KR101979625B1 - Low-emissivity coat and functional building material including low-emissivity coat for windows - Google Patents

Low-emissivity coat and functional building material including low-emissivity coat for windows Download PDF

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KR101979625B1
KR101979625B1 KR1020150099652A KR20150099652A KR101979625B1 KR 101979625 B1 KR101979625 B1 KR 101979625B1 KR 1020150099652 A KR1020150099652 A KR 1020150099652A KR 20150099652 A KR20150099652 A KR 20150099652A KR 101979625 B1 KR101979625 B1 KR 101979625B1
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layer
low
dielectric layer
silicon
zirconium
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KR1020150099652A
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Korean (ko)
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KR20160010332A (en
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유현우
전윤기
권대훈
박성진
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(주)엘지하우시스
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    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/22Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
    • C03C17/225Nitrides
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
    • C03C17/3602Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
    • C03C17/361Coatings of the type glass/metal/inorganic compound/metal/inorganic compound/other
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
    • C03C17/3602Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
    • C03C17/3681Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the multilayer coating being used in glazing, e.g. windows or windscreens
    • EFIXED CONSTRUCTIONS
    • E06DOORS, WINDOWS, SHUTTERS, OR ROLLER BLINDS IN GENERAL; LADDERS
    • E06BFIXED OR MOVABLE CLOSURES FOR OPENINGS IN BUILDINGS, VEHICLES, FENCES OR LIKE ENCLOSURES IN GENERAL, e.g. DOORS, WINDOWS, BLINDS, GATES
    • E06B5/00Doors, windows, or like closures for special purposes; Border constructions therefor

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Civil Engineering (AREA)
  • Structural Engineering (AREA)
  • Surface Treatment Of Glass (AREA)

Abstract

Sequentially, a first dielectric layer comprising silicon aluminum nitride; Low radiation layer; And a second dielectric layer comprising silicon aluminum nitride, wherein the refractive index of the first dielectric layer is higher than the refractive index of the second dielectric layer, and a functional building material for a window comprising the same.

Description

TECHNICAL FIELD [0001] The present invention relates to a functional building material for a window including a low-emission coating and a low-emission coating. BACKGROUND OF THE INVENTION < RTI ID = 0.0 >

Low-emission coatings, and low-emission coatings.

Low-emissivity glass refers to glass in which a low-emission layer containing a metal with a high reflectance in the infrared region is deposited as a thin film, such as silver (Ag). These low-emission glass is a functional material that reflects radiation in the infrared region, shields outdoor solar radiation in summer, and conserves indoor radiant heat in winter, thereby reducing energy consumption of buildings.

Since silver (Ag) used as such a low-emission layer is oxidized when exposed to air, a dielectric layer is deposited on the upper and lower portions of the low-emission layer as an oxidation-resistant layer, but these alone can not effectively prevent oxidation.

In addition, the glass is usually subjected to a tempering process in order to improve the impact strength and the heat resistance to enhance the stability. Such a strengthening process is performed, for example, at a high temperature condition of about 700 캜. Alkali ions such as sodium ions (Na + ) are discharged from the inside of the glass due to the strengthening process at a high temperature condition and moved toward the low radiation coating. Partially pushing out the low radiation layer formed of the alkali ions moved by silver The low-emission coating can be damaged, such as silver oxide being formed on the surface as the silver (Ag) is oxidized to the surface of the low-emission glass.

One embodiment of the present invention provides a low emissivity coating that provides excellent durability by effectively improving heat resistance and abrasion resistance.

Another embodiment of the present invention provides a functional building material for a window comprising the low emissivity coating.

In one embodiment of the present invention, sequentially, a first dielectric layer comprising silicon aluminum nitride; Low radiation layer; And a second dielectric layer comprising silicon aluminum nitride, wherein the refractive index of the first dielectric layer is lower than the refractive index of the second dielectric layer.

The first dielectric layer may have a refractive index of about 2.1 to about 2.3 at a wavelength of 550 nm.

The second dielectric layer may have a refractive index of about 1.8 to about 2.0 at a wavelength of 550 nm.

The thickness of the first dielectric layer may be between about 20 nm and about 60 nm.

The thickness of the second dielectric layer may be between about 20 nm and about 60 nm.

And a barrier layer laminated on at least one side of the low-emission layer, wherein the barrier layer includes a metal and may not include a metal oxide.

Wherein the barrier layer is selected from the group consisting of Ni, Cr, Nb, Ni-Cr, Ti, Ni-Ti, And may include at least one metal.

The thickness of the barrier layer may be from about 0.5 nm to about 3.0 nm.

The low-emission layer may include at least one selected from the group consisting of Ag, Au, Cu, Al, Pt, Pd, and combinations thereof.

The thickness of the low emissivity layer may be from about 5 nm to about 25 nm.

A metal layer on the second dielectric layer; A metal oxide layer; And a silicon-based or zirconium-based composite metal oxynitride layer.

The metal layer may include at least one selected from the group consisting of silicon, aluminum, titanium, zirconium, a silicon compound metal, a titanium compound metal, a zirconium compound metal and a combination thereof, and may have a thickness of about 0.5 nm to about 5 nm.

