WO2015088267A1 - 저방사 코팅막, 이의 제조방법 및 이를 포함하는 창호용 기능성 건축 자재 - Google Patents
저방사 코팅막, 이의 제조방법 및 이를 포함하는 창호용 기능성 건축 자재 Download PDFInfo
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- WO2015088267A1 WO2015088267A1 PCT/KR2014/012218 KR2014012218W WO2015088267A1 WO 2015088267 A1 WO2015088267 A1 WO 2015088267A1 KR 2014012218 W KR2014012218 W KR 2014012218W WO 2015088267 A1 WO2015088267 A1 WO 2015088267A1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/36—Successively applying liquids or other fluent materials, e.g. without intermediate treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/50—Multilayers
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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
- C03C17/36—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
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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
- C03C17/36—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
- C03C17/3626—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 one layer at least containing a nitride, oxynitride, boronitride or carbonitride
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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
- C03C17/36—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
- C03C17/3644—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 the metal being silver
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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
- C03C17/36—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
- C03C17/3657—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 the multilayer coating having optical properties
- C03C17/366—Low-emissivity or solar control coatings
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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
- C03C17/36—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
- C03C17/3689—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 one oxide layer being obtained by oxidation of a metallic layer
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/004—Reflecting paints; Signal paints
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
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- E—FIXED CONSTRUCTIONS
- E06—DOORS, WINDOWS, SHUTTERS, OR ROLLER BLINDS IN GENERAL; LADDERS
- E06B—FIXED OR MOVABLE CLOSURES FOR OPENINGS IN BUILDINGS, VEHICLES, FENCES OR LIKE ENCLOSURES IN GENERAL, e.g. DOORS, WINDOWS, BLINDS, GATES
- E06B3/00—Window sashes, door leaves, or like elements for closing wall or like openings; Layout of fixed or moving closures, e.g. windows in wall or like openings; Features of rigidly-mounted outer frames relating to the mounting of wing frames
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- E—FIXED CONSTRUCTIONS
- E06—DOORS, WINDOWS, SHUTTERS, OR ROLLER BLINDS IN GENERAL; LADDERS
- E06B—FIXED OR MOVABLE CLOSURES FOR OPENINGS IN BUILDINGS, VEHICLES, FENCES OR LIKE ENCLOSURES IN GENERAL, e.g. DOORS, WINDOWS, BLINDS, GATES
- E06B9/00—Screening or protective devices for wall or similar openings, with or without operating or securing mechanisms; Closures of similar construction
- E06B9/24—Screens or other constructions affording protection against light, especially against sunshine; Similar screens for privacy or appearance; Slat blinds
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K9/00—Screening of apparatus or components against electric or magnetic fields
- H05K9/0001—Rooms or chambers
- H05K9/0003—Shielded walls, floors, ceilings, e.g. wallpaper, wall panel, electro-conductive plaster, concrete, cement, mortar
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- E—FIXED CONSTRUCTIONS
- E06—DOORS, WINDOWS, SHUTTERS, OR ROLLER BLINDS IN GENERAL; LADDERS
- E06B—FIXED OR MOVABLE CLOSURES FOR OPENINGS IN BUILDINGS, VEHICLES, FENCES OR LIKE ENCLOSURES IN GENERAL, e.g. DOORS, WINDOWS, BLINDS, GATES
- E06B9/00—Screening or protective devices for wall or similar openings, with or without operating or securing mechanisms; Closures of similar construction
- E06B9/24—Screens or other constructions affording protection against light, especially against sunshine; Similar screens for privacy or appearance; Slat blinds
- E06B2009/2417—Light path control; means to control reflection
Definitions
- the present invention relates to a low-emissivity coating film, a method for manufacturing the same, and a functional building material for windows and doors including the same.
- Low-emissivity glass refers to glass in which a low-emissivity layer containing a metal having high reflectance in the infrared region, such as silver, is deposited as a thin film.
- the low radiation glass is a functional material that reflects the radiation in the infrared region to block solar radiation in the summer and preserve the radiant heat in the winter to save energy in buildings.
- silver (Ag) used as a low emission layer is oxidized when exposed to air, and thus a dielectric layer is deposited as an anti-oxidation film on the upper and lower portions of the low emission layer. This dielectric layer also serves to increase the visible light transmittance.
- the present invention Low-emissivity coating layer; And a top coating layer, the top coating layer is to provide a low-emission coating film having a multi-layer structure including a metal layer, a metal oxide layer and a silicon-based composite metal oxynitride layer sequentially from the low-emission coating layer.
