KR20150129290A

KR20150129290A - Low-emissivity coat, method for preparing low-emissivity coat and functional building material including low-emissivity coat for windows

Info

Publication number: KR20150129290A
Application number: KR1020150061472A
Authority: KR
Inventors: 유현우; 전윤기; 권대훈
Original assignee: (주)엘지하우시스
Priority date: 2014-05-08
Filing date: 2015-04-30
Publication date: 2015-11-19
Also published as: KR101979623B1

Abstract

A low-emission layer, a dielectric layer, and an outer protective layer sequentially,
The outer protective layer provides a low emissivity coating formed in a single layer or multi-layer structure in which one or more layers comprising metal and metal oxide are laminated.

Description

TECHNICAL FIELD [0001] The present invention relates to a low-emissivity functional coating material for a window, including a low-emission coating, 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 includes a low-emission layer, a dielectric layer, and an outer protective layer sequentially, wherein the outer protective layer is a single layer or a multilayer structure formed by stacking one or more layers including metal and metal oxide Radiation coating.

The metal and the metal oxide may be at least one metal selected from the group consisting of silicon, aluminum, titanium, zirconium, a silicon-based metal alloy, a titanium-based metal alloy, a zirconium-based metal alloy and combinations thereof, and metal oxides thereof.

Each of the layers including the metal and the metal oxide as the layers forming the outer protective layer may include a metal lower region formed of a metal and a metal oxide upper region formed of a metal oxide.

The thickness of the metal oxide upper region may account for 50 to 92% of the thickness of each layer forming the outer protective layer.

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.

The thickness of the metal oxide upper region may be 0.5 nm to 3.0 nm.

Each of the layers forming the outer protective layer may have a thickness of 0.5 nm to 5 nm.

The outer protective layer may include one to ten layers including the metal and the metal oxide.

The total thickness of the outer protective layer may be 1 nm to 50 nm.

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 a metal on the dielectric layer by a sputtering method to form a metal layer; And

&Lt; RTI ID = 0.0 > a < / RTI >

In the method of manufacturing the low spin coating, the step of forming the metal layer and the step of forming the layer including the metal oxide upper region and the metal lower region therefrom are repeated one or more times to form the metal oxide upper region and the metal lower region The outer protective layer having a multi-layer structure in which one or more layers are stacked.

In another embodiment of the present invention, a transparent substrate; And a low-emission coating formed 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 an outer protective layer formed in a multi-layer structure included in a low emissivity coating according to another embodiment of the present invention.
3 is a schematic cross-sectional view of a low emissivity coating according to another embodiment of the present invention.
4 is a schematic cross-sectional view of a functional building material for a window according to another embodiment of the present invention.
FIG. 5 is a graph showing the results of measurement of visible light transmittance of the glass coated with the low-emission coating prepared in Examples and Comparative Examples.
FIG. 6 shows changes in the color index measured after being left under acidic conditions for the glass coated with the low emissivity coating prepared in Examples and Comparative Examples.
Fig. 7 is an optical microscope image observed after being left 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. The outer protective layer has a multi-layer structure in which one or more layers including a metal and a metal oxide are stacked.

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 may include one or more layers including a metal and a metal oxide,

1, the outer protective layer 130 may be formed by depositing a metal from the top of the dielectric layer 120, for example, by post-oxidation The metal oxide and the metal oxide are formed simultaneously to form a metal oxide and a layer including the metal and the metal oxide is formed into a single layer (for example, the 130a layer in FIG. 1 is first formed into a single layer).

The low emissivity coating 100 may include an outer protective layer 130 having a multi-layer structure having chemical resistance, moisture resistance, and abrasion resistance as described above at an outermost position, for example, Durability against 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 insulating 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 formed of titanium oxide, tin zinc oxide, zinc oxide, zinc aluminum oxide, tin oxide, bismuth oxide, silicon nitride, silicon aluminum nitride, silicon tin nitride, And at least one selected from the group consisting of, but not limited to. (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.

The dielectric layer 120 may be composed of a plurality of layers of two or more layers.