Wherein the metal oxide layer contains at least one selected from the group consisting of silicon oxide, aluminum oxide, titanium oxide, zirconium oxide, silicon compound metal oxide, titanium compound metal oxide, zirconium compound metal oxide, nm to about 5 nm.

The thickness of the silicon-based or zirconium-based composite metal oxynitride layer may be about 2 nm to about 20 nm.

In another embodiment of the present invention, a transparent substrate; And a low-emission coating coated on at least one side of the transparent substrate.

The transparent substrate may be a glass or transparent plastic substrate having a visible light transmittance of about 80% to about 100%.

The low emissivity coating can achieve excellent durability by effectively improving heat resistance, moisture resistance, acid resistance and abrasion resistance.

Figure 1 is a schematic cross-sectional view of a low emissivity coating according to one embodiment of the present invention.
Figure 2 is a schematic cross-sectional view of a low emissivity coating according to one embodiment further comprising a barrier layer.
3 is a schematic cross-sectional view of a low emissivity coating according to one embodiment further comprising a barrier layer and a protective layer.
4 is a schematic cross-sectional view of a functional building material for a window according to another embodiment of the present invention.
5 is an optical microscope image of the surface of the low emissivity coating after evaluation of heat resistance under specific conditions for the low emissivity coating prepared in Example 1 and Comparative Example 1 of the present invention.
6 is an optical microscope image of the surface of the low emissivity coating after evaluation of moisture resistance under specific conditions for the low emissivity coating prepared in Example 1 and Comparative Example 1 of the present invention.
7 is an optical microscope image of the surface of the low emissivity coating after evaluation of chemical resistance under specific conditions for the low emissivity coating prepared in Example 1 and Comparative Example 1 of the present invention.
8 is a graph showing the change in color index of each low-emission coating prepared in Example 1 and Comparative Example 1 after moisture resistance evaluation under specific conditions.

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings, which will be readily apparent to those skilled in the art to which the present invention pertains. The present invention may be embodied in many different forms and is not limited to the embodiments described herein.

In order to clearly illustrate the present invention, parts not related to the description are omitted, and the same or similar components are denoted by the same reference numerals throughout the specification.

In the drawings, the thickness is enlarged to clearly represent the layers and regions. In the drawings, for the convenience of explanation, the thicknesses of some layers and regions are exaggerated.

Hereinafter, the formation of any structure in the "upper (or lower)" or the "upper (or lower)" of the substrate means that any structure is formed in contact with the upper surface (or lower surface) of the substrate However, the present invention is not limited to not including other configurations between the substrate and any structure formed on (or under) the substrate.

In one embodiment of the present invention, sequentially, a first dielectric layer comprising silicon aluminum nitride; Low radiation layer; And a second dielectric layer comprising silicon aluminum nitride, wherein the refractive index of the first dielectric layer is lower than the refractive index of the second dielectric layer.

The low emissivity coating can be formed as a multilayer thin film structure based on a low emissivity layer that selectively reflects far infrared rays among solar radiation and can be formed by lowering the emissivity to a low emissivity, ) Effect.

The low-emission coating is formed as described above. For example, when applied as a coating film of a window glass, it minimizes heat transfer between indoor and outdoor by reflecting outdoor solar radiation in summer and preserving indoor heating radiation in winter, It is a functional material that brings energy saving effect of buildings.

'Emissivity' is the rate at which an object absorbs, transmits, and reflects energy with a certain wavelength. That is, in this specification, the emissivity refers to the degree of absorption of infrared energy in the infrared wavelength range. Specifically, when the far infrared ray corresponding to the wavelength range of about 5 탆 to about 50 탆 is applied, Means the ratio of infrared energy absorbed to infrared energy.

According to Kirchhoff's law, the infrared energy absorbed by an object is equal to the infrared energy emitted by the object again, so the absorption and emissivity of the object are the same.

Also, because the infrared energy that is not absorbed is reflected from the surface of the object, the higher the reflectance of the object to the infrared energy, the lower the emissivity. Numerically, it has a relation of (emissivity = 1 - infrared reflectance).

Such emissivity can be measured by various methods commonly known in the art, and can be measured by a facility such as a Fourier transform infrared spectroscope (FT-IR) according to the KSL2514 standard.

The absorption rate, that is, the emissivity, of far-infrared rays exhibiting such a strong heat action, such as an arbitrary object, for example, low-emission glass, may have a very important meaning in measuring the heat insulation performance.

As described above, the low-emission coating is used as a coating on a transparent substrate such as, for example, glass to maintain a predetermined transmittance property in the visible light region, thereby realizing excellent light-emitting properties. In the infrared region, It can be used as functional building material for energy-saving window which can provide excellent insulation effect.

In order to improve the impact resistance and heat resistance, a functional building material such as a window glass is inevitably subjected to a tempering process performed at a high temperature of about 700 ° C. or more. Alkali ions such as sodium ion (Na + ) escape and diffuse into the low radiation coating film. As the alkali ions are diffused, the low spinning layer of the low spinning coating film is pressurized by the diffusion of the alkali ions, and the Ag, Au, Cu, Al, Pt, Pd, And oxidation occurs while exposed to the air, thereby damaging the low radiation coating.

