KR101970495B1 - Low-emissivity coat, method for preparing low-emissivity coat and functional building material including low-emissivity coat for windows - Google Patents

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

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KR101970495B1
KR101970495B1 KR1020150063332A KR20150063332A KR101970495B1 KR 101970495 B1 KR101970495 B1 KR 101970495B1 KR 1020150063332 A KR1020150063332 A KR 1020150063332A KR 20150063332 A KR20150063332 A KR 20150063332A KR 101970495 B1 KR101970495 B1 KR 101970495B1
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layer
low
outer protective
protective layer
emissivity
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KR1020150063332A
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KR20150139425A (en
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권대훈
전윤기
김웅길
유현우
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(주)엘지하우시스
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL 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
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL 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
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
    • C03C17/3429—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating
    • C03C17/3435—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating comprising a nitride, oxynitride, boronitride or carbonitride
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL 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
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36—Surface 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
    • C03C17/3602—Surface 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
    • C03C17/361—Coatings of the type glass/metal/inorganic compound/metal/inorganic compound/other
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL 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
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36—Surface 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
    • C03C17/3602—Surface 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
    • C03C17/3618—Coatings of type glass/inorganic compound/other inorganic layers, at least one layer being metallic

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

Abstract

Wherein the outer protective layer comprises a first outer protective layer and a second outer protective layer sequentially laminated to the dielectric layer, wherein the first outer protective layer and the second outer protective layer are sequentially laminated, Zirconium oxide, and the second outer protective layer provides a low emissivity coating comprising a composite metal oxynitride.

Description

TECHNICAL FIELD [0001] The present invention relates to a low-emissivity functional coating material for a window, including a low-emission coating, a method of producing a low-emission coating, and a low-

Low-emission coatings, methods of making 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.

In general, silver (Ag) used as a low-emission layer is oxidized when exposed to air, so that a dielectric layer is deposited on the upper and lower portions of the low-emission layer using an oxidation-resistant layer. This dielectric layer also serves to increase the visible light transmittance.

One embodiment of the present invention provides a low emissivity coating with improved durability.

Another embodiment of the present invention provides a method of making the low emissivity coating.

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, the outer protective layer sequentially includes a first outer protective layer and a second outer protective layer sequentially stacked on the dielectric layer, including a low radiation layer, a dielectric layer, and an outer protective layer The first outer protective layer comprises zirconium oxide and the second outer protective layer provides a low emissivity coating comprising a composite metal oxynitride.

The zirconium oxide may be represented by ZrO x , where 1.9 < x < 2.

The composite metal oxynitride may include an oxynitride of a zirconium (Zr) based composite metal.

The first outer protective layer may have a thickness of 1 nm to 5 nm.

The second outer protective layer may have a thickness of 1 nm to 20 nm.

Wherein the dielectric layer comprises at least one selected from the group consisting of a metal oxide, a metal nitride, and combinations thereof, or at least one of bismuth (Bi), boron (B), aluminum (Al), silicon (Si) (Mg), antimony (Sb), beryllium (Be), and combinations thereof.

The dielectric layer may comprise at least one selected from the group consisting of titanium oxide, zinc tin oxide, zinc oxide, aluminum zinc oxide, tin oxide, bismuth oxide, silicon nitride, silicon aluminum nitride, silicon nitride tin and combinations thereof .

The thickness of the dielectric layer may be between 5 nm and 60 nm.

The low spinning layer may comprise at least one selected from the group consisting of Ag, Au, Cu, Al, Pt, ion doped metal oxides, and combinations thereof.

The low emissivity layer may have an emissivity of 0.01 to 0.3.

The thickness of the low spinning layer may be between 5 nm and 25 nm.

The low emissivity coating may further comprise a low emissivity protection metal layer between the low emissivity layer and the dielectric layer.

The low radiation protection metal layer may include one selected from the group consisting of Ni, Cr, an alloy of Ni and Cr, Ti, and combinations thereof.

And the dielectric layer and the outer protective layer are sequentially laminated on both sides of the low radiation layer.