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 may have a single-layered structure (see FIG. 1) or may have a multi-layered structure including two or more layers, such as layers 130a and 130b including metal and metal oxides have. FIG. 2 is a cross-sectional view of the outer protective layer 130 of the multi-layer structure in which the outer protective layer 130 forms a multi-layer structure. 2, the multilayered outer protective layer 130 may be a structure in which two or more layers 130a, 130b, 130f, etc., including metal and metal oxides, are sequentially stacked on top of the dielectric layer 120 .

The metal and the metal oxide may be at least one metal selected from the group consisting of silicon, aluminum, titanium, zirconium, a silicon-based metal alloy, a titanium-based metal alloy, a zirconium-based metal alloy, .

The type of the metal may be selected to suit the characteristics to be implemented depending on the use of the low spin coating. For example, when the metal is zirconium and the metal oxide is zirconium oxide, the low spin coating may be excellent in both chemical resistance, moisture resistance, and abrasion resistance.

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.

Each of the layers 130a, 130b, and 130f forming the outer protective layer 130 includes a metal lower region formed of a metal and a metal oxide upper region formed of a metal oxide.

In FIG. 2, each layer (130a, 130b, 130f, etc. in FIG. 2) is formed to include the metal oxide upper region A and the metal lower region B, respectively.

The thickness y of the metal oxide upper region A accounts for about 50 to about 92%, specifically about 70 to about 92% of the thickness x of each layer forming the outer protective layer 130 .

For example, the thickness of the metal oxide overlying region may be from about 0.5 nm to about 3.0 nm.

The metal oxide upper region (A) includes a metal oxide. As can be seen from the manufacturing method of the low-radiation coating to be described later, the metal oxide upper region A can be formed by nearly completely oxidizing the metal according to the low-emission coating manufacturing method described later, For example, the metal oxide upper region A may be made of only a metal oxide. Therefore, the content of the metal oxide in the thus formed metal oxide upper region (A) may be very high, and the content of the non-oxidized metal may be very low or substantially not included.

According to the method of manufacturing a low-emission coating to be described later, a metal layer is first formed by vapor deposition, and then a post-oxidation treatment and a metal oxide deposition are simultaneously performed to form a layer including the metal oxide upper region A and the metal lower region B can do.

The outer protective layer 130 includes the metal oxide upper region A and the metal lower region B to inhibit chemical attack species such as O ₂ , H ₂ O, S and Cl ^- Thereby improving chemical durability such as moisture resistance and chemical resistance, and exhibiting improved mechanical durability due to the formation of a high-density metal oxide layer.

In addition, the upper region A of the metal oxide can be formed at a high density to further improve the mechanical strength. For example, the upper region A of the high-density metal oxide formed by simultaneously performing the post-oxidation treatment and the metal oxide deposition in accordance with the manufacturing method described later has more excellent mechanical durability.

When the outer protective layer has a multilayer structure, the thickness of each layer (130a, 130b, 130f, etc. in FIG. 2) forming the outer protective layer is about 0.5 nm to about 5 nm, specifically about 0.5 nm to about 3 nm, Specifically, it may be from about 0.5 nm to about 1 nm. For example, each of the layers (130a, 130b, and 130f in FIG. 2) forming the outer protective layer may be formed by depositing a metal on the upper surface of the dielectric layer 120 to form a metal layer, The lower part may be formed by oxidizing a part while simultaneously depositing a metal oxide on the surface. As the metal layer is partially oxidized beneath the surface, some oxidized portions are distinguished from the bottom metal region B where the unoxidized metal is present on the bottom side, and the metal top region A, together with the metal oxide deposited on the top surface, .

The thickness range of each layer forming the outer protective layer is easily controlled so that the metal oxide upper region A and the metal lower region B have an appropriate content ratio and thereby the outer protective layer is formed (Such as 130a, 130b, 130f in Fig. 2) may be improved in chemical resistance, moisture resistance, and wear resistance.

When the outer protective layer has a multi-layer structure, for example, two to ten, specifically two to five, layers (130a, 130b, 130f, etc. in Fig. 2) forming the outer protective layer And, for example, two to five of them may be stacked and included.

The outer protective layer 130 may have a single layer structure or a multi-layer structure, and the outer protective layer 130 may provide excellent durability.

