infrared reflective metal layer 10 10 10 10 10 10 First upper metal protective layer 0.8 0.8 0.8 0.8 0.5 0.8 Second auxiliary dielectric layer 11 11 11 11 11 11 Second dielectric layer 65 65 65 68 70 68 3rd auxiliary dielectric layer 11 11 11 11 11 11 Second lower metal protective layer 0.8 0.8 0.8 0.8 0.5 - Second infrared reflective metal layer 15 15 15 15 15 15 Second upper metal protective layer 0.8 0.8 0.8 0.8 0.5 0.8 4th auxiliary dielectric layer 11 11 11 11 11 11 Third dielectric layer 34 34 34 34 34 34 Overcoat layer 2 2 2 2 2 2 Composition of metal protective layer NiCrO _0.05 NiCrO _0.1 NiCrO _0.2 NiCrO _0.5 NiCr NiCrO _0.05

(Thickness nm) Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 Comparative Example 9 First dielectric layer 33 33 33 33 33 33 First auxiliary dielectric layer 11 11 11 11 11 11 First lower metal protective layer 0.8 0.8 0.8 0.8 0.3 2.5 First infrared reflective metal layer 10 10 10 10 10 10 First upper metal protective layer 0.8 0.8 0.8 - 0.3 2.5 Second auxiliary dielectric layer 11 11 11 11 11 11 Second dielectric layer 68 65 65 68 68 68 3rd auxiliary dielectric layer 11 11 11 11 11 11 Second lower metal protective layer 0.8 0.8 0.8 - 0.3 2.5 Second infrared reflective metal layer 15 15 15 15 15 15 Second upper metal protective layer 0.8 0.8 0.8 0.8 0.3 2.5 4th auxiliary dielectric layer 11 11 11 11 11 11 Third dielectric layer 34 34 34 34 34 34 Overcoat layer 2 2 2 2 2 2 Composition of metal protective layer NiCrO _0.05
(First upper and second upper metal protective layers) NiCrO _0.03 NiCrO _0.25 NiCrO _0.05 NiCrO _0.05 NiCrO _0.05

Test Example 1: Evaluation of properties of glass

The physical properties of the low-emission glasses prepared in Examples 1 to 3 and Comparative Examples 1 to 9 were measured in the following manner, and the results are shown in Table 3.

Specifically, the low-emission glass prepared in Examples and Comparative Examples was heat-treated at 650° C. for 5 minutes and then quenched, and then the physical properties were evaluated.

(1) visible light transmittance

The visible light transmittance was measured by measuring the transmission spectrum in the visible light wavelength region (380 to 780 nm) using a spectrophotometer (Spectrophotometer, Rambda950, manufactured by Perkinelmer), and calculated according to the KS L 2514 standard.

(2) the reflection color of the glass surface

In a wavelength range of 380 to 780 nm, a 10° reflection color of the glass surface was measured according to the KS L 2514 standard using a D65 standard light source.

(3) sheet resistance

Sheet resistance was measured using a surface resistance meter (non-contact type sheet resistance meter, manufactured by SURAGUS). The sheet resistance of glass is a value measured by a silver (Ag) layer that is an infrared reflective metal layer targeting solar rays, and is one of the evaluation properties that can measure its performance as a low-emission glass even after heat treatment.

(4) scratch resistance

After spraying distilled water mixed with quartz powder on the coated surface of the manufactured glass, a 0.5mm-thick nylon brush was moved back and forth horizontally 200 times with the coated surface of the glass, and the number of scratches generated on the coated surface was measured. Evaluated.

(5) Moisture resistance (number of pinholes)

The prepared low-emission glass was stored at 30° C. and 80% relative humidity for 7 days, and then the number of pinholes generated on the surface of the overcoat layer was measured to evaluate moisture resistance.

(6) emissivity

Emissivity was calculated based on the KS L 2525 standard by measuring the reflection spectrum in the infrared wavelength region (2,500 to 25,000 nm) using FT-IR after heat treatment of the low-emissivity glass.