In another embodiment of the present invention,

Preparing a low emissivity layer in which a dielectric layer is laminated on at least one side of the low emissivity layer;

Depositing zirconium on the dielectric layer by a sputtering method to form a zirconium layer;

Depositing the zirconium layer followed by post-oxidation to deposit zirconium oxide and simultaneously oxidizing the zirconium in the zirconium layer to form a first outer protective layer comprising zirconium oxide; And

A sputtering process is performed with a reactive gas targeting the outer protective layer composite metal to deposit a composite metal oxynitride on the first outer protective layer to form a second outer protective layer containing a composite metal oxide nitride A method of making a low emissivity coating comprising:

In another embodiment of the present invention, a transparent substrate; And a low emissivity 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 80% to 100%.

The low emissivity coating is improved in chemical resistance, moisture resistance and abrasion resistance to realize excellent durability.

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 another embodiment of the present invention.
3 is a schematic cross-sectional view of a functional building material for a window according to another embodiment of the present invention.
Fig. 4 is an optical microscope image of the glass coated with the low emissivity coating prepared in Examples and Comparative Examples and observing the degree of occurrence of corrosion after being left under acidic conditions.
Fig. 5 is an optical microscope image observed after standing under specific conditions for moisture resistance evaluation on the glass coated with the low emissivity coating prepared in Examples and Comparative Examples. Fig.

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 invention, a low radiation coating, which in turn comprises a low radiation layer, a dielectric layer and an outer protective layer, is provided. Wherein the outer protective layer comprises a first outer protective layer and a second outer protective layer sequentially laminated to the dielectric layer, the first outer protective layer comprises zirconium oxide, and the second outer protective layer comprises a composite metal Oxynitride.

The low emissivity coating includes an outer protective layer having a multi-layered structure to effectively improve chemical resistance, moisture resistance, and abrasion resistance to realize excellent durability.

Figure 1 is a cross-sectional view of a low emissivity coating 100 comprising a low emissivity layer 110, a dielectric layer 120, and an outer emissive layer 130, according to one embodiment of the present invention. The outer protective layer 130 includes a first outer protective layer 130a and a second outer protective layer 130b.

The outer protective layer 130 may be manufactured by depositing zirconium first on the dielectric layer 120, for example, and then forming a zirconium oxide layer by a post-oxidation treatment according to a method of manufacturing a low spin coating as described later.

The low radiation coating 100 is formed by forming the first outer protective layer 130a and the second outer protective layer 130b as the outermost outer protective layer 130, thereby improving the chemical resistance, moisture resistance and abrasion resistance Durability against acid, moisture, friction, heat treatment, bending, etc. is improved.

The low emissivity coating 100 may be formed as a multilayer thin film structure based on a low emissivity layer 110 that selectively reflects far infrared radiation among the sun radiation and may be formed as a low emissivity , And low-e (low emissivity) effect.

The low-emission coating 100 is formed as described above. For example, when applied as a coating film of a window glass, the low-radiation coating 100 reflects outdoor solar radiation in summer and preserves indoor heating radiation in winter, It is a functional material that minimizes the 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 100 is used as a coating film on a transparent substrate such as glass, for example, to maintain a predetermined transmittance property in the visible light region, thereby realizing excellent light- It can be used as a functional building material for energy-saving windows that can provide excellent thermal insulation effect by lowering the emissivity.

The low emissivity layer 110 is a layer of an electrically conductive material, e.g. a metal, which may have a low emissivity, i. E. It has a low sheet resistance and hence a low emissivity. For example, the low emissivity layer 110 may 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 110 in the emissivity range can realize both good light fastness and heat insulation effect by appropriately adjusting the visible light transmittance and the infrared emissivity. The low emissivity layer 110 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 radiation layer 110 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 spinning layer 110 may include, but is not limited to, at least one selected from the group consisting of Ag, Au, Cu, Al, Pt, ion doped metal oxides, Metal known to be able to be implemented can be used without limitation. The ion doping metal oxide includes, for example, indium tin oxide (ITO), fluorine doped tin oxide (FTO), Al doped zinc oxide (AZO), gallium zinc oxide (GZO) and the like. In one embodiment, the low spinning layer 110 can be a layer formed of silver (Ag), so 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 110 may be, for example, from about 5 nm to about 25 nm. The low emissivity layer 110 having a thickness in this range is suitable for simultaneously realizing low infrared emissivity and high visible light transmittance.

