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US20050238923A1 - Hybrid coating stack - Google Patents

Hybrid coating stack Download PDF

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Publication number
US20050238923A1
US20050238923A1 US10/832,600 US83260004A US2005238923A1 US 20050238923 A1 US20050238923 A1 US 20050238923A1 US 83260004 A US83260004 A US 83260004A US 2005238923 A1 US2005238923 A1 US 2005238923A1
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US
United States
Prior art keywords
coating
refractive index
topcoat
topcoat layer
qwot
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
US10/832,600
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English (en)
Inventor
James Thiel
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Vitro SAB de CV
Vitro Flat Glass LLC
Original Assignee
Individual
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=34993321&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=US20050238923(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Individual filed Critical Individual
Priority to US10/832,600 priority Critical patent/US20050238923A1/en
Assigned to PPG INDUSTRIES OHIO, INC. reassignment PPG INDUSTRIES OHIO, INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: THIEL, JAMES P.
Priority to EP05749344.7A priority patent/EP1742889B8/fr
Priority to PCT/US2005/013286 priority patent/WO2005115940A1/fr
Priority to RU2006141646/03A priority patent/RU2329979C1/ru
Priority to MXPA06012103A priority patent/MXPA06012103A/es
Priority to ES05749344T priority patent/ES2715210T3/es
Priority to PL05749344T priority patent/PL1742889T3/pl
Priority to CN200580013433XA priority patent/CN1946645B/zh
Priority to CA2563945A priority patent/CA2563945C/fr
Priority to JP2007510796A priority patent/JP4768722B2/ja
Publication of US20050238923A1 publication Critical patent/US20050238923A1/en
Priority to US11/756,664 priority patent/US7648768B2/en
Assigned to VITRO, S.A.B. DE C.V. reassignment VITRO, S.A.B. DE C.V. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: PPG INDUSTRIES OHIO, INC.
Assigned to VITRO, S.A.B. DE C.V. reassignment VITRO, S.A.B. DE C.V. CORRECTIVE ASSIGNMENT TO CORRECT THE ASSIGNEE ADDRESS PREVIOUSLY RECORDED AT REEL: 040473 FRAME: 0455. ASSIGNOR(S) HEREBY CONFIRMS THE ASSIGNMENT. Assignors: PPG INDUSTRIES OHIO, INC.
Assigned to VITRO FLAT GLASS LLC reassignment VITRO FLAT GLASS LLC ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: VITRO, S.A.B. DE C.V.
Abandoned legal-status Critical Current

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Classifications

    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10165—Functional features of the laminated safety glass or glazing
    • B32B17/10174—Coatings of a metallic or dielectric material on a constituent layer of glass or polymer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10761—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing vinyl acetal
    • 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
    • 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
    • C03C17/3681—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 being used in glazing, e.g. windows or windscreens
    • 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
    • C03C2217/00—Coatings on glass
    • C03C2217/70—Properties of coatings
    • C03C2217/73—Anti-reflective coatings with specific characteristics
    • C03C2217/734—Anti-reflective coatings with specific characteristics comprising an alternation of high and low refractive indexes

Definitions

  • This invention relates generally to coatings and coated articles and, more particularly, to coatings having a solar control coating with a durability-enhancing topcoat and to articles coated therewith.
  • Solar control coatings are known for controlling the amount of solar radiation passing into buildings, vehicles, and other structures. These solar control coatings can block or reflect selected electromagnetic wavelengths and can help reduce the costs of heating and/or cooling.
  • Conventional solar control coatings typically include an infrared reflecting metal layer positioned between two dielectric layers.
  • Conventional dielectric layers typically include metal oxides.
  • a thin protective overcoat, such as titania, is deposited over the outermost dielectric layer to help protect the underlying layers from chemical and mechanical damage. Examples of known solar control coatings are disclosed in U.S. Pat. Nos. 4,610,771; 4,716,086; and 4,898,789.
  • Coated substrates such as glass substrates coated with solar control coatings
  • An example of a laminated article is a conventional automotive windshield.
  • An example of a non-laminated article is a conventional architectural window.
  • Known solar control coatings are well suited for their intended purpose of modifying the solar control properties of the coated article.