- the present invention Low-emissivity coating layer; And a top coating layer, wherein the top coating layer provides a low-emission coating film having a multi-layered structure sequentially comprising a metal layer, a metal oxide layer, and a silicon-based composite metal oxynitride layer from the low-emission coating layer.
- the metal layer may include at least one selected from silicon, aluminum, titanium, zirconium, silicon-based composite metals, titanium-based composite metals, zirconium-based composite metals, and combinations thereof.
- the metal oxide layer may include at least one selected from 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.
- the low radiation coating layer may have a multi-layer structure including a first dielectric layer, a first low radiation protection layer, a low radiation layer, a second low radiation protection layer, and a second dielectric layer sequentially from the substrate.
- the first dielectric layer or the second dielectric layer is a group consisting of titanium oxide, tin zinc oxide, zinc oxide, zinc aluminum oxide, tin oxide, bismuth oxide, silicon nitride, silicon aluminum nitride, silicon tin nitride and combinations thereof At least one selected from, or in at least one, bismuth (Bi), boron (B), aluminum (Al), silicon (Si), magnesium (Mg), antimony (Sb), beryllium (Be) and their At least one element selected from the group consisting of combinations may be doped.
- the first low radiation protection layer or the second low radiation protection layer includes nickel (Ni), chromium (Cr), an alloy of nickel (Ni) and chromium (Cr), and a combination thereof under titanium (Ti). It may include at least one selected from.
- the low emission layer may include at least one selected from the group consisting of silver (Ag), gold (Au), copper (Cu), aluminum (Al), platinum (Pt), ion doped metal oxides, and combinations thereof. have.
- the thickness of the metal layer may be 0.5nm to 5nm.
- the thickness of the metal oxide layer may be 0.5nm to 5nm.
- the silicon-based composite metal oxynitride layer may have a thickness of 2 nm to 20 nm.
- a low-emission coating layer laminated on at least one side of the substrate (a) preparing a low-emission coating layer laminated on at least one side of the substrate; (b) depositing a metal on top of the low emissive coating layer to form a metal layer; And (c) forming a metal oxide layer on the metal layer and depositing a silicon-based composite metal oxynitride to form a silicon-based composite metal oxynitride layer.
- the metal layer may include at least one selected from silicon, aluminum, titanium, zirconium, silicon-based composite metals, titanium-based composite metals, zirconium-based composite metals, and combinations thereof.
- the formation of the metal oxide layer in (c) may be performed by partially oxidizing the surface of the metal layer through a post oxidation process of the surface of the metal layer.
- the post-oxidation process may be performed using at least one reactive gas selected from the group consisting of oxygen (O 2 ), nitrogen (N 2 ) and argon (Ar).
- the partial oxidation of the surface of the metal layer and the deposition of the silicon-based composite metal oxynitride may be performed continuously in-situ.
- the low-emissivity coating film according to the present invention is excellent in wear resistance, which is a mechanical property, and excellent in moisture resistance, acid resistance, and base resistance, which are chemical properties.
- the oxidation of the surface of the metal layer and the deposition of the silicon-based composite metal oxynitride may be continuously performed in-situ through a post-oxidation process on the surface of the metal layer. The efficiency can be increased.
- FIG. 1 is a schematic cross-sectional view of a low-emissivity coating film according to an embodiment of the present invention.
- Figure 2 shows the scratch degree by observing the low-emission coating film according to an embodiment of the present invention under an optical microscope under a specific condition.
- Figure 3 shows the degree of corrosion by observing the low-emission coating film according to an embodiment of the present invention under an optical microscope under a specific condition.
- Figure 4 shows the change value of the color index measured under acidic conditions of the low-emission coating film according to an embodiment of the present invention.
- Figure 5 shows the change in the color index of the low-emission coating film according to an embodiment of the present invention measured under basic conditions.
- the inventors of the present invention while studying a low-emissive glass film, to prepare a low-emission coating film comprising a top coating layer of a multi-layer structure comprising a metal layer, a metal oxide layer and a silicon-based composite metal oxynitride layer sequentially, The present invention was completed by confirming that both mechanical and chemical properties were excellent.
- any configuration is formed on the “top (or bottom)" of the substrate or “top (or bottom)” of the substrate means that any configuration is formed in contact with the top (or bottom) of the substrate.
- it is not limited to not including other configurations between the substrate and any configuration formed on (or under) the substrate.