Accordingly, the low-emission coating according to an embodiment of the present invention is characterized in that the first dielectric layer and the second dielectric layer include silicon-aluminum nitride (SiAlN x ), and the refractive index of the first dielectric layer is the second By appropriately adjusting the silicon aluminum and nitrogen contents of the silicon aluminum nitride to be relatively higher than the refractive index of the dielectric layer in the respective layers, the first dielectric layer is formed by the migration of the alkali ions by the strengthening process, The second dielectric layer can effectively prevent the damage of the low radiation coating due to the strengthening process while effectively preventing the metal or metal ions such as Ag, Au, Cu, Al, Pt, and Pd contained in the radiation layer from moving So that excellent heat resistance and excellent abrasion resistance can be realized.

Specifically, the first dielectric layer includes a silicon aluminum nitride having a relatively high content of silicon aluminum and a low nitrogen content and a low density so as to have a higher refractive index than the second dielectric layer, And diffusion of oxygen can be effectively suppressed.

At the same time, the second dielectric layer is relatively low in silicon aluminum content so as to have a lower refractive index than the first dielectric layer, but has high nitrogen content and high density silicon aluminum nitride, thereby further improving mechanical durability have.

Accordingly, the low-spin coating effectively prevents damage to the low-spin coating due to a high-temperature tempering process that is essentially required after coating, for example, on a transparent substrate such as glass, thereby improving heat resistance and abrasion resistance, Can be maintained.

Figure 1 schematically illustrates a cross-section of a low emissivity coating 100 according to one embodiment of the present invention. The low spin coating (100) comprises sequentially forming a first dielectric layer (110) comprising silicon aluminum nitride; A low emissivity layer 130; And a second dielectric layer (120) comprising silicon aluminum nitride, wherein the refractive index of the first dielectric layer (110) is higher than that of the second dielectric layer (120).

The low emissivity layer 130 is a layer formed of an electrically conductive material, e. G., Metal, which may have a low emissivity, i. E. Has a low sheet resistance and accordingly low emissivity. For example, the low emissivity layer 130 can have an emissivity of from about 0.01 to about 0.3, specifically from about 0.01 to about 0.2, and more specifically from about 0.01 to about 0.1, From about 0.01 to about 0.08.

The low emissivity layer 130 in the emissivity range can realize both excellent light fastness and heat insulating effect by appropriately adjusting the visible light transmittance and the infrared emissivity. The low emissivity layer 130 having such emissivity may have a sheet resistance of, for example, from about 0.78? / Sq to about 6.42? / Sq, but is not limited thereto.

The low-emission layer 130 functions to selectively transmit and reflect sun rays, and specifically has a low reflectance because of high reflectivity to radiation in the infrared region. The low-emission layer 130 may include at least one selected from the group consisting of Ag, Au, Cu, Al, Pt, Pd, and combinations thereof, but is not limited thereto. May be used without limitation.

In one embodiment, the low spinning layer 130 may be a layer formed of silver (Ag), such that the low spin coating 100 can achieve high electrical conductivity, low water absorption in the visible light range, durability, etc. have.

The thickness of the low emissivity layer 130 may be, for example, from about 5 nm to about 25 nm. The low emissivity layer 130 having a thickness in this range is suitable for simultaneously realizing a low infrared emissivity and a high visible light transmittance.

The first dielectric layer 110 may have a refractive index of about 2.1 to about 2.3 at a wavelength of about 550 nm. The composition of the silicon aluminum nitride contained in the first dielectric layer 110 may be adjusted to a relatively low level of density while the content of silicon aluminum is relatively high while the content of silicon aluminum is relatively high so that a high- Diffusion of alkali ions diffused from the glass can be effectively suppressed.

The second dielectric layer 120 may have a refractive index of about 1.8 to about 2.0 at a wavelength of about 550 nm. The composition of the silicon aluminum nitride contained in the second dielectric layer 120 is adjusted to a relatively high silicon aluminum content and a high density of nitrogen so as to realize a low refractive index within the above range, It is possible to effectively prevent damage to the low-radiation coating by the process.

Each of the first dielectric layer 110 and the second dielectric layer 120 may be formed by using silicon aluminum as a sputtering target and depositing it in a reactive gas atmosphere containing nitrogen, The refractive index of each dielectric layer can be adjusted by appropriately adjusting the content of nitrogen contained in the reactive gas, but the present invention is not limited thereto.

For example, the first dielectric layer 110 may be formed by depositing the first dielectric layer 110 in a reactive gas atmosphere having a lower nitrogen content than that of the second dielectric layer 120, The density of the silicon aluminum nitride can be formed at a lower level while the content of silicon aluminum is relatively higher and the content of nitrogen is lower.

Specifically, the first dielectric layer 110 is formed by depositing silicon aluminum as a sputtering target in a reactive gas atmosphere with a flow rate ratio of argon gas to nitrogen gas of, for example, about 5: 1 to about 8: 1 can do. The first dielectric layer 110 may be formed to have a refractive index of about 2.1 to about 2.3 at a wavelength of about 550 nm by depositing under a reactive gas atmosphere having a flow rate ratio within the above range.