  • conventional solar control coatings can be susceptible to mechanical or chemical damage during handling even with a conventional protective overcoat. While it would be possible to increase the mechanical and/or chemical durability of a conventional solar control coating stack by increasing the thickness of the outer protective overcoat, such an increase in thickness would also impact other parameters of the coated article, such as the reflectance, transmittance, or emissivity of the article and could significantly change the transmission characteristics, solar performance properties, and aesthetics of the coated article. This would be disadvantageous, particularly for coated glass articles destined for use in the automotive field where solar control properties, such as transmittance and/or reflectance, are controlled to meet government regulations. Additionally, increasing the thickness of the protective overcoat could also adversely impact upon the processing parameters of the coated article, such as adversely impacting the bending, annealing, tempering, or laminating processes.
  • Coating stacks for non-solar control purposes are known.
  • conventional camera lenses typically include an anti-reflective coating made up of a series of layers of high and low refractive index materials. These layers reduce visible light reflection when taking photographs. While these anti-reflective lens coatings are adequate for their intended purpose of reducing visible light reflection, they do not have infrared reflective metal layers and, thus, provide little or no solar control properties. While one might consider adding a conventional lens coating to a conventional solar control coating stack, such a combination would not be feasible since the resultant coating stack would not meet the optical and/or solar reflecting characteristics typically required for solar control articles, such as automotive transparencies and architectural transparencies.
  • a coating comprises a functional coating, such as a solar control coating comprising at least one metal layer.
  • a topcoat is formed over at least a portion of the functional coating.
  • the topcoat comprises a first topcoat layer having a thickness in the range of 0.5 Quarter Wave Optical Thickness (QWOT) to 1.5 QWOT with respect to a reference wavelength of 550 nm and a first refractive index, and a second topcoat layer having a thickness in the range of 0.5 QWOT to 1.5 QWOT with respect to a reference wavelength of 550 nm and a second refractive index different from the first refractive index.
  • QWOT Quarter Wave Optical Thickness
  • one of the first topcoat layer or the second topcoat layer comprises at least one metal oxide selected from oxides of aluminum, silicon, yttrium, tin, and mixtures thereof, and the other of the first topcoat layer or second topcoat layer comprises at least one metal oxide selected from oxides of titanium, zirconium, niobium, bismuth, tungsten, zinc, tin, and mixtures thereof.
  • the topcoat can further include a third topcoat layer having a thickness in the range of 0.5 QWOT to 1.5 QWOT.
  • the third topcoat layer comprises silica.
  • Another coating comprises a functional coating, such as a solar control coating comprising at least one infrared reflective metal layer.
  • a topcoat is formed over at least a portion of the functional coating.
  • the topcoat comprises a first topcoat layer deposited over at least a portion of the functional coating and a second topcoat layer deposited over at least a portion of the first topcoat layer.
  • the refractive index of the first topcoat layer can differ from the refractive index of the second topcoat layer by a value in the range of 0.2 to 1.
  • a coated article comprises a substrate and a coating as defined above deposited over at least a portion of the substrate.
  • Another coated article comprises a substrate and a coating deposited over at least a portion of the substrate.
  • the coating comprises: (a) a functional coating comprising a first metal oxide layer, a second metal oxide layer, and an infrared reflective metal layer positioned between the first and second metal oxide layers, and (b) a topcoat formed over the functional coating and comprising a first topcoat layer and a second topcoat layer, wherein the first topcoat layer has a thickness in the range of 0.5 QWOT to 1.5 QWOT with respect to a reference wavelength of 550 nm and a first refractive index of either (i) less than or equal to 2 or (ii) greater than 2, and the second topcoat layer has a thickness in the range of 0.5 QWOT to 1.5 QWOT with respect to a wavelength of 550 nm and a second refractive index of (i) greater than 2 when the first refractive index is less than or equal 2 or (ii) less than or equal to 2 when the first refractive index is greater than 2.
  • FIG. 1 is a cross-sectional view (not to scale) of a monolithic article having a hybrid coating incorporating features of the invention
  • FIG. 2 is a cross-sectional view (not to scale) of a laminated article having a hybrid coating incorporating features of the invention
  • FIG. 3 is a graph of percent reflectance versus wavelength (nanometers) comparing a single silver layer coating having a topcoat of the invention with a similar single silver layer coating without the topcoat of the invention;
  • FIG. 4 is a graph of percent reflectance versus wavelength (nanometers) comparing a double silver layer coating having a topcoat of the invention with a similar double silver layer coating without the topcoat of the invention.
  • each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.
  • all ranges disclosed herein are to be understood to encompass any and all subranges subsumed therein.