A lower radiation protection metal layer (not shown) may be further disposed between the lower radiation layer 110 and the dielectric layer 120.

The low radiation protection metal layer is made of a metal having excellent light absorption performance and functions to control sunlight and the color of the low radiation protection coating 100 can be controlled by controlling the material and thickness of the low radiation protection metal layer have.

The low radiation protective metal layer may have an extinction coefficient in the visible light range of about 1.5 to about 3.5. The extinction coefficient is a value derived from an optical constant, which is an inherent characteristic of the material of the work, and the optical constant is represented by n-ik in the equation. Here, n is the refractive index of the real part, and k, the imaginary part, is the extinction coefficient (also called the absorption coefficient, extinction coefficient, extinction coefficient, etc.). The extinction coefficient is a function of the wavelength (λ), and in the case of metals, the extinction coefficient is generally greater than zero. The extinction coefficient, k, is the absorption coefficient, α and α = (4πk) / λ. The absorption coefficient, α, is given by I = I0exp (-αd) when the thickness of the medium through which the light passes is d The intensity (I) of light passing through due to the absorption of light by the medium is reduced as compared with the intensity (I0) of the incident light.

The low-radiation-shielding metal layer absorbs a certain portion of the visible light by using the metal having the extinction coefficient of the visible light region in the range, so that the low-radiation coating 100 has a predetermined color.

For example, the low-radiation-shielding metal layer may include at least one selected from the group consisting of Ni, Cr, an alloy of Ni and Cr, Ti, and combinations thereof, but is not limited thereto.

The dielectric layer 120 can function as an oxidation preventing layer of the low emission layer 120 because the metal used as the low emission layer 120 is generally oxidized and the dielectric layer 120 can increase the visible light transmittance It also plays a role.

The dielectric layer 120 may include various metal oxides, metal nitrides, and the like, but not limited thereto, and known materials used for protecting the low radiation layer may be used without limitation.

For example, the dielectric layer 120 may be selected from the group consisting of titanium oxide, zinc tin oxide, zinc oxide, aluminum zinc oxide, tin oxide, bismuth oxide, silicon nitride, silicon nitride aluminum, silicon nitride tin, But it is not limited thereto. (B), aluminum (Al), silicon (Si), magnesium (Mg), antimony (Sb), beryllium (Be), and combinations thereof in the metal oxide and / At least one element selected from among the elements can be doped. As a result, it is possible to contribute to improvement in durability.

The optical performance of the low spin coating 100 may be controlled by appropriately adjusting the material and physical properties of the dielectric layer 120.

In one embodiment, the dielectric layer 120 may be a layer formed of silicon aluminum nitride. The dielectric layer formed of silicon aluminum nitride can be formed together with the outer protective layer 130 to give a better heat resistance effect to the heat applied during the process, .

The dielectric layer 120 may be composed of a plurality of layers of two or more layers. For example, a dielectric layer 120 composed of two first dielectric layers and a second dielectric layer may be present symmetrically with the low radiation layer 110 therebetween.

The dielectric layer 120 may be made of a dielectric material having a refractive index of about 1.5 to about 2.3 and may be formed of a dielectric material having a thickness of about 0.01 to about 10 nm to realize a desired level of transmittance, Can be adjusted.

The thickness of the dielectric layer 120 may be, for example, about 5 nm to about 60 nm. The thickness of the dielectric layer 120 can be variously adjusted depending on the constituent positions and materials in order to realize the optical performance (transmittance, reflectance, and color index) of the entire multilayer thin film in accordance with the target performance, It is possible to effectively control the optical performance of the dielectric layer 120 including the dielectric layer 120 having the dielectric layer 120 and to realize an appropriate production rate.