The first dielectric layer 110 may be formed by depositing a predetermined substrate, for example, a predetermined substrate on which the low-emission coating 100 is to be applied. The predetermined substrate may be, for example, But is not limited thereto.

In addition, for example, the second dielectric layer 120 may be deposited in a reactive gas atmosphere having a higher nitrogen content than the first dielectric layer 110 so that the composition of the silicon aluminum nitride included in the second dielectric layer 120 may be silicon The density of the silicon aluminum nitride can be formed at a higher level while the content of aluminum is relatively lower and the content of nitrogen is higher.

Specifically, the second dielectric layer 120 is formed by depositing silicon aluminum as a sputtering target in a reactive gas atmosphere with a flow rate ratio of argon gas to nitrogen gas of, for example, about 1: 1 to about 4: 1 can do. The second dielectric layer 120 may be formed to have a refractive index of about 1.8 to about 2.0 at a wavelength of about 550 nm by depositing under a reactive gas atmosphere having a flow rate in the above range.

The second dielectric layer 120 may be deposited on the barrier layer 140, which may further include the low-emission layer 130, as described below.

The refractive index of the first dielectric layer 110 may be about 2.1 to about 2.3 at a wavelength of about 550 nm by appropriately adjusting the content of the nitrogen included in the reactive gas, 120 may be realized at a level of about 1.8 to about 2.0, but the method of controlling the respective refractive indexes is not limited to the above-described method.

The thickness of the first dielectric layer 110 may be, for example, about 20 nm to about 60 nm. By having a thickness within the above range, the movement of the alkali ion can be sufficiently suppressed at a high temperature condition without excessively increasing the thickness of the low radiation coating 100, thereby sufficiently preventing damage to the low radiation coating 100 .

The thickness of the second dielectric layer 120 may be, for example, from about 20 nm to about 60 nm. By having the thickness within the above range, the occurrence of scratches and the like can be sufficiently suppressed during the reinforcing process without excessively increasing the thickness of the low spinning coating 100, thereby effectively preventing damage to the low spinning coating, thereby achieving a high level of durability .

In one embodiment, the low-emission layer 130 may further include a barrier layer deposited on at least one side of the low-emission layer 130, and the barrier layer may include a metal and may not include a metal oxide. Figure 2 schematically shows a cross-sectional view of a low emissivity coating 200 according to an embodiment in which the barrier layer 140 is further included.

The barrier layer 140 is deposited on at least one side of the low-emission layer 130 to prevent corrosion of the low-emission layer 130. For example, the barrier layer 140 may be laminated on one side or both sides of the low-emission layer 130, and may be laminated on both sides to prevent corrosion of the low-emission layer 130 can do.

Generally, in order to protect the low radiation layer, a metal oxide layer is laminated on both sides or a metal layer and a metal oxide layer are sequentially laminated. In the case where the metal oxide layer is included, the low radiation glass The metal oxide layer at the edge face of the rim has a problem of promoting the corrosion of the low radiation layer.

In a low spin coating 200 according to an embodiment of the present invention, a barrier layer 140 including a metal other than a metal oxide is laminated on at least one side of the low spinning layer 130, The durability of the low spin coating 130 can be maintained at an excellent level by effectively reducing the corrosion of the low spin coating layer 130 by oxygen or water supplied from the edge face of the glass.

For example, when the barrier layer 140 is formed of Ni, Cr, Nb, Ni-Cr, Ti, Ni-Ti, A combination of at least one metal selected from the group consisting of a combination of metals and the combination of the low emission layer 130 can effectively prevent corrosion.

The thickness of the barrier layer 140 may be, for example, from about 0.5 nm to about 3.0 nm. By having the thickness range, the corrosion resistance of the low radiation layer can be improved without excessively increasing the thickness of the low radiation coating 200.

The low spin coating 100, 200 can be formed sequentially from the upper surface of the substrate to be coated using the known deposition method, for example, by the sputtering method , But is not limited thereto.

In one embodiment, the second dielectric layer 120 may further include a protective layer on top of the second dielectric layer 120, and Figure 3 further illustrates a cross section of the low radiation coating 300 according to one embodiment further comprising a barrier layer and a protective layer. . Specifically, the protective layer 150 may include a metal layer 151 from the second dielectric layer 120; A metal oxide layer 152; And a silicon-based or zirconium-based composite metal oxynitride layer 153 sequentially in this order.

The metal layer 151 is formed on the second dielectric layer 120. The surface of the metal layer 151 is partially oxidized through a post-oxidation process to form a metal oxide layer 152 , It may mean a layer that is not partially oxidized and remains.

The metal layer 151 may include at least one selected from the group consisting of silicon (Si), aluminum (Al), titanium (Ti), zirconium (Zr), silicon based composite metal, titanium based composite metal, zirconium based composite metal, More preferably, it includes zirconium or zirconium-based composite metals, but is not limited thereto.

That is, since the metal layer 151 is formed on the second dielectric layer 120, the metal layer 151 prevents diffusion of chemical reactants such as O 2 , H 2 O and Na + (300) can have excellent chemical properties such as moisture resistance, acid resistance, and alkali resistance.