- the present invention Low-emissivity coating layer; And a top coating layer, wherein the top coating layer provides a low-emission coating film having a multi-layered structure sequentially comprising a metal layer, a metal oxide layer, and a silicon-based composite metal oxynitride layer from the low-emission coating layer.
- FIG. 1 is a schematic cross-sectional view of a low-emissivity coating film according to an embodiment of the present invention.
- the low-emissivity coating film is a substrate 100; A multilayer structure sequentially comprising a first dielectric layer 210, a first low radiation protection layer 220, a low radiation layer 230, a second low radiation protection layer 240 and a second dielectric layer 250 from the base material Low-emissivity coating of the layer 200; And a top coating layer 300 having a multi-layer structure including a metal layer 310, a metal oxide layer 320, and a silicon-based composite metal oxynitride layer 330 sequentially from the low-emissivity coating layer.
- the substrate 100 may be a transparent substrate having high visible light transmittance, and may be, for example, a glass or transparent plastic substrate having about 80% to about 100% visible light transmittance.
- the substrate may be used without limitation, for example, glass used for construction, and may be, for example, about 2 mm to about 12 mm thick, and may vary depending on the purpose and function of use, but is not limited thereto. .
- the low radiation coating layer 200 is formed of the first dielectric layer 210, the first low radiation protection layer 220, the low radiation layer 230, the second low radiation protection layer 240 and the second dielectric layer 250 from the substrate. ) May be a multilayer structure including sequentially.
- the optical performance of the low-emissivity coating film may be controlled by appropriately adjusting materials and physical properties of the first dielectric layer 210 and the second dielectric layer 250.
- the first dielectric layer 210 and the second dielectric layer 250 may be formed of a dielectric material having a refractive index of about 1.5 to about 2.3, and a desired target for transmittance, reflectance, transmission, and reflection color according to the value of the refractive index. The thickness can be adjusted to achieve a level.
- the thickness of the first dielectric layer 210 and the second dielectric layer 250 may be, for example, about 5 nm to about 60 nm.
- the thicknesses of the first dielectric layer 210 and the second dielectric layer 250 may vary depending on the location and material configured to implement optical performance (transmittance, reflectance, color index) of the entire multilayer thin film in accordance with a target performance. It can be controlled, and by including the first dielectric layer 210 and the second dielectric layer 250 having a thickness in the above range it is possible to effectively control the optical performance by the first dielectric layer 210 and the second dielectric layer 250 Therefore, the proper production speed can be achieved.
- the first dielectric layer 210 and the second dielectric layer 250 may be formed of a material having a light extinction coefficient close to zero.
- An extinction coefficient greater than zero means that the incident light is absorbed in the dielectric layer before reaching the light absorbing metal layer, which is a factor that inhibits the transparent field of view.
- the extinction coefficients of the first dielectric layer 210 and the second dielectric layer 250 may have, for example, less than about 0.1 in the visible region (wavelength range of about 380nm to about 780nm).
- the first dielectric layer 210 and the second dielectric layer 250 may help to secure a transparent field of view by securing excellent lightability.
- the low emissive layer 230 is a layer formed of an electrically conductive material, for example a metal, which may have a low emissivity, that is, has a low sheet resistance and thus has a low emissivity.
- the low emissivity layer 230 may have an emissivity of about 0.01 to about 0.3, specifically about 0.01 to about 0.2, more specifically about 0.01 to about 0.1, even more specifically About 0.01 to about 0.08.
- the low-emissivity layer 230 of the emissivity range can simultaneously realize excellent light properties and adiabatic effect by appropriately adjusting the visible light transmittance and the infrared emissivity.
- the low-emissivity layer 230 having the emissivity as described above may have a sheet resistance of, for example, about 0.78 kW / sq to about 6.42 kW / sq of a thin film, but is not limited thereto.
- the low radiation layer 230 performs a function of selectively transmitting and reflecting solar radiation, and specifically, has a low emissivity due to high reflectance of radiation in the infrared region.
- the low emission layer 230 may include at least one selected from the group consisting of silver (Ag), gold (Au), copper (Cu), aluminum (Al), platinum (Pt), ion doped metal oxides, and combinations thereof.
- Metals known to be able to include, but are not limited to, low radiation performance can be used without limitation.
- the ion doped 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.
- the low-emissivity layer 230 may be a layer formed of silver (Ag), as a result of which the low-emission coating layer may implement a high electrical conductivity, low absorption in the visible light region, durability, etc. Can be.