The dielectric layer 120 may be formed of a material having a light extinction coefficient close to zero. When the extinction coefficient is larger than 0, it means that the incident light is absorbed in the dielectric layer before reaching the light-absorbing metal layer, which is a factor that hinders the securing of the transparent field of view. Thus, the extinction coefficient of the dielectric layer 120 may have, for example, less than about 0.1 in the visible light range (about 380 nm to about 780 nm wavelength range). As a result, the dielectric layer 120 can secure transparency by securing excellent light-receiving properties.

As described above, the outer protective layer 130 includes a first outer protective layer 130a and a second outer protective layer 130b. The first outer protective layer 130a and the second outer protective layer 130b are sequentially formed on the dielectric layer 120, As shown in FIG.

The outer protective layer 130 protects the low radiation layer 11 by blocking oxygen, moisture, etc. from the outside with respect to the low radiation layer 11, thereby suppressing physical and chemical diffusion, Thereby improving the chemical resistance and moisture resistance of the substrate.

The first outer protective layer 130a includes zirconium oxide. For example, the first outer protection layer 130a may be formed of a zirconium oxide layer containing zirconium oxide as a main component. The zirconium oxide may be represented by ZrO x and may include oxygen in a content of 1.5 < x < 2.

The zirconium oxide layer may be formed to have a higher oxygen content than that produced by the low-emission coating manufacturing method described below.

According to the method of manufacturing a low spin coating to be described later, first, a zirconium layer is deposited by a sputtering method to form a zirconium layer, and then, after oxidation, oxygen is implanted into the zirconium layer to oxidize the zirconium, The first outer protective layer containing zirconium oxide is formed as a high-density thin film. The zirconium oxide formed by oxidizing zirconium and the zirconium oxide newly formed are formed into a single layer to be the first outer protective layer 130a.

The metal oxide layer may be formed by a post-oxidation method. Post-oxidation methods include natural oxidation, reactive sputtering, plasma treatment, e-beam method, and the like, and post-oxidation treatment can be performed using at least one method.

The first outer protective layer 130a thus produced may have a higher oxygen content, so that the zirconium oxide represented by ZrO x may contain oxygen at a high content of 1.9 < x < 2.

In addition, the first outer protective layer 130a thus manufactured may be bulky and formed at a high density. When the first outer protective layer 130a is formed at a high density, oxygen, moisture, etc. are shielded from the outside more effectively to protect the low-radiation layer 11, thereby suppressing physical and chemical diffusion, The chemical resistance and the moisture resistance can be improved, and the mechanical durability can be further improved.

And the second outer protective layer 130b includes a composite metal oxynitride. For example, the first outer protection layer 130a may be formed of a composite metal oxide nitride layer containing a composite metal oxide nitride as a main component.

The composite metal oxynitride may include an oxynitride of a zirconium (Zr) based composite metal.

Examples of the zirconium (Zr) based composite metal include ZrSi, ZrNi, ZrCr, ZrTi, and the like, but are not limited thereto.

The composite metal oxynitride layer may be formed to include a higher content of oxygen and nitrogen than that produced by the low-emission coating manufacturing method described later.

According to a method of manufacturing a low radiation coating to be described later, the composite metal oxynitride layer is formed by sputtering a composite metal together with a reactive gas to deposit a composite metal oxynitride on the first outer protective layer, And the second outer protective layer 130b is formed by forming the composite metal oxynitride thereon.

The second outer protective layer 130b thus produced may contain oxygen and nitrogen in a higher content as the content of oxygen and nitrogen becomes higher.

In addition, the second outer protective layer 130b thus produced may be formed of a composite metal oxynitride. If the second outer protective layer 130b is formed of a composite metal oxynitride, it is more effective to shield oxygen, moisture and the like from the outside to protect the low-emission layer 11, thereby suppressing physical and chemical diffusion, The chemical resistance and moisture resistance of the spin coating can be improved, and the mechanical durability can be further improved.