The thickness of the metal layer 151 is preferably 0.5 nm to 5 nm, but is not limited thereto. For example, when the surface of the metal layer 151 is partially oxidized through a post-oxidation process on the surface of the metal layer 151 to form the metal oxide layer 152, the thickness of the metal layer 151 is not partially oxidized, Can mean final thickness

If the thickness of the metal layer 151 is less than 0.5 nm, there is a problem that excellent chemical properties such as moisture resistance, acid resistance, and basic resistance of the low spin coating 300 are deteriorated. When the thickness of the metal layer 151 exceeds 5 nm There is a problem that the transmittance of the low radiation coating 300 is reduced.

Since the metal oxide layer 152 is formed on the metal layer 151 and the metal oxide layer 152 is formed, the metal oxide layer 152 is excellent in mechanical characteristics of the low spin coating film and is excellent in the characteristics such as O 2 , H 2 O and Na + By inhibiting the diffusion of chemical reactants, the chemical properties are excellent.

Particularly, when the formation of the metal oxide layer 152 is performed by partially oxidizing the surface of the metal layer 151 through a post-oxidation process on the surface of the metal layer 151, the metal is oxidized by a post- Density bulk metal oxide layer 152 can be formed in accordance with such volume expansion, which has the advantage of further increasing the hardness of the low spin coating 300. [

That is, in the case where the metal oxide layer 152 is formed by partially oxidizing the surface of the metal layer 151 through the post-oxidation process on the surface of the metal layer 151 according to the present invention, when only the metal oxide layer 152 of the uppermost coating layer is omitted The hardness of the low radiation coating 300 can be significantly increased.

The metal oxide layer 152, silicon oxide (SiO 2), aluminum oxide (Al 2 O 3), titanium oxide (TiO 2), zirconium oxide (ZrO 2), silicon-based composite metal oxide, the titanium-based composite metal oxide, zirconium Based composite metal oxide, and a combination thereof, and more preferably at least one selected from zirconium oxide or zirconium-based composite metal oxide, but is not limited thereto.

The thickness of the metal oxide layer 152 is preferably 0.5 nm to 5 nm, but is not limited thereto. For example, when the surface of the metal layer 151 is partially oxidized through the post-oxidation process of the surface of the metal layer 151, the metal layer 151 may have an initial thickness of 1 nm to 10 nm And 0.5 nm to 5 nm of the surface of the metal layer 151 is oxidized by the post-oxidation process, so that it can be the thickness of the metal oxide layer 152.

The silicon-based or zirconium-based composite metal oxynitride layer 153 is formed by depositing a silicon-based or zirconium-based composite metal oxynitride. The silicon-based or zirconium-based composite metal oxynitride is an alloy oxynitride in which silicon or zirconium is a main component And the mechanical properties such as abrasion resistance can be further improved by the excellent hardness of the silicon-based or zirconium-based composite metal oxynitride layer 153.

For example, the silicon-based composite metal oxynitride may include silicon aluminum oxynitride, and the zirconium-based composite metal oxynitride may include zirconium aluminum oxynitride, , But is not limited thereto.

At this time, the deposition of the silicon-based or zirconium-based composite metal oxynitride can be performed at the same time as forming the metal oxide layer by partially oxidizing the surface of the metal layer, as described above.

The thickness of the silicon-based or zirconium-based composite metal oxynitride layer 153 may be 2 nm to 20 nm. If the thickness of the silicon-based or zirconium-based composite metal oxide nitride layer 153 is less than 2 nm, mechanical properties such as abrasion resistance may deteriorate. If the thickness of the silicon-based or zirconium-based composite metal oxide nitride layer 153 exceeds 20 nm There is a problem that the transmittance is reduced.

In another embodiment of the present invention, a transparent substrate; And the low radiation coating coated on at least one side of the transparent substrate.

4 is a cross-sectional view of the functional building material 400 for a window, and may be a structure in which a low radiation coating 300 is coated on at least one side of the base 160, for example, one side or both sides. Specifically, the functional building material 400 for a window includes a first dielectric layer 110 on at least one side of the substrate 160, the low-emission layer 130 in which the barrier layer 140 is laminated on both sides, The protective layer 150 may include a metal layer 151 and a metal oxide layer 152 sequentially from the upper portion of the second dielectric layer 120. The protective layer 150 may be formed by sequentially stacking a dielectric layer 120 and a protective layer 150, And a silicon-based or zirconium-based composite metal oxynitride layer 153.

The low dielectric layer 130, the second dielectric layer 120, and the protective layer 150, on which the first dielectric layer 110 and the barrier layer 140 are laminated on both surfaces, are as described above in one embodiment.

The substrate 160 may be a transparent substrate having a high visible light transmittance, for example, a glass or transparent plastic substrate having a visible light transmittance of about 80% to about 100%. The substrate 160 can be, for example, glass used for construction, without limitation, and can be, for example, from about 2 mm to about 12 mm thick and can vary depending on the purpose and function of use, It is not.

The low spin coating can be achieved by controlling the transmittance and the reflectance according to the wavelength of light by adjusting the material and thickness of each layer constituting the low spin coating in order to realize an optical spectrum suitable for the purpose of use. For example, the low spin coating improves light fastness by increasing the visible light transmittance, thereby securing a clear visual field while reducing the infrared emissivity and securing an excellent heat insulating effect.