(7) Heat transmittance rate

It was calculated according to the ASHRAE standard using WINDOW, a glass performance calculation program manufactured by NFRC in the United States. As for the multilayer glass standard, low-emission glass (Example or Comparative Example) having a thickness of 6 mm / Ar gas of 12 mm / transparent glass of 6 mm was applied, and the unit was W/m 2 K.

(8) Solar ray transmittance

The transmittance of solar rays was measured using a spectrophotometer (Spectrophotometer, Rambda950, manufactured by Perkinelmer) in the visible and near-infrared wavelength ranges (300 to 2500 nm) and calculated according to the KS L 2514 standard.

division Visible light transmittance
(%) Reflection color Sheet resistance
(Ω/□) scratch Number of pinholes Emissivity
(%) Heat tube
Flow rate Solar ray transmittance (%) Y L a* b* Example 1 73.6 3.1 19.7 2 -8.2 2.6 4 4 0.028 1.64 30 Example 2 74.2 3.8 23 1.7 -8.5 2.7 9 pieces 6 pieces 0.028 1.64 29 Example 3 74.8 4.3 24.6 1.6 -8.6 2.6 15 pcs 5 pieces 0.028 1.64 29 compare
Example 1 72.5 6.8 31.3 5.9 6.4 5.7 30 or more 16 pcs 0.064 1.71 30 Comparative Example 2 71.5 4.2 24.3 2.9 -5.1 3.2 4 Three 0.033 1.65 28 Comparative Example 3 73.8 3.6 21.8 2.2 -8.5 2.2 20 pcs 6 pieces 0.022 1.63 30 Comparative Example 4 70 3.2 20.8 4.5 -6.8 3.2 2 4 0.033 1.65 27 Comparative Example 5 70.2 4.2 24.3 2.8 -4.9 3 6 pieces Three 0.031 1.65 28 Comparative Example 6 72.8 6.5 30.6 4 -5.2 4.8 30 or more 14 pieces 0.052 1.69 30 Comparative Example 7 76.2 3.2 20.8 1.8 -8.0 2.2 22 pieces 7 pieces 0.022 1.63 32 Comparative Example 8 68.5 5.2 27.3 9.1 13.5 7.2 30 or more 30 or more 0.084 1.75 38 Comparative Example 9 65.0 8.9 35.8 -1.6 -10.5 2.9 4 5 pieces 0.030 1.65 28

As shown in Table 3, the low-emission glass of Examples 1 to 3 has a sheet resistance as low as 3.0Ω/□ or less, has excellent durability such as moisture resistance (number of pinholes) and scratch resistance, and has a strong color of the glass surface. It had a blue color and showed a high visible light transmittance of 73% or more.

On the other hand, the low-emissivity glass of Comparative Example 1 in which the metal protective layer is made _{of NiCrO 0.5 , Comparative Example 6 in which the metal protective layer is made of NiCrO 0.25} , and the thin metal protective layer in Comparative Example 8 has high sheet resistance, scratch resistance, moisture resistance, and The emissivity was insufficient. In addition, Comparative Example 2 in which the metal protective layer was made of NiCr, Comparative Example 4 in which the first lower metal protective layer and the second lower metal protective layer were thin, Comparative Example 8 in which the metal protective layer was thin, and Comparative Example 9 in which the metal protective layer was thick. The low-emission glass of was insufficient in visible light transmittance. In addition, the low-emission glass of Comparative Example 3 not including the lower metal protective layer and Comparative Example 7 including the first upper metal protective layer and the second lower metal protective layer lacked scratch resistance. In addition, the low-emission glass of Comparative Example 5 in which the _{metal protective layer was made of NiCrO 0.03 had insufficient visible light transmittance.}

Example 4.

The thickness of each layer is adjusted as described in Table 4, and the glass substrate, the first dielectric layer, the first auxiliary dielectric layer, the first lower metal protective layer, the first infrared reflective metal layer, the first upper metal protective layer, and the second auxiliary dielectric layer , A low-emission glass was manufactured in the same manner as in Example 1, except that the second dielectric layer and the overcoat layer were sequentially stacked.