- the first low radiation protection layer 220 and the second low radiation protection layer 240 are made of a metal having excellent light absorption performance to control sunlight, and the first low radiation protection layer 220 and By adjusting the material, thickness, etc. of the second low-emission protective layer 240 may be adjusted the color implemented by the low-emission coating film.
- the first low emission protection layer 220 and the second low emission protection layer 240 may have an extinction coefficient in the visible light region of about 1.5 to about 3.5.
- the extinction coefficient is a value derived from an optical constant that is a material-specific property of a material, and the optical constant is expressed as n-ik in a formula.
- the real part n is the refractive index
- the imaginary part k is called the extinction coefficient (also called absorption coefficient, extinction coefficient, extinction coefficient, etc.).
- the extinction coefficient is a function of the wavelength [lambda], and for metals the extinction coefficient is generally greater than zero.
- the first low radiation protection layer 220 and the second low radiation protection layer 240 absorb a certain portion of visible light by using a metal having an extinction coefficient of the visible light region in the above range, thereby preventing the low radiation coating film. It has a predetermined color.
- the first low radiation protection layer 220 and the second low radiation protection layer 240 are, for example, nickel (Ni), chromium (Cr), an alloy of nickel (Ni) and chromium (Cr), and titanium ( Ti) and combinations thereof, and at least one selected from the group including, but is not limited to.
- the top coating layer 300 may have a multi-layered structure including a metal layer 310, a metal oxide layer 320, and a silicon-based composite metal oxynitride layer 330 sequentially from the low radiation coating layer 200.
- the metal layer 310 is formed by being deposited on the low radiation coating layer 200.
- the metal oxide layer 320 is formed by partially oxidizing the surface of the metal layer 310 through a post-oxidation process on the surface of the metal layer 310, it may mean a layer that is not partially oxidized. Due to the formation of the metal layer 310, the chemical properties of the low-emissivity coating film is excellent.
- the metal layer 310 includes silicon (Si), aluminum (Al), titanium (Ti), zirconium (Zr), indium (In), tin (Sn), thallium (Tl), lead (Pb), and tin (Sb). And bismuth (Bi), hafnium (Hf), vanadium (V), niobium (Nb), tantalum (Ta), and combinations thereof, and may include at least one metal selected from silicon, aluminum, titanium, It is preferable to include at least one selected from zirconium, silicon-based composite metals, titanium-based composite metals, zirconium-based composite metals and combinations thereof, and more preferably include zirconium or zirconium-based composite metals, but is not limited thereto.
- the metal layer 310 may improve the chemical properties of the low-emissivity coating film by inhibiting the process of diffusion of the chemical reactants, such as O 2 , H 2 O and Na + into the low-emission layer 230.
- the metal layer 310 since the metal layer 310 is formed by being deposited on the low-emissivity coating layer 200, the metal layer 310 by inhibiting the diffusion of chemical reactants such as O 2 , H 2 O and Na + , low-emission coating film It can have excellent chemical properties such as moisture resistance, acid resistance, base resistance.
- the thickness of the metal layer 310 is preferably 0.5nm to 5nm, but is not limited thereto.
- the thickness of the metal layer 310 is not partially oxidized, and the final thickness remains. Can mean.
- the thickness of the metal layer 310 is less than 0.5 nm, there is a problem that excellent chemical properties such as moisture resistance, acid resistance, base resistance of the low-emission coating film is lowered, and when the thickness of the metal layer 310 exceeds 5 nm, There is a problem that the transmittance of the radiation coating film is reduced.
- the metal oxide layer 320 is formed on the metal layer 310, and due to the formation of the metal oxide layer 320, excellent mechanical properties of the low-emissivity coating film, O 2 , H 2 O and Na + etc. By inhibiting the diffusion of the same chemical reactants, the chemical properties are excellent.
- the metal oxide layer 320 when the formation of the metal oxide layer 320 is performed by partially oxidizing the surface of the metal layer through a post-oxidation process of the surface of the metal layer 310, the metal is oxidized by the post-oxidation process, thereby expanding the volume when forming the metal oxide. This happens, the high-density metal oxide layer 320 can be formed by this volume expansion, there is an advantage that can further increase the hardness of the low-emission coating film.
- the metal oxide layer 320 when the metal oxide layer 320 is formed by partially oxidizing the surface of the metal layer 310 through a post-oxidation process on the surface of the metal layer 310, the metal oxide layer 320 of the uppermost coating layer is lower than the case where only the metal oxide layer is omitted.