By controlling the material and thickness of each layer constituting the low spin coating, it is possible to finely control the optical performance such as hue, reflectivity and transmittance of the high reflection surface of the low spin coating as seen from the outside.

Hereinafter, examples and comparative examples of the present invention will be described. The following embodiments are only examples of the present invention, and the present invention is not limited to the following embodiments.

( Example )

Using a magnetron sputtering evaporator (manufacturer Selcos, trade name Cetus-S), a low emissivity coating of a multilayer structure coated on a transparent glass substrate was prepared as follows.

Example  One

A SiAl target (manufactured by GfE, Germany) having Si: Al = 9: 1 was deposited on a transparent glass substrate having a thickness of 6 mm under an atmosphere of argon / nitrogen (argon: nitrogen flow rate = 80: A barrier layer is formed by depositing NiCr to a thickness of 0.5 nm on the upper surface of the first dielectric layer in an atmosphere of 100% argon to form a barrier layer, and a 100% argon atmosphere To form a low-emission layer having a thickness of 7 nm, an NiCr layer having a thickness of 0.5 nm was deposited on the upper surface of the low-emission layer in an atmosphere of 100% argon to form a barrier layer, : A SiAl target (manufactured by GfE, Germany) having Al = 9: 1 was deposited under a nitrogen / argon / nitrogene (argon: nitrogen flow rate = 80:20) atmosphere to form a second dielectric layer having a thickness of 35 nm . Subsequently, zirconium is deposited on the upper surface of the second dielectric layer as a protective layer in an atmosphere of 100% argon to form a zirconium layer having a thickness of 4 to 5 nm, and then a post-oxidation process is performed on the surface of the metal layer, The surface of the zirconium layer was partially oxidized to form a zirconium oxide layer having a thickness of 3 to 4 nm. The surface of the zirconium layer was partially oxidized to form a zirconium oxide layer, and silicon aluminum oxynitride was deposited to form a silicon aluminum oxynitride A low emissivity coating coated on a clear glass substrate was prepared by forming a layer.

The low spin coating had a refractive index of 2.15 for the first dielectric layer and a refractive index of 1.94 for the second dielectric layer at a wavelength of 550 nm.

Comparative Example 1 (the refractive index of the first dielectric layer is the same as the refractive index of the second dielectric layer)

A SiAl target (manufactured by GfE, Germany) having Si: Al = 9: 1 was deposited on a transparent glass substrate having a thickness of 6 mm under the atmosphere of argon / nitrogen (argon: nitrogen flow rate = 80:20) Depositing a first dielectric layer having a thickness of 35 nm on the first dielectric layer and depositing a zinc aluminum oxide on the upper surface of the first dielectric layer under an atmosphere of 100% argon to form a zinc aluminum oxide layer having a thickness of 6 nm, A barrier layer was formed by depositing NiCr to a thickness of 0.5 nm in an argon atmosphere of 100%, Ag was deposited on the upper surface of the barrier layer in an atmosphere of 100% argon to form a low-emission layer with a thickness of 7 nm, A barrier layer was formed by depositing NiCr to a thickness of 0.5 nm in an atmosphere of 100% argon to form a barrier layer. On the upper surface of the barrier layer, zinc aluminum oxide A SiAl target (manufactured by GfE, Germany) having Si: Al = 9: 1 was coated on the upper surface of the aluminum oxide layer to form a 6 nm thick zinc oxide layer on the upper surface of the aluminum oxide layer, and a reactive gas containing argon / Under the atmosphere of argon: nitrogen = 80: 20) to form a second dielectric layer with a thickness of 35 nm.

The low spin coating had a refractive index of 1.94 for the first dielectric layer and a refractive index of 1.94 for the second dielectric layer at a wavelength of 550 nm.

Comparative Example  2 ( Comparative Example  1 to the protective layer)

A zinc-aluminum oxide layer, a barrier layer, a low-emission layer, a barrier layer, and a zinc-aluminum-oxide layer were formed in sequence on the upper surface of the second dielectric layer in the same manner as in Comparative Example 1, As a protective layer, zirconium is deposited in a 100% argon atmosphere to form a 4 to 5 nm thick zirconium layer, and a post-oxidation process is performed on the surface of the metal layer to partially oxidize the surface of the zirconium layer to form a 3-4 nm thick zirconium oxide A surface of the zirconium layer is partially oxidized to form a zirconium oxide layer and silicon aluminum oxynitride is deposited to form a silicon aluminum oxynitride layer having a thickness of 10 nm to form a low- Coating.

The low spin coating had a refractive index of 1.94 for the first dielectric layer and a refractive index of 1.94 for the second dielectric layer at a wavelength of 550 nm.