The first outer protective layer 130a and the second outer protective layer 130b are formed together to remarkably improve moisture resistance, chemical resistance, and durability. That is, when the oxide semiconductor layer is formed of only a single layer of a zirconium oxide layer or a composite metal oxide nitride layer, there is a limit to improve moisture resistance, chemical resistance and durability even when the thickness is increased. It is possible to achieve synergistic effects and achieve moisture resistance, chemical resistance and durability that are significantly superior to those achievable with a single layer.

The first outer protection layer 130a may be formed to a thickness of about 1 nm to about 5 nm. By forming the first outer protective layer 130a with a thickness within the above range, a high visible light transmittance can be maintained, and superior durability can be realized while securing excellent light-emitting properties.

The second outer protective layer 130b may be formed to a thickness of about 1 nm to about 20 nm. By forming the second outer protective layer 130b with the thickness within the above range, a high visible light transmittance can be maintained, and superior durability can be realized while securing excellent light-emitting properties.

2 is a cross-sectional view of a low-emission coating 300 according to another embodiment of the present invention, in which the dielectric layer 320 and the outer protection layer 330 are sequentially stacked on both sides of the low- Thereby forming a symmetrical structure. 3, each of the outer protection layers 330 has a structure in which two first outer protection layers 330a and a second outer protection layer 330b are sequentially stacked after the dielectric layer 320. In addition,

The low emissivity coatings 100, 300 may further include additional layers other than the structures described above to implement the desired optical performance.

In another embodiment of the present invention, there is provided a method of making a low emissivity coating comprising the steps of:

A method of making the low emissivity coating comprises:

Preparing a low emissivity layer in which a dielectric layer is laminated on at least one side of the low emissivity layer;

Depositing zirconium on the dielectric layer by a sputtering method to form a zirconium layer;

Depositing the zirconium layer followed by post-oxidation to form a zirconium oxide, thereby oxidizing the zirconium layer to form a first outer protective layer comprising zirconium oxide;

Depositing a composite metal oxide nitride on the first outer protection layer by a sputtering method to form a composite metal oxide nitride layer; And

The composite metal oxynitride layer is formed by sputtering a composite metal together with a reactive gas to deposit a composite metal oxynitride on the first outer protective layer, thereby forming a second outer protection layer To form a layer 130b.

delete

The low emissivity coatings 100, 300 described above may be produced by the method of making the low emissivity coating.

Wherein the outer protective layer is formed of a structure including a first outer protective layer formed of a zirconium oxide layer and a second outer protective layer formed of a composite metal oxide nitride layer by the manufacturing method, The coating can further improve the chemical resistance, moisture resistance and abrasion resistance and have excellent durability as described above.

In the method of making the low emissivity coating, a detailed description of the low emissivity layer and the dielectric layer is as described above in one embodiment of the present invention.

In the method of producing the low-emission coating, the low-emission layer in which the dielectric layer is laminated on at least one side of the low-emission layer, for example, one surface or both surfaces, may be prepared by a known deposition method and is not particularly limited.

The step of depositing zirconium or composite metal oxynitride by the above sputtering method can be performed, for example, under a sputter power condition at room temperature, about 100w to about 2000w, but is not limited thereto. The sputtering can be performed by a known method, for example, by targeting zirconium in a plasma state of a reactive gas, or by targeting a composite metal in a plasma state of a reactive gas.

The zirconium layer may be formed to a thickness of, for example, about 2 nm to about 4 nm.

After the metal layer is formed by vapor deposition and then a post oxidation treatment is performed, oxygen is impregnated into the metal layer formed earlier and the metal is oxidized. Thereby oxidizing below the surface of the metal layer to form a metal oxide and form a first outer protective layer.

Similarly, a second outer protective layer including a composite metal oxide nitride is formed by sputtering a composite metal oxide on the first outer protective layer by sputtering together with a reactive gas.

Since the first outer protective layer and the second outer protective layer thus formed can be formed at high density, the resulting low emissivity coating can exhibit excellent chemical resistance, moisture resistance and abrasion resistance.

A detailed description of each layer in the method of making the low emissivity coating is as described above for the low emissivity coating.