  • a stated range of “1 to 10” should be considered to include any and all subranges between (and inclusive of) the minimum value of 1 and the maximum value of 10; that is, all subranges beginning with a minimum value of 1 or more and ending with a maximum value of 10 or less, e.g., 1 to 3.7, 5.5 to 10, or 6.5 to 9.5, just to name a few.
  • the terms “deposited over”, “applied over”, or “formed over” mean deposited, applied, or formed on but not necessarily in contact with the surface.
  • a material “deposited over” a substrate does not preclude the presence of one or more other materials of the same or different composition located between the deposited material and the substrate.
  • all references referred to herein are to be understood as being incorporated by reference in their entirety.
  • the terms “visible region” or “visible light” refer to electromagnetic radiation having a wavelength in the range of 400 nm to 700 nm.
  • the terms “infrared region” or “infrared radiation” refer to electromagnetic radiation having a wavelength in the range of greater than 700 nm to 100,000 nm.
  • ultraviolet region or “ultraviolet radiation” mean electromagnetic energy having a wavelength in the range of 300 nm to less than 400 nm.
  • film refers to a region of a coating having a desired or selected composition.
  • a “layer” comprises one or more “films”.
  • a “coating” or “coating stack” is comprised of one or more “layers”. All quarter wave optical thicknesses values herein are defined relative to a reference wavelength of 550 nm.
  • FIG. 1 An exemplary coated article 10 incorporating features of the invention is shown in FIG. 1 .
  • the article 10 includes a substrate 12 which can have at least one major surface.
  • a hybrid coating 14 of the invention can be formed over at least a portion of the substrate 12 .
  • the hybrid coating 14 comprises at least one functional coating 16 formed over at least a portion of the substrate 12 , e.g., over at least a portion of a major surface, and an anti-reflective topcoat 18 of the invention formed over at least a portion of the functional coating 16 .
  • the article 10 can be a monolithic article, as shown in FIG. 1 .
  • monolithic is meant having a single structural substrate or primary ply.
  • primary ply is meant a primary support or structural member.
  • the invention can be practiced to form a laminated article.
  • the substrate 12 can be of any desired dimensions, e.g., length, width, shape, or thickness, and can be of any desired material having any desired characteristics, such as opaque, translucent, or transparent to visible light.
  • transparent is meant having a transmittance of visible light through the substrate of greater than 0% up to 100%.
  • translucent is meant allowing electromagnetic energy (e.g., visible light) to pass through the substrate but diffusing this energy such that objects on the side of the substrate opposite to the viewer are not clearly visible.
  • opaque is meant having a visible light transmittance of less than 0.001%.
  • suitable substrates include, but are not limited to, plastic substrates (such as acrylic polymers, such as polyacrylates; polyalkylmethacrylates, such as polymethylmethacrylates, polyethylmethacrylates, polypropylmethacrylates, and the like; polyurethanes; polycarbonates; polyalkylterephthalates, such as polyethyleneterephthalate (PET), polypropyleneterephthalates, polybutyleneterephthalates, and the like; polysiloxane-containing polymers; or copolymers of any monomers for preparing these, or any mixtures thereof); metal substrates, such as but not limited to galvanized steel, stainless steel, and aluminum; ceramic substrates; tile substrates; glass substrates; fiberglass substrates; or mixtures or combinations of any of the above.
  • plastic substrates such as acrylic polymers, such as polyacrylates; polyalkylmethacrylates, such as polymethylmethacrylates, polyethylmethacrylates, polypropylmethacrylates,
  • the substrate can be conventional untinted soda-lime-silica glass, i.e., “clear glass”, or can be tinted or otherwise colored glass, borosilicate glass, leaded glass, tempered, untempered, annealed, or heat-strengthened glass.
  • the glass can be of any type, such as conventional float glass or flat glass, and can be of any composition having any optical properties, e.g., any value of visible radiation transmission, ultraviolet radiation transmission, infrared radiation transmission, and/or total solar energy transmission.
  • Typical automotive-type glasses can have such colors as blue, green, bronze, gray, and non-exclusive examples of these glasses include glasses commercially available from PPG Industries, Inc.
  • the glass can be untempered, heat treated, or heat strengthened glass.
  • heat treated means heated to a temperature sufficient to bend or anneal or temper the glass.
  • heat strengthened means annealed, tempered, or at least partially tempered.
  • the substrate 12 is or comprises glass, such as but not limited to a glass sheet, such as a sheet of flat glass or window glass.