Example 5.

Low-emission in the same manner as in Example 4, except for _{coating (composed of NiCrO 0.1} ) in an atmosphere containing oxygen and argon in a volume ratio of 10:90 when the first lower metal protective layer and the first upper metal protective layer were prepared. Glass was made.

Example 6.

Low-emission in the same manner as in Example 4, except for _{coating (composed of NiCrO 0.2} ) in an atmosphere containing oxygen and argon in a volume ratio of 20:80 when the first lower metal protective layer and the first upper metal protective layer were prepared. Glass was made.

Comparative Example 10.

A low-emissivity glass was manufactured in the same manner as in Example 4, except that the first lower metal protective layer and the first upper metal protective layer were coated under an argon atmosphere (composed of NiCr).

Comparative Example 11.

Low-emission in the same manner as in Example 4, except that _{coating (consisting of NiCrO 0.03} ) in an atmosphere containing oxygen and argon in a volume ratio of 3:97 when manufacturing the first lower metal protective layer and the first upper metal protective layer Glass was made.

Comparative Example 12.

Low emission in the same manner as in Example 4, except for _{coating (composed of NiCrO 0.25} ) in an atmosphere containing oxygen and argon in a volume ratio of 25:75 when the first lower metal protective layer and the first upper metal protective layer were prepared. Glass was made.

Comparative Example 13.

Low-emission in the same manner as in Example 4, except for _{coating (composed of NiCrO 0.5} ) in an atmosphere containing oxygen and argon in a 50:50 volume ratio when manufacturing the first lower metal protective layer and the first upper metal protective layer. Glass was made.

Comparative Example 14.

A low-emission glass was manufactured in the same manner as in Example 4, except that the thicknesses of the first lower metal protective layer and the first upper metal protective layer were adjusted as described in Table 5.

Comparative Example 15.

A low-emission glass was manufactured in the same manner as in Example 4, except that coating (consisting of NiCr) under an argon atmosphere when the first lower metal protective layer was prepared.

(Thickness nm) Example 4 Example 5 Example 6 Comparative Example 10 Comparative Example 11 First dielectric layer 33 33 33 33 33 First auxiliary dielectric layer 11 11 11 11 11 First lower metal protective layer 0.8 0.8 0.8 0.8 0.8 First infrared reflective metal layer 10 10 10 10 10 First upper metal protective layer 0.8 0.8 0.8 0.8 0.8 Second auxiliary dielectric layer 11 11 11 11 11 Second dielectric layer 65 65 65 65 65 Overcoat layer 2 2 2 2 2 Composition of metal protective layer NiCrO _0.05 NiCrO _0.1 NiCrO _0.2 NiCr NiCrO _0.03

(Thickness nm) Comparative Example 12 Comparative Example 13 Comparative Example 14 Comparative Example 15 First dielectric layer 33 33 33 33 First auxiliary dielectric layer 11 11 11 11 First lower metal protective layer 0.8 0.8 - 0.8 First infrared reflective metal layer 10 10 10 10 First upper metal protective layer 0.8 0.8 0.8 0.8 Second auxiliary dielectric layer 11 11 11 11 Second dielectric layer 65 65 65 65 Overcoat layer 2 2 2 2 Composition of metal protective layer NiCrO _0.25 NiCrO _0.5 NiCrO _0.05 NiCrO _0.05
(First upper metal protective layer)

Test Example 2: Evaluation of properties of glass

The physical properties of the low-emission glasses prepared in Examples 4 to 6 and Comparative Examples 10 to 15 were measured in the following manner, and the results are shown in Table 6.