In order to realize an optical spectrum suitable for the purpose of use, the low-emission coatings 100 and 300 may be formed by adjusting the material and thickness of each layer constituting the low-emission coatings 100 and 300, Can be achieved by controlling the reflectance. For example, the low radiation coatings (100, 300) can increase the visible light transmittance to improve the light fastness, thereby ensuring a clear visual field while reducing the infrared emissivity and securing an excellent heat insulating effect.

The low radiation coatings 100 and 300 may be formed by adjusting the material and the thickness of each layer constituting the low radiation coating 100 and 300 so as to improve the optical performance such as color, reflectivity, and transmittance of the high reflection surface of the low- Fine control may be possible.

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.

3 is a sectional view of the functional building material 450 for a window and may be a structure in which a low radiation coating 400 is coated on at least one side of the base material 440, for example, one side or both sides. The functional building material 450 may have a structure in which a low emission layer 410, a dielectric layer 420, and an outer protection layer 430 are sequentially stacked on at least one surface of the base material 440 The outer protective layer 430 has a structure in which a first outer protective layer 430a and a second outer protective layer 430b are sequentially stacked.

3, the low radiation coating 400 has a dielectric layer 420 and an outer protective layer 430 formed on only one side of the low radiation layer 410. However, as shown in FIG. 2, The dielectric layer 420 and the outer protective layer 430 may be formed as described above.

Details of the low radiation coating 400, the low emission layer 410, the dielectric layer 420, the outer protection layer 430, and the metal oxide layers 430a and 430b are as described above.

The substrate 440 can be a transparent substrate having a high visible light transmittance and can be, for example, a glass or transparent plastic substrate having a visible light transmittance of about 80% to about 100%. The substrate 440 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.

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 )

Example  One

Using a magnetron sputtering evaporator (Selcos Cetus-S), low-emission glass was prepared by laminating a low-emission coating of a multilayer structure on a transparent glass substrate as described below.

Silicon nitride aluminum was deposited on a 6 mm thick transparent glass substrate in an atmosphere of argon / nitrogen (argon 80 vol%, nitrogen 20 vol%) to form a first dielectric layer 35 nm thick and 100 vol% argon on the first dielectric layer. (NiCr), silver (Ag) and nickel chrome (NiCr) were sequentially deposited under the atmosphere to form a first low-emission metal protective layer 1 nm thick, a low-emission layer 7 nm thick and a second low- And a second dielectric layer having a thickness of 35 nm was formed on the second low-emission metal protective layer by depositing silicon nitride on the atmosphere of argon / nitrogen (argon 80 vol%, nitrogen 20 vol%).

Subsequently, zirconium was deposited on the upper surface of the second dielectric layer under the conditions of 100% argon atmosphere, 2 mTorr and 500 W sputter power to form a zirconium layer to a thickness of 3 nm, and then subjected to post oxidation treatment to oxidize the zirconium layer from the surface To form a zirconium oxide to form a 5 nm thick first outer protective layer (ZrOx, x = 1.92 measured using Angle resolved XPS).

Subsequently, a composite metal was deposited as a target on the upper surface of the first outer protective layer under a reactive gas atmosphere, 2 mTorr, and 500 W sputter power to form a zirconium silicon oxynitride layer to a thickness of 10 nm to form a second outer protective layer.

The thickness of each layer was measured using a depth profiler (dektakXT, BRUKER). In the low emissivity coating prepared above, each layer of the outer protective layer was formed at a high density.

Comparative Example  One

Using a magnetron sputtering evaporator (Selcos Cetus-S), low-emission glass was prepared by laminating a low-emission coating of a multilayer structure on a transparent glass substrate as described below.

Silicon aluminum nitride was deposited on a 6 mm thick transparent glass substrate under argon / nitrogen (argon 80 vol%, nitrogen 20 vol%) atmosphere to form a first dielectric layer 40 nm thick, and argon (NiCr), silver (Ag), and nickel chrome (NiCr) were deposited in a 100 volume% atmosphere to form a first low emissive metal protective layer having a thickness of 1 nm, a low emissivity layer having a thickness of 7 nm, A silicon nitride layer was deposited on the second low emissive metal protective layer in an atmosphere of argon / nitrogen (argon 80 vol%, nitrogen 20 vol%) to form a second dielectric layer 35 nm thick Respectively.