  • a glass substrate can typically be up to 10 mm thick, e.g., in the range of 1 mm to 10 mm thick, e.g., less than 10 mm thick, e.g., 1 mm to 5 mm thick, e.g., 1.5 mm to 2.5 mm, e.g., 1.6 mm to 2.3 mm.
  • the substrate 12 can be a flat substrate or can be shaped, bent, or curved.
  • flat substrate a substrate lying primarily in a single geometric plane, e.g., such as a piece of flat glass produced by a conventional float glass process.
  • shaped or “bent” is meant a substrate that is not flat.
  • a functional coating 16 can be formed over at least a portion of the substrate 12 .
  • “functional coating” is meant a coating that modifies one or more physical or optical properties of the substrate on which it is deposited, e.g., optical, thermal, chemical or mechanical properties, and is not intended to be entirely removed from the substrate during subsequent processing.
  • the functional coating 16 can have one or more functional coating films or layers of the same or different composition or functionality.
  • the functional coating 16 can be, for example, an electrically conductive coating used to make heatable windows, such as is disclosed in U.S. Pat. Nos. 5,653,903 and 5,028,759, or a single-film or multi-film coating used as an antenna.
  • the functional coating 16 can be a solar control coating.
  • the terms “solar control coating” and/or “low emissivity coating” refer to a coating comprised of one or more layers or films that affect the solar properties of the coated article, such as but not limited to the shading coefficient and/or the amount of solar radiation, for example, visible, infrared (IR), or ultraviolet (UV) radiation, reflected from and/or passing through the coated article 10 .
  • a solar control coating can block, absorb or filter selected portions of the solar spectrum, such as but not limited to the IR, UV, and/or visible spectrums.
  • solar control coatings that can be used in the practice of the invention are found in, but are not limited to, U.S. Pat. Nos. 4,898,789; 5,821,001; 4,716,086; 4,610,771; 4,902,580; 4,716,086; 4,806,220; 4,898,790; 4,834,857; 4,948,677; 5,059,295; and 5,028,759, and also in U.S. patent application Ser. Nos. 09/058,440 and 60/355,912.
  • the functional coating 16 can affect the emissivity of the coated article, i.e., can be a low emissivity coating.
  • a low emissivity coating allows short wavelength energy, e.g., visible or ultraviolet energy to be transmitted through the coating but reflects longer wavelength energy, such as infrared energy.
  • low emissivity is meant emissivity less than 0.4, such as less than 0.3, such as less than 0.2, such as less than 0.1, such as less than or equal to 0.05. The lower the emissivity, the more infrared wavelength energy is reflected.
  • Non-limiting examples of low emissivity coatings are found in U.S. Pat. Nos. 4,952,423 and 4,504,109 and British reference GB 2,302,102.
  • the functional coating 16 can include one or more anti-reflective coating films comprising dielectric or anti-reflective materials, such as metal oxides, oxides of metal alloys, or doped metal oxides and/or doped metal alloys that are transparent to visible light.
  • the functional coating 16 can also include one or more infrared reflective films comprising a reflective metal, e.g., a noble metal such as gold, copper or silver, or combinations or alloys thereof, and can further comprise one or more primer films or barrier films, such as titanium, nickel, chrome, nickel-chrome alloy, niobium, zirconium, or other primers known in the art, located over and/or under the metal reflective layer(s).
  • suitable functional coatings 16 for use with the invention are commercially available from PPG Industries, Inc. of Pittsburgh, Pa. under the SUNGATE® and SOLARBAN® families of coatings.
  • the functional coating 16 can include one or more coating units 26 as shown in FIG. 1 .
  • the coating unit(s) 26 can comprise a first dielectric layer 28 , an infrared reflective metal layer 30 , a primer layer 32 , and a second dielectric layer 34 .
  • the first and/or second dielectric layers 28 , 34 and the reflective metal layer 30 can be of any of the general materials described above and can be of any desired thickness.
  • the functional coating 16 can include one coating unit 26 or can include a plurality of coating units 26 formed over the substrate 12 .
  • the functional coating 16 can be deposited over the substrate 12 by any conventional method, such as conventional physical vapor deposition (PVD) or chemical vapor deposition (CVD) processes. Suitable deposition processes include, but are not limited to, spray pyrolysis, sol-gel, electron beam evaporation, or vacuum sputtering such as magnetron sputter vapor deposition (MSVD). In one embodiment, the functional coating 16 can be deposited by MSVD. Examples of MSVD coating devices and methods will be well understood by one of ordinary skill in the art and are described, for example, in U.S. Pat. Nos. 4,