Comparative Example  3 ( Comparative Example  In 2 Zinc aluminum oxide layer  remove)

A SiAl target (manufactured by GfE, Germany) having Si: Al = 9: 1 was deposited on a transparent glass substrate having a thickness of 6 mm under the atmosphere of argon / nitrogen (argon: nitrogen flow rate = 80:20) A barrier layer is formed by depositing NiCr to a thickness of 0.5 nm on the upper surface of the first dielectric layer in an atmosphere of 100% argon to form a barrier layer, and a 100% argon atmosphere To form a low-emission layer having a thickness of 7 nm, an NiCr layer having a thickness of 0.5 nm was deposited on the upper surface of the low-emission layer in an atmosphere of 100% argon to form a barrier layer, : A SiAl target (manufactured by GfE, Germany) having Al = 9: 1 was deposited under a nitrogen / argon / nitrogene (argon: nitrogen flow rate = 80:20) atmosphere to form a second dielectric layer having a thickness of 35 nm And , Zirconium is deposited on the upper surface of the second dielectric layer as a protective layer in an atmosphere of 100% argon to form a zirconium layer having a thickness of 4 to 5 nm and then a post-oxidation process is performed on the surface of the metal layer, Oxidized to form a zirconium oxide layer having a thickness of 3 to 4 nm, a surface of the zirconium layer is partially oxidized to form a zirconium oxide layer, and silicon aluminum oxynitride is deposited to form a silicon aluminum oxynitride layer having a thickness of 10 nm To produce a low emissivity coating coated on a clear glass substrate.

The low spin coating had a refractive index of 1.94 for the first dielectric layer and a refractive index of 1.94 for the second dielectric layer at a wavelength of 550 nm.

evaluation

The properties of the low emissivity coating coated on the transparent glass substrate of Example 1 and Comparative Example 1-3 were evaluated as described below and are shown in Table 1 below.

1. Evaluation of refractive index

The refractive indices at a wavelength of about 550 nm were calculated for each of the first and second dielectric layers of the low spin coating coated on the transparent glass substrate of Example 1 and Comparative Example 1-3.

Measuring method: The optical spectrum of each dielectric layer as a single layer was measured for a wavelength of 250 to 4500 nm using a spectrophotometer (manufactured by SHIMADZU, manufactured by SolidSpec-3700) to obtain transmission, coating reflection and glass reflection, The refractive index values were calculated by substituting the values into the equations, and the values for the wavelengths of about 550 nm were evaluated as the refractive indexes.

2. Evaluation of heat resistance

The low emissivity coatings coated on the transparent glass substrates of Example 1 and Comparative Example 1-3 were subjected to a strengthening test to measure the heat resistance.

Measuring method: Measured using a laboratory box furnace (AJEON HEATING INDUSTRIAL CO. LTD.). Specifically, the inside temperature of the large electric furnace was set at 700 캜 and left for 7 minutes I took it out. Subsequently, the sample was allowed to stand at room temperature to be slowly cooled, and then the degree of defects on the surface of each low-radiated coating was observed using an optical microscope (Nikon, ECLIPSE LV 100, X200).

The surface of each of the low-emission coatings thus observed was photographed with the above-mentioned optical microscope image and is shown in Fig.

3. Evaluation of moisture resistance

Under the conditions of 100 ° C and 98% RH (humidity), 14 (light) was applied to the transparent glass substrate coated with the transparent glass substrate of Example 1 and Comparative Example 1-3 using a constant temperature and humidity chamber (LSISON, And the humidity resistance was measured.

Measurement method: The number of corrosion points was measured using an optical microscope (Nikon, ECLIPSE LV 100) (X200).

Thus, the surface of the low emissivity coating with corrosion after the moisture resistance evaluation was photographed with the above optical microscope image and is shown in Fig.

4. Chemical resistance evaluation

The low emissivity coating coated on the transparent glass substrate of Example 1 and Comparative Example 1-3 was immersed in a Sigma Aldrich HCl solution of pH 2 at room temperature for 30 minutes to measure chemical resistance.

Measurement method: A change in color index before and after immersion was measured using a spectrophotometer (KONICA MINOLTA, model name VTLCM-700).

7 shows a graph of measured change in color index, and the surface of the low-radiated coating having the color index changed after measurement of chemical resistance was photographed with an optical microscope (Nikon, ECLIPSE LV 100) (X200) Respectively.

Specifically, in the graph of Fig. 8, the color (T) on the X axis represents the color transmitted through the transparent glass substrate coated with the low radiation coating, the color (R) represents the color reflected from the low radiation coated surface, S) represents the color reflected from the transparent glass substrate surface, and ΔE = (ΔL 2 + Δa 2 + Δb 2 ) 1/2 on the Y axis represents the color index change value.

5. Evaluation of wear resistance

The abrasion resistance before and after the strengthening test was measured for the low emissivity coatings coated on the clear glass substrates of Example 1 and Comparative Example 1-3, respectively.

Measuring method: A wear resistance test was performed using a washing machine (MANNA, MGR-460), and visually observing whether or not scratches occurred on the surface of each low-radiated coating were observed, and scratches And the mechanical durability was evaluated. The scratches were observed to have a width of at least about 50 탆 which is the minimum size that can be distinguished upon visual observation.

6. Evaluation of edge face corrosion

The low spin coating coated on the transparent glass substrate of Example 1 and Comparative Example 1-3 was allowed to stand for 14 days under the conditions of 98 ° C and 100% RH (humidity) to measure the corrosion depth of the low spinning layer Respectively.

Measurement method: An optical microscope image of the low-emission layer of the end face was photographed using an optical microscope (Nikon, ECLIPSE LV 100, X200) and the depth of the low-emission layer was measured.