- the hardness of the radiation coating film can be significantly increased.
- the metal oxide layer 320 may be formed of silicon oxide (SiO 2 ), aluminum oxide (Al 2 O 3 ), titanium oxide (TiO 2 ), zirconium oxide (ZrO 2 ), indium oxide (In 2 O 3 ), tin oxide ( SnO 2 ), thallium oxide (TlO 2 ), lead oxide (PbO 2 ), tin oxide (SbO 2 ), bismuth oxide (Bi 2 O 3 ), hafnium oxide (HfO 2 ), vanadium oxide (V 2 O 3 ), It may include at least one metal oxide selected from the group consisting of niobium oxide (Nb 2 O 5 ), tantalum oxide (Ta 2 O 3 ) and combinations thereof, and include silicon oxide, aluminum oxide, titanium oxide, zirconium oxide, and silicon-based It is preferable to include at least one selected from a composite metal oxide, a titanium-based composite metal oxide, a zirconium-based composite metal oxide, and a combination thereof, and more preferably include
- the thickness of the metal oxide layer 320 is preferably 0.5 nm to 5 nm, but is not limited thereto.
- the initial thickness of the metal layer 310 is 1 nm to 10 nm.
- 0.5 nm to 5 nm of the surface of the metal layer 310 is oxidized, which may be the thickness of the metal oxide layer 320.
- the silicon-based composite metal oxynitride layer 330 is formed by depositing a silicon-based composite metal oxynitride, and the silicon-based composite metal oxynitride is an alloy oxynitride whose main component is silicon in the composite metal.
- the excellent hardness of) has the advantage of improving the mechanical properties such as wear resistance.
- the deposition of the silicon-based composite metal oxynitride may be continuously performed in-situ with some oxidation of the metal layer surface.
- the silicon-based composite metal oxynitride layer 330 may have a thickness of about 2 nm to about 20 nm. In this case, when the thickness of the silicon-aluminum-based composite metal oxynitride layer 330 is less than 2 nm, there is a problem that mechanical properties such as wear resistance are lowered, and when the thickness of the silicon-based composite metal oxynitride layer 330 exceeds 20 nm, There is a problem that the transmittance is reduced.
- the low-emissivity coating layer may be formed of a multi-layered thin film structure based on the low-emissivity layer 230 that selectively reflects far infrared rays among solar radiation, and lowers the emissivity to low emissivity, that is, Low-e : It gives excellent insulation performance by low emissivity effect.
- the low-emissivity coating film is formed as described above, for example, when applied as a coating film of the window glass, by minimizing the movement of heat between the indoor and outdoor by reflecting the outdoor solar radiation heat in the summer and preserving the indoor radiant heat in winter, It is a functional material that brings the energy saving effect of buildings.
- Emissivity means the rate at which an object absorbs, transmits, and reflects energy with any particular wavelength. That is, in the present specification, the emissivity indicates the degree of absorption of infrared energy in the infrared wavelength region, and specifically, when far infrared rays corresponding to a wavelength region of about 5 ⁇ m to about 50 ⁇ m exhibiting strong thermal action are applied, It means the ratio of infrared energy absorbed with respect to infrared energy.
- the infrared energy absorbed by an object is the same as the infrared energy emitted by the object, so the absorption and emissivity of the object are the same.
- Such emissivity can be measured through a variety of methods commonly known in the art, and can be measured with a facility such as a Fourier Transform Infrared Spectrometer (FT-IR), for example, by the KSL2514 standard.
- FT-IR Fourier Transform Infrared Spectrometer
- Absorption, or emissivity, to far-infrared rays exhibiting such a strong thermal action, such as any object, for example low-emissive glass, can represent a very important meaning in measuring thermal insulation performance.
- the low-emissivity coating film according to the present invention is excellent in wear resistance, which is a mechanical property, and excellent in moisture resistance, acid resistance, and base resistance, which are chemical properties.
- the present invention comprises the steps of (a) preparing a low-emission coating layer laminated on at least one side of the substrate; (b) depositing a metal on top of the low emissive coating layer to form a metal layer; And (c) forming a metal oxide layer on the metal layer and depositing a silicon-based composite metal oxynitride to form a silicon-based composite metal oxynitride layer.
- Step (a) is a step of preparing a low-emission coating layer laminated on at least one side of the substrate, the low-emission coating layer laminated on at least one side of the substrate may be prepared by a known lamination method, it is not particularly limited.