In addition, each of the layers (130a, 130b, and 130f in FIG. 2) forming the outer protective layer of a single layer structure or the outer protective layer of a multi-layer structure is formed by depositing a metal on the metal surface And a metal oxide is deposited on the surface of the metal layer at the same time to form a densely formed oxide layer having a high density and the metal oxide upper region A has a substantially completely oxidized oxide Or is almost completely oxidized from the surface side of the metal layer, so that a high content of metal oxide is formed densely and durability can be effectively improved.

When the outer protective layer has a multi-layer structure, each layer forming the outer protective layer (130a, 130b, 130f, etc. in FIG. 2) is formed to have excellent durability and the total thickness of the outer protective layer It is possible to obtain more excellent durability.

The total thickness of the outer protective layer 130 may be, for example, about 1 nm to about 50 nm, specifically about 1 nm to about 30 nm, and more specifically, for example, about 1 nm to about 10 nm. The low emissivity coating 100 including the outer protective layer 130 having the thickness in the above range maintains high visible light transmittance, thereby ensuring excellent light fastness while at the same time achieving further improved durability.

3 is a cross-sectional view of a low emissivity coating 300 according to another embodiment of the present invention in which the dielectric layer 320 and the outer protective layer 330 are sequentially stacked on both sides of the low emissivity layer 310 Thereby forming a symmetrical structure. In FIG. 3, each of the outer protective layers 330 has a multi-layer structure including two layers 330a and 330b including a metal and a metal oxide.

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 fabricating a semiconductor device, comprising: preparing a low emissivity layer in which a dielectric layer is laminated on at least one side of a low emissivity layer; Depositing a metal on the dielectric layer by a sputtering method to form a metal layer; And forming a metal oxide by depositing the metal layer followed by a post oxidation treatment and a metal oxide deposition to form a layer including a metal oxide upper region and a metal lower region, to provide.

The outer protective layer may have a single-layer structure including a metal oxide upper region and a metal lower region.

Alternatively, the step of forming the metal layer and the step of forming the layer including the metal oxide upper region and the metal lower region therefrom are repeated one or more times to form two layers including the metal oxide upper region and the metal lower region The outer protective layer of the multi-layered structure can be formed.

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

The outer protective layer may be formed as a single layer or a multi-layer structure including at least one metal oxide layer by the above-described manufacturing method, thereby further improving the chemical resistance, moisture resistance, and abrasion resistance of the low- Can be given.

And forming a low radiation protection metal layer between the low radiation layer and the dielectric layer.

In the method of making the low emissivity coating, a detailed description of the low emissivity layer, the low emissivity protection metal 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 a metal by the sputtering method to form a metal layer can be performed, for example, under a sputter power condition at room temperature, about 100 W to about 2000 W, but is not limited thereto. The sputtering can be performed by a known method, for example, by targeting a metal in a plasma state in an argon atmosphere.

The metal layer may be formed to a thickness of, for example, from about 0.5 nm to about 5 nm, specifically, from about 0.5 nm to about 3 nm.

After the metal layer is formed by vapor deposition, a metal oxide is deposited together with a post-oxidation treatment to deposit a metal oxide on the metal layer at the same time as the metal layer is oxidized.

In the metal layer, oxygen is not permeated during the post-oxidation treatment, and the metal remaining unoxidized forms a metal lower region.

As a result, a layer including a metal oxide upper region and a metal lower region is formed.

The thickness of the outer protective layer of the single layer structure or the layer including the metal oxide upper region and the metallic lower region as each layer forming the outer protective layer of the multi-layer structure may be, for example, about 0.5 nm to about 5 nm, , From about 0.5 nm to about 3 nm, and more specifically, from about 0.5 nm to about 1 nm. The metal oxide upper region of the above-mentioned metal and metal oxide layer having a thickness in the above range is almost completely oxidized as described above, that is, the metal oxide content is very high, and as a result, the chemical resistance, moisture resistance, Is excellent.

Wherein the outer protective layer is formed by repeating the step of forming the metal layer and the step of forming a layer including the metal oxide upper region and the metal lower region from the metal protective layer one or more times, Layer structure in which one or more layers including a region and a metal lower region are stacked.

In addition, as described above, each of the metal oxide upper regions is densely formed to have a high density and almost completely oxidized, so that the durability can be effectively improved. As a result, the metal oxide upper regions having improved durability are stacked to form a single layer or a multi-layer structure, so that the outer protective layer can realize more excellent durability.