Moisture resistance
(Count)
Chemical resistance (ΔE) Abrasion resistance (minute) End
Corrosive depth (㎛)
Example 1 2 Permeation (T): 0.09
Coating Reflectance (R): 0.06
Glass reflection (S): 0.05
Before reinforcement: 6 minutes
After fortification: 6 minutes
80
Comparative Example 1 More than 200 Permeation (T): 0.14
Coating Reflectance (R): 1.77
Glass reflection (S): 0.98
Before reinforcement: 5 minutes
After fortification: 1 minute
1800
Comparative Example 2 60 Permeation (T): 0.21
Coating Reflectance (R): 0.23
Glass reflection (S): 0.29
Before reinforcement: 5 minutes
After fortification: 5 minutes
1800
Comparative Example 3 5 Permeation (T): 0.04
Coating Reflectance (R): 0.06
Glass reflection (S): 0.07
Before reinforcement: 10 minutes
After fortification: 1 minute
100

As shown in Table 1, the low-emission coating of Example 1 exhibited excellent resistance to moisture due to only a few corrosion points, and a remarkably small change in color index, which was excellent in chemical resistance. In particular, It can be clearly seen that both the heat resistance and the abrasion resistance are remarkably excellent even when the scratches start to occur even after the application of the scratches. In addition, it can be confirmed that the corrosion depth at the end face is significantly reduced to 80 탆, which effectively reduces edge corrosion.

On the other hand, in the low spin coating of Comparative Example 1, the number of corrosion points increased by a factor of 100, the moisture resistance was remarkably inferior, the color index change value was remarkably large and the chemical resistance was inferior, and after the high temperature tempering process was applied, It is found that the low-radiation coating is damaged because the time for starting to start is only one minute, which is inferior in heat resistance and abrasion resistance. In addition, the corrosion depth on the end face increased by 100 times, indicating that the corrosion occurred remarkably on the end face.

In addition, the low spin coating of Comparative Example 2 has good anti-abrasion properties measured at about 5 minutes before and after strengthening, but the number of corrosion points is 60, which is inferior in moisture resistance and has a large change in color index, which is inferior in chemical resistance. In addition, it can be seen that the corrosion depth on the end face is deep and the corrosion has remarkably occurred.

In addition, the low spin coating of Comparative Example 3 had five corrosion points with good moisture resistance and a small change in color index, which is excellent in chemical resistance. However, after application of a high temperature tempering process, Is only one minute, which is a value corresponding to 1/6 of that of Example 1, so that the low radiation coating is remarkably damaged and the heat resistance and abrasion resistance are remarkably inferior. In addition, it can be confirmed that the corrosion depth of the end face is 100 μm, and the corrosion of the end face is further promoted by the damage of the low radiation coating.

100, 200, 300: low radiation coating
400: low emission glass
110: first dielectric layer
120: second dielectric layer
130: low radiation layer
140: barrier layer
150: protective layer
151: metal layer
152: metal oxide layer
153: a silicon-based or zirconium-based composite metal oxynitride layer
160: substrate

Claims (18)

Sequentially, a first dielectric layer comprising silicon aluminum nitride; Low radiation layer; And a second dielectric layer comprising silicon aluminum nitride,
Further comprising a barrier layer having a refractive index higher than that of the second dielectric layer and stacked on both sides of the lower radiation layer, wherein the barrier layer includes a metal and does not include a metal oxide,
The first dielectric layer is formed by depositing silicon aluminum as a sputtering target in a reactive gas atmosphere having a flow ratio of argon gas to nitrogen gas in a range of 5: 1 to 8: 1,
The second dielectric layer is formed by depositing silicon aluminum as a sputtering target in a reactive gas atmosphere having a flow ratio of argon gas to nitrogen gas of 1: 1 to 4: 1
Low radiation coating.
The method according to claim 1,
Wherein the first dielectric layer has a refractive index of 2.1 to 2.3 at a wavelength of 550 nm
Low radiation coating.
The method according to claim 1,
Wherein the second dielectric layer has a refractive index of 1.8 to 2.0 at a wavelength of 550 nm
Low radiation coating.
delete delete delete delete delete delete The method according to claim 1,
Wherein the barrier layer has a thickness of 0.5 nm to 3.0 nm
Low radiation coating.
The method according to claim 1,
A metal layer on the second dielectric layer; A metal oxide layer; And a silicon-based or zirconium-based composite metal oxynitride layer,
Low radiation coating.
12. The method of claim 11,
Wherein the metal layer comprises at least one selected from the group consisting of silicon, aluminum, titanium, zirconium, a silicon based composite metal, a titanium based composite metal, a zirconium based composite metal and combinations thereof,
Low radiation coating.
12. The method of claim 11,
Wherein the metal oxide layer contains at least one selected from the group consisting of silicon oxide, aluminum oxide, titanium oxide, zirconium oxide, silicon based composite metal oxide, titanium based composite metal oxide, zirconium based composite metal oxide and combinations thereof, 5 nm
Low radiation coating.
12. The method of claim 11,
The thickness of the silicon-based or zirconium-based composite metal oxynitride layer is preferably from 2 nm to 20 nm
Low radiation coating.
delete delete delete delete
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