- the step (b) is to form a metal layer by depositing a metal on top of the low emissive coating layer, wherein the metal layer may be formed by depositing a metal on the low emissive coating layer by a known deposition method.
- the metal oxide layer is formed on the metal layer, and the silicon-based composite metal oxynitride is deposited to form a silicon-based composite metal oxynitride layer.
- the formation of the metal oxide layer is preferably performed by partially oxidizing the surface of the metal layer through a post-oxidation process of the surface of the metal layer, but is not limited thereto.
- the post-oxidation process may be performed using at least one reactive gas selected from the group consisting of oxygen (O 2 ), nitrogen (N 2 ) and argon (Ar).
- the present invention also provides a functional building material for windows and doors comprising the low-emissivity coating film.
- the building material includes the low-emission coating film, thereby securing excellent heat insulating performance and optical properties due to the Roy effect, and having excellent durability as described above, thereby improving heat resistance performance.
- the building material may be, for example, heat-treated to improve wind resistance performance, and may be used as a building material for a high-rise building.
- a multi-layer low-emission coating layer and a multi-layer top layer were prepared by laminating on a transparent glass substrate as follows.
- Silicon aluminum nitride was deposited on a 6 mm thick transparent glass substrate in an argon / nitrogen (argon 80% by volume, nitrogen 20% by volume) atmosphere to form a first dielectric layer having a thickness of 35 nm, and argon on the first dielectric layer
- Nickel chromium (NiCr), silver (Ag), and nickel chromium (NiCr) were deposited in a 100% by volume atmosphere to form a first low emission protective layer having a thickness of 1 nm, a low emission layer having a thickness of 7 nm, and a second low emission protective layer having a thickness of 1 nm.
- a second dielectric layer having a thickness of 35 nm by depositing silicon aluminum nitride under an argon / nitrogen (argon 80% by volume, nitrogen 20% by volume) atmosphere on the second low-emission protective layer.
- a spin coating layer was prepared.
- zirconium is deposited on the second dielectric layer in an argon 100% atmosphere to form a zirconium layer having a thickness of 4 to 5 nm, and a post oxidation process is performed on the surface of the metal layer to partially oxidize the surface of the zirconium layer to have a thickness of 3 to 4 nm.
- the zirconium oxide layer of was formed, and the uppermost coating layer of the multilayer structure was prepared by continuously depositing silicon aluminum oxynitride in-situ and forming a silicon aluminum oxynitride layer having a thickness of 10 nm.
- Example 2 The same procedure as in Example 1 was carried out except that the preparation of the uppermost coating layer of the multilayer structure was omitted.
- Example 2 The same procedure as in Example 1 was carried out except that the formation of the silicon aluminum oxynitride layer was omitted from the uppermost coating layer of the multilayer structure.
- Example 1 Except for omitting the formation of the zirconium layer by oxidizing all of the zirconium layer in the uppermost coating layer of the multilayer structure was the same as in Example 1.
- Figure 2 shows the scratch degree by observing the low-emission coating film according to an embodiment of the present invention under an optical microscope under a specific condition.
- Comparative Example 1 was confirmed that the wear resistance is bad due to the occurrence of about 10 area scratches (area scratch), Comparative Example 2 also has eight hairline scratches (hairline scratch) Abrasion resistance was bad due to the degree of occurrence, and Comparative Example 3 also had about 6 thin hair scratches (hairline scratch) was confirmed that the wear resistance is bad.
- Example 1 only three hairline scratches were generated, and compared with Comparative Examples 1 to 3, it was confirmed that the wear resistance was remarkably improved due to the laminated structure of the uppermost coating layer having excellent hardness.
- Figure 3 shows the degree of corrosion by observing the low-emission coating film according to an embodiment of the present invention under an optical microscope under a specific condition.
- Comparative Example 1 was confirmed that the number of corrosion points more than 200, the degree of corrosion is remarkably high, Comparative Example 2 also the number of corrosion points 21 days 3 Dogs occurred on day 7 and day 7, Comparative Example 3 also occurred in the number of corrosion points 71 days on day 3, 186 days on day 7, it was confirmed that the degree of corrosion is high. On the other hand, in Example 1, the number of corrosion points occurred on the third day and six on the seventh day, and almost no corrosion occurred.
- the zirconium layer, the zirconium oxide layer, and the silicon aluminum Compared with Comparative Examples 1 to 3, the zirconium layer, the zirconium oxide layer, and the silicon aluminum
- the formation of the oxynitride layer inhibits the process of diffusion of chemical reactants, such as O 2 , H 2 O, and Na + , into the low-emission layer 230, thereby further improving the moisture resistance of the low-emission coating layer. I could confirm it.