The thickness of the metal oxide overlying region may be controlled by adjusting the degree of metal oxide deposition following metal deposition such that the thickness of the metal oxide overlying region is from about 50 to about 92% of the thickness of each layer forming the outer passivation layer, . A detailed description of the metal oxide upper region and the metal lower region is as described above with respect to the low spin coating.

The total thickness of the outer protective layer may specifically be about 1 nm to about 50 nm, more specifically about 1 nm to about 30 nm, and may also be about 1 nm to about 10 nm, for example.

The low spin coating including the outer protective layer having the thickness in the above range maintains a high visible light transmittance, thereby ensuring excellent light fastness and at the same time, realizing a further improved durability.

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.

4 is a cross-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 And the outer protective layer 430 may have a multi-layer structure including three metal oxide layers 430a and 430b. The low radiation coating 400, the low radiation layer 410, the dielectric layer 420, the outer protection layer 430 and the metal oxide layers 430a and 430b are as described above in one embodiment of the present invention.

4, 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. 3, The dielectric layer 420 and the outer protective layer 430 may be formed 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 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 sequentially deposited under a 100 volume% atmosphere to form a first low-emission metal protective layer of 0.5 nm thickness, a low-emission layer of 7 nm thickness, 2 low-radiation metal protective layer was formed on the second low-radiation outer protective layer, and silicon aluminum nitride was deposited on the second low-radiation outer protective layer in an atmosphere of argon / nitrogen (argon 80 vol%, nitrogen 20 vol% 2 dielectric layer.

Then, zirconium was deposited on the second dielectric layer under the conditions of 100% argon atmosphere, 2 mTorr, and 500 W sputter power to form a zirconium layer having a thickness of 4 to 5 nm. Then, the surface of the zirconium layer was exposed to a high- The surface of the zirconium layer is oxidized by O ₂ and N ₂ mixed plasma treatment for 120 seconds to form a zirconium oxide having a thickness of 3 to 4 nm to form a metal oxide upper region of the zirconium oxide and a lower metal region of the zirconium below the metal oxide upper region , Thereby forming an outer protective layer including the metal oxide upper region and the metal lower region.

Comparative Example One

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 chromium (NiCr) were deposited under a 100 volume% atmosphere to form a first low-radiation outer protective layer 0.5 nm thick, a low radiation layer 7 nm thick, And a second dielectric layer with a thickness of 40 nm was deposited on the second low-radiation outer protective layer under argon / nitrogene (80 vol% argon, 20 vol% nitrogen) .

evaluation

1. Evaluation of outer protective layer thickness

The thickness of the outer protective layer and the thickness of the metal oxide upper region in the outer protective layer of the low spin coating prepared in Example 1 were measured (depth profiler, dektakXT, BRUKER) and are shown in Table 1 below.

division Thickness (unit: nm) Total thickness of the outer protective layer (unit: nm) Example 1 Metal oxide upper region 4 12-14 Metal bottom region 0.5

2. Optical characteristics and durability evaluation

Visible light transmittance was measured using a Taber spectrophotometer (haze-gard plus, BYK Gardner) for the glasses coated with the low emissivity coating prepared according to Example 1 and Comparative Example 1, and the Taber abrasion tester (manufactured by Taber Abraser, The abrasion resistance test was performed 100 times under the condition of 1 kg / mm ² using a Erichsen Model 5135 Rotary Platform abraser, and then observed with an optical microscope (X200) to calculate the number of scratches. As a result, the measured visible light transmittance and the number of scratches are shown in Table 2. (The numbers shown in the following Table 2 were calculated to have a width of 5 mu m or more, which is the minimum size that can be discriminated when observed with an optical microscope (X200) in a scratch).

division Visible light transmittance
(Transmittance) (%) Hayes Number of scratches Example 1 86.6 0.08 3 to 5 Comparative Example 1 89.3 0.06 10 to 15

As shown in Table 2, it was confirmed that the visible light transmittance and the haze characteristics of Example 1 were almost the same as those of Comparative Example 1. From the results of Table 1, it can be expected that excellent light fastness and abrasion resistance are realized at the same time.