Specifically, the low-emission glass prepared in Examples and Comparative Examples was heat-treated at 650° C. for 5 minutes and quenched, and then the physical properties were evaluated, and the evaluation method was performed in the same manner as in Test Example 1.

division Visible light transmittance
(%) Reflection color Sheet resistance
(Ω/□) scratch Number of pinholes Emissivity
(%) Heat tube
Flow rate Solar ray transmittance (%) Y L a* b* Example 4 78.4 6.5 30.6 2.5 -14.8 6.8 4 Three 0.081 1.75 54 Example 5 79.2 5.4 27.8 3.2 -15.2 6.8 8 pieces 9 pieces 0.081 1.75 56 Example 6 80 5.9 29.2 4.5 -15.2 7 14 pieces 20 pcs 0.083 1.75 60 compare
Yes 10 72.1 6.5 30.6 1.8 -16.8 7.6 Three Three 0.09 1.76 50 Comparative Example 11 75.8 6.9 31.6 2.2 -16.5 7 Three 2 0.083 1.76 52 Comparative Example 12 75.5 12.1 41.4 9.2 -8.5 8.1 18 pieces 30 or more 0.097 1.78 64 Comparative Example 13 60.4 14.9 45.5 18.6 -4.9 16.8 30 or more 30 or more 0.221 1.99 69 Comparative Example 14 80.9 5.4 27.8 3.5 -16.5 5.6 9 pieces 4 0.067 1.72 56 Comparative Example 15 74 6.9 31.6 1.4 -17 7.5 Three 5 pieces 0.089 1.76 52

As shown in Table 6, the low-emission glass of Examples 4 to 6 has a low sheet resistance of 7.0 Ω/□ or less, has excellent durability such as moisture resistance (number of pinholes) and scratch resistance, and has a strong color of the glass surface. It had a blue color and showed a high visible light transmittance of 78% or more.

On the other hand, the low-emission glass of Comparative Example 10 in which the metal protective layer was made of NiCr had a visible light transmittance of 75% or less. In addition, the low-emission glass of Comparative Example 11 in which the _{metal protective layer was made of NiCrO 0.03 had insufficient visible light transmittance.} In addition, _{the low-emissivity glass of Comparative Example 12 in which the metal protective layer was made of NiCrO 0.25} had a large number of pinholes and was poor in moisture resistance. In addition, _{the low-emissivity glass of Comparative Example 13 in which the metal protective layer was made of NiCrO 0.5} lacked sheet resistance, scratch resistance, and moisture resistance, and had insufficient visible light transmittance and emissivity. In addition, the low-emissivity glass of Comparative Example 14 that did not include the first lower metal protective layer had insufficient emissivity. In addition, the low-emission glass of Comparative Example 15 in which the first lower metal protective layer was made of NiCr had insufficient visible light transmittance.

Claims (7)

Glass substrate; And
Including; an infrared reflecting metal layer and a lamination unit including an upper metal protective layer and a lower metal protective layer respectively disposed above and below the infrared reflecting metal layer,
The upper metal protection layer and the lower metal protection layer each independently contain an oxide of at least one metal selected from the group consisting of nickel, chromium, and nickel-chromium alloy, low-emission glass. The method according to claim 1,
A low-emission glass comprising a repeating unit in which a first dielectric layer, a first auxiliary dielectric layer, a first lower metal protective layer, a first infrared reflective metal layer, a first upper metal protective layer, and a second auxiliary dielectric layer are sequentially stacked. The method according to claim 2,
The first dielectric layer has an average thickness of 25 to 50 nm,
The first auxiliary dielectric layer and the second auxiliary dielectric layer each independently have an average thickness of 6 to 12 nm,
The first lower metal protective layer and the first upper metal protective layer each independently have an average thickness of 0.5 to 2 nm,
The first infrared reflecting metal layer has an average thickness of 5 to 15 nm, low-emission glass. The method according to claim 2,
The glass further comprises an overcoat layer, low-emission glass. The method according to claim 2,
The first dielectric layer includes SiAlNx, has a refractive index of 1.8 to 2.5, an absorption coefficient of 0.1 or less, and x is 1.0 to 1.8. The method according to claim 2,
The first auxiliary dielectric layer and the second auxiliary dielectric layer each independently include ZnAlOy, and y is 0.5 to 1.5, low-emission glass. The method according to claim 1,
The lower metal protective layer and the upper metal protective layer each independently contain NiCrOz, and the z is 0.05 to 0.2, low-emission glass.