- Figure 4 shows the change value of the color index measured under acidic conditions of the low-emission coating film according to an embodiment of the present invention.
- the color (T) of the X axis represents a color transmitted through the transparent glass substrate coated with a low-emission coating
- color (R) represents a color reflected from the low-emission coating surface
- color (S ) Represents the color reflected on the surface of the transparent glass substrate
- ⁇ E ( ⁇ L 2 + ⁇ a 2 + ⁇ b 2 ) 1/2 on the Y axis represents a color index change value.
- Comparative Examples 1 to 3 it was confirmed that the change in color index is noticeable. On the other hand, in Example 1, the color index was hardly changed. Compared with Comparative Examples 1 to 3, due to the formation of the zirconium layer, the zirconium oxide layer and the silicon aluminum oxynitride layer, O 2 , H 2 O and Na + By inhibiting the process of the chemical reactants introduced from the outside such as diffusion into the low-emissivity layer 230, it was confirmed that the acid resistance of the low-emission coating film is further improved.
- Figure 5 shows the change in the color index of the low-emission coating film according to an embodiment of the present invention measured under basic conditions.
- the color (T) of the X axis represents a color transmitted through the transparent glass substrate coated with a low-emission coating
- color (R) represents a color reflected from the low-emission coating surface
- color (S ) Represents the color reflected on the surface of the transparent glass substrate
- ⁇ E ( ⁇ L 2 + ⁇ a 2 + ⁇ b 2 ) 1/2 on the Y axis represents a color index change value.
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Abstract
Description
구분 | 실시예 1 | 비교예 1 | 비교예 2 | 비교예 3 |
스크래치 형태 | 가느다란선 스크래치(hairline scratch) | 면적 스크래치(area scratch) | 가느다란선 스크래치(hairline scratch) | 가느다란선 스크래치(hairline scratch) |
스크래치 개수 | 3개 | 10개 | 8개 | 6개 |
구분 | 실시예 1 | 비교예 1 | 비교예 2 | 비교예 3 |
부식점의 개수(3일차) | 2개 | 200개 이상 | 21개 | 71개 |
부식점의 개수(7일차) | 6개 | 200개 이상 | 57개 | 186개 |
Claims (17)
- 기재; 저방사 코팅층; 및 최상부 코팅층을 포함하고,상기 최상부 코팅층은 상기 저방사 코팅층으로부터 금속층, 금속 산화물층 및 실리콘계 복합금속 산화질화물층을 순차적으로 포함하는 다층 구조인저방사 코팅막.
- 제1항에 있어서,상기 금속층은 실리콘, 알루미늄, 티타늄, 지르코늄, 실리콘계 복합금속, 티타늄계 복합금속, 지르코늄계 복합금속 및 이들의 조합으로부터 선택된 적어도 하나를 포함하는저방사 코팅막.
- 제1항에 있어서,상기 금속 산화물층은 실리콘 산화물, 알루미늄 산화물, 티타늄 산화물, 지르코늄 산화물, 실리콘계 복합금속 산화물, 티타늄계 복합금속 산화물, 지르코늄계 복합금속 산화물, 및 이들의 조합으로부터 선택된 적어도 하나를 포함하는저방사 코팅막.
- 제1항에 있어서,상기 저방사 코팅층은 상기 기재로부터 제1유전체층, 제1저방사 보호층, 저방사층, 제2저방사 보호층 및 제2유전체층을 순차적으로 포함하는 다층 구조인저방사 코팅막.
- 제4항에 있어서,상기 제1유전체층 또는 상기 제2유전체층은 티타늄옥사이드, 주석아연옥사이드, 아연옥사이드, 아연알루미늄옥사이드, 주석옥사이드, 비스무스옥사이드, 실리콘나이트라이드, 실리콘알루미늄나이트라이드, 실리콘주석나이트라이드 및 이들의 조합으로 이루어진 군에서 선택된 적어도 하나를 포함하거나,상기 적어도 하나에, 비스무스(Bi), 붕소(B), 알루미늄(Al), 규소(Si), 마그네슘(Mg), 안티몬(Sb), 베릴륨(Be) 및 이들의 조합으로 이루어진 군에서 선택된 적어도 하나의 원소가 도핑된저방사 코팅막.