FIG. 5 is a graph showing the results of measurement of visible light transmittance of the glass coated with the low emissivity coating prepared in Example 1 and Comparative Example 1. FIG. It can be seen that the transmittance is reduced as compared with Comparative Example 1 in the wavelength region of 300 nm to 400 nm which is the UV region in Example 1, and ultraviolet blocking effect can be obtained.

3. Chemical resistance evaluation

The low-emission coated glass prepared in Example 1 and Comparative Example 1 was immersed in a Sigma Aldrich HCl solution at pH 2 for 10 minutes at room temperature, and the low spin coating of Example 1 and Comparative Example 1 was observed under an optical microscope (X200). 6 is an optical microscope image obtained in the above.

4. Evaluation of moisture resistance

The glass coated with the low emissivity coating prepared according to Example 1 and Comparative Examples 1 and 2 was subjected to heat treatment under the condition of 40 ° C and 90% RH (humidity) using a constant temperature and humidity chamber (LSIS, EBS-35B) The moisture resistance was evaluated (day 1 and day 3), and the degree of corrosion was observed using an optical microscope (X200). Fig. 7 is an image obtained by photographing the result with an optical microscope image. Fig. 7 (a) is an image obtained on the first day, and Fig. 7 (b) is an image obtained on the third day.

As can be seen from the figure, the number of corrosion points generated in Example 1 was significantly reduced as compared to Curve 1.

Therefore, it can be confirmed that the moisture resistance of Example 1 is further improved as compared with Comparative Example 1-2.

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
440: substrate
450: Functional building materials for windows

Claims

A low-emission layer, a dielectric layer, and an outer protective layer sequentially,
Wherein the outer protective layer is formed as a single layer or a multi-layer structure in which one or more layers including a metal and a metal oxide are laminated.

The method according to claim 1,
Wherein the metal and the metal oxide are at least one metal selected from the group consisting of silicon, aluminum, titanium, zirconium, a silicon-based metal alloy, a titanium-based metal alloy, a zirconium-
Low radiation coating.

The method according to claim 1,
Wherein the layers including the metal and the metal oxide as the layers forming the outer protective layer each include a metal lower region formed of a metal and a metal oxide upper region formed of a metal oxide
Low radiation coating.

The method of claim 3,
Wherein the thickness of the metal oxide upper region accounts for 50 to 92% of the thickness of each layer forming the outer protective layer
Low radiation coating.

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.

6. The method of claim 5,
Wherein the low radiation protection metal layer comprises one selected from the group consisting of Ni, Cr, an alloy of Ni and Cr, Ti, and combinations thereof.
Low radiation coating.

5. The method of claim 4,
Wherein the thickness of the metal oxide upper region is 0.5 nm to 3.0 nm
Low radiation coating.

The method according to claim 1,
Wherein the thickness of each layer forming the outer protective layer is 0.5 nm to 5 nm
Low radiation coating.

The method according to claim 1,
Wherein the outer protective layer is formed by laminating two to ten layers including the metal and the metal oxide
Low radiation coating.

The method according to claim 1,
The total thickness of the outer protective layer is preferably 1 nm to 50 nm
Low radiation coating.

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 a metal on the dielectric layer by a sputtering method to form a metal layer; And
Forming a metal oxide by depositing the metal layer followed by post-oxidation and metal oxide deposition to form a layer including a metal oxide upper region and a metal lower region;
&Lt; / RTI >

13. The method of claim 12,
Forming the metal layer, and forming a layer including the metal oxide upper region and the metal lower region from the metal layer, wherein the layer including the metal oxide upper region and the metal lower region is formed by laminating two or more layers Forming an outer protective layer of a multi-layered structure
A method of making a low radiation coating.

13. The method of claim 12,
Wherein the metal and the metal oxide are at least one metal selected from the group consisting of silicon, aluminum, titanium, zirconium, a silicon-based metal alloy, a titanium-based metal alloy, a zirconium-
A method of making a low radiation coating.

Transparent substrate; And
Comprising a low emissivity coating according to any one of claims 1 to 11 formed on at least one side of the transparent substrate
Functional building materials for windows.

16. The method of claim 15,
The transparent substrate may be a glass or transparent plastic substrate having a visible light transmittance of 80% to 100%
Functional building materials for windows.