Comparative Example  2

Using a magnetron sputtering evaporator (Selcos Cetus-S), low-emission glass was prepared by laminating a low-emission coating of a multilayer structure on a transparent glass substrate as described below.

Silicon aluminum nitride was deposited on a 6 mm thick transparent glass substrate under argon / nitrogen (argon 80 vol%, nitrogen 20 vol%) atmosphere to form a first dielectric layer 40 nm thick, and argon (NiCr), silver (Ag), and nickel chrome (NiCr) were deposited in a 100 volume% atmosphere to form a first low emissive metal protective layer having a thickness of 1 nm, a low emissivity layer having a thickness of 7 nm, A silicon nitride layer was deposited on the second low emissive metal protective layer in an atmosphere of argon / nitrogen (argon 80 vol%, nitrogen 20 vol%) to form a second dielectric layer 35 nm thick Respectively.

Subsequently, a zirconium oxide layer was deposited on the upper surface of the second dielectric layer by reactive sputtering under the conditions of 100% argon atmosphere, 2 mTorr, and 500 W sputter power to form a zirconium oxide layer with a thickness of 5 nm.

Comparative Example  3

Using a magnetron sputtering evaporator (Selcos Cetus-S), low-emission glass was prepared by laminating a low-emission coating of a multilayer structure on a transparent glass substrate as described below.

Silicon aluminum nitride was deposited on a 6 mm thick transparent glass substrate under argon / nitrogen (argon 80 vol%, nitrogen 20 vol%) atmosphere to form a first dielectric layer 40 nm thick, and argon (NiCr), silver (Ag), and nickel chrome (NiCr) were deposited in a 100 volume% atmosphere to form a first low emissive metal protective layer having a thickness of 1 nm, a low emissivity layer having a thickness of 7 nm, A silicon nitride layer was deposited on the second low emissive metal protective layer in an atmosphere of argon / nitrogen (argon 80 vol%, nitrogen 20 vol%) to form a second dielectric layer 35 nm thick Respectively.

Subsequently, a zirconium oxide target was deposited on the upper surface of the second dielectric layer by reactive sputtering under the conditions of 100% argon atmosphere, 2 mTorr, and 500 W sputter power, and a zirconium oxide layer (ZrOx, x = 1.77: Angle resolved XPS ) Was formed to a thickness of 15 nm.

evaluation

1. Chemical resistance evaluation

(Manufactured by KONICA MINOLTA, model VTLCM-700) while immersing the glass coated with the low spin coating prepared in Example 1 and Comparative Example 1-2 at room temperature in a Sigma Aldrich HCl solution of pH 2 for 30 minutes, Was used to measure the change in color index before and after immersion, and the graph thus prepared was shown in FIG. In the graph of FIG. 4, the color T in 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, And ΔE = (ΔL 2 + Δa 2 + Δb 2 ) 1/2 on the Y axis represents the color index change value.

As shown in the graph of FIG. 4, since the change in color index of Example 1 is smaller than that of Comparative Example 1, it can be confirmed that the chemical resistance of Example 1 is better than that of Comparative Example 1.

2. Evaluation of moisture resistance

The glass coated with the low emissivity coating prepared in accordance with Example 1 and Comparative Examples 1 to 3 was subjected to heat treatment under the conditions of 100 ° C and 98% RH (humidity) using a constant temperature and humidity chamber (LSISON, EBS-35B) Moisture resistance evaluation (1st day, 4th day, 9th day, 14th day) was performed, and the degree of corrosion was observed using an optical microscope (X200). 5 is an image obtained by photographing the result with an optical microscope image.