- 제4항에 있어서,상기 제1저방사 보호층 또는 상기 제2저방사 보호층은 니켈(Ni), 크롬(Cr), 니켈(Ni)과 크롬(Cr)의 합금, 티타늄(Ti) 밑 이들의 조합을 포함하는 군으로부터 선택된 적어도 하나를 포함하는저방사 코팅막.
- 제4항에 있어서,상기 저방사층은 은(Ag), 금(Au), 구리(Cu), 알루미늄(Al), 백금(Pt), 이온 도핑 금속 산화물 및 이들의 조합을 포함하는 군으로부터 선택된 적어도 하나를 포함하는저방사 코팅막.
- 제1항에 있어서,상기 금속층의 두께는 0.5nm 내지 5nm인저방사 코팅막.
- 제1항에 있어서,상기 금속 산화물층의 두께는 0.5nm 내지 5nm인저방사 코팅막.
- 제1항에 있어서,상기 실리콘계 복합금속 산화질화물층의 두께는 2nm 내지 20nm인저방사 코팅막.
- (a) 기재의 적어도 일면에 적층된 저방사 코팅층을 준비하는 단계;(b) 상기 저방사 코팅층의 상부에 금속을 증착하여 금속층을 형성하는 단계; 및(c) 상기 금속층 상부에 금속 산화물층을 형성하고, 실리콘계 복합금속 산화질화물을 증착하여 실리콘계 복합금속 산화질화물층을 형성하는 단계를 포함하는저방사 코팅막의 제조방법.
- 제11항에 있어서,상기 (b)에서 금속층은 실리콘, 알루미늄, 티타늄, 지르코늄, 실리콘계 복합금속, 티타늄계 복합금속, 지르코늄계 복합금속 및 이들의 조합으로부터 선택된 적어도 하나를 포함하는저방사 코팅막의 제조방법.
- 제11항에 있어서,상기 (c)에서 금속 산화물층은 실리콘 산화물, 알루미늄 산화물, 티타늄 산화물, 지르코늄 산화물, 실리콘계 복합금속 산화물, 티타늄계 복합금속 산화물, 지르코늄계 복합금속 산화물, 및 이들의 조합으로부터 선택된 적어도 하나를 포함하는저방사 코팅막의 제조방법.
- 제11항에 있어서,상기 (c)에서 금속 산화물층의 형성은 상기 금속층 표면의 후산화 공정을 통해 상기 금속층 표면을 일부 산화시켜 수행되는 것인저방사 코팅막의 제조방법.
- 제14항에 있어서,상기 후산화 공정은 산소(O2), 질소(N2) 및 아르곤(Ar)로 이루어진 군으로부터 선택된 적어도 하나의 반응성 가스를 사용하여 수행되는저방사 코팅막의 제조방법.
- 제14항에 있어서,상기 (c)에서 금속층 표면의 일부 산화와 실리콘계 복합금속 산화질화물의 증착은 인시츄(in-situ)에서 연속적으로 수행되는 것인저방사 코팅막의 제조방법.
- 제1항 내지 제10항 중 어느 한 항에 따른 저방사 코팅막을 포함하는창호용 기능성 건축 자재.
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JP2016538641A JP6518670B2 (ja) | 2013-12-12 | 2014-12-11 | 低放射コーティング膜、その製造方法及びそれを含む窓用機能性建築資材 |
US15/100,637 US9903154B2 (en) | 2013-12-12 | 2014-12-11 | Low-emissivity coating film, method for manufacturing same, and functional construction material for window and doors including same |
EP14869874.9A EP3081605B1 (en) | 2013-12-12 | 2014-12-11 | Low-emissivity coating film, method for manufacturing same, and functional construction material for window and doors including same |
CN201480066966.3A CN105814149B (zh) | 2013-12-12 | 2014-12-11 | 低辐射涂敷膜、其的制备方法及包含其的窗户用功能性建材 |
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Also Published As
Publication number | Publication date |
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US20160298384A1 (en) | 2016-10-13 |
JP2017500266A (ja) | 2017-01-05 |
EP3081605A4 (en) | 2016-11-30 |
JP6518670B2 (ja) | 2019-05-22 |
CN105814149A (zh) | 2016-07-27 |
CN105814149B (zh) | 2019-11-22 |
KR20150069533A (ko) | 2015-06-23 |
US9903154B2 (en) | 2018-02-27 |
KR101788368B1 (ko) | 2017-10-20 |
EP3081605A1 (en) | 2016-10-19 |
EP3081605B1 (en) | 2019-04-17 |
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