The number of corrosion points occurred during 14 days from the 14-day image observed in FIG. 5 is counted, and is shown in Table 1 below.

division Example 1 Comparative Example 1 Comparative Example 2 Comparative Example 3 Number of corrosion points Less than 30 More than 200 More than 80 More than 80

As can be seen from FIG. 5 and Table 1, the number of corrosion points generated in Example 1 was significantly reduced compared to Comparative Examples 1-3. Comparing Comparative Example 2 and Comparative Example 3, the moisture resistance was not improved even though the composite metal oxynitride layer was formed thicker than Comparative Example 3. On the contrary, it can be confirmed that Embodiment 1 is remarkably improved compared to Comparative Example 2.

From the above results, it can be confirmed that the moisture resistance of Example 1 is further improved as compared with Comparative Example 1-3.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, And falls within the scope of the invention.

100, 300, 400: low radiation coating
110, 310, 410: low radiation layer
120, 320, 420: dielectric layer
130, 330, 430: outer protective layer
130a, 330a, 430a: a first outer protective layer
130b, 330b, and 430b: a second outer protective layer
440: substrate
450: Functional building materials for windows

Claims (17)

A low-emission layer, a dielectric layer, and an outer protective layer sequentially,
Wherein the outer protective layer comprises a first outer protective layer and a second outer protective layer sequentially stacked on the dielectric layer,
Wherein the first outer protective layer comprises zirconium oxide and the second outer protective layer comprises a composite metal oxynitride,
Wherein the zirconium oxide is represented by ZrO x , wherein 1.9 < x < 2
Low radiation coating.
The method according to claim 1,
Wherein the composite metal oxynitride comprises an oxynitride of a zirconium (Zr) based composite metal
Low radiation coating.
delete The method according to claim 1,
Wherein the first outer protective layer has a thickness of 1 nm to 5 nm
Low radiation coating.
The method according to claim 1,
Wherein the second outer protective layer has a thickness of 1 nm to 20 nm
Low radiation coating.
The method according to claim 1,
Wherein the dielectric layer comprises at least one selected from the group consisting of a metal oxide, a metal nitride, and combinations thereof,
At least one selected from the group consisting of bismuth (Bi), boron (B), aluminum (Al), silicon (Si), magnesium (Mg), antimony (Sb), beryllium (Be) Lt; RTI ID = 0.0 &gt; doped &lt; / RTI &gt;
Low radiation coating.
The method according to claim 1,
Wherein the dielectric layer comprises at least one selected from the group consisting of titanium oxide, zinc tin oxide, zinc oxide, aluminum zinc oxide, tin oxide, bismuth oxide, silicon nitride, silicon aluminum nitride, silicon nitride tin and combinations thereof
Low radiation coating.
delete The method according to claim 1,
Wherein the low spinning layer comprises at least one selected from the group consisting of Ag, Au, Cu, Al, Pt, ion doped metal oxides, and combinations thereof
Low radiation coating.
The method according to claim 1,
Wherein the low emissivity layer has an emissivity of 0.01 to 0.3
Low radiation coating.
delete The method according to claim 1,
Further comprising a low radiation protection metal layer between the low radiation layer and the dielectric layer
Low radiation coating.
delete The method according to claim 1,
Wherein the dielectric layer and the outer protective layer are sequentially stacked on both sides of the low radiation layer
Low radiation coating.
Preparing a low emissivity layer in which a dielectric layer is laminated on at least one side of the low emissivity layer;
Depositing zirconium on the dielectric layer by a sputtering method to form a zirconium layer;
Depositing the zirconium layer followed by post-oxidation to form a zirconium oxide, thereby forming a first outer protective layer comprising zirconium oxide; And
Depositing a composite metal oxynitride layer on the first outer protective layer by sputtering with a reactive gas to form a second outer protective layer comprising a composite metal oxynitride; Including,
Wherein the zirconium oxide is represented by ZrO x , wherein 1.9 < x < 2
RTI ID = 0.0 &gt; a &lt; / RTI &gt; outer protective layer.
delete delete
KR1020150063332A 2014-06-02 2015-05-06 Low-emissivity coat, method for preparing low-emissivity coat and functional building material including low-emissivity coat for windows KR101970495B1 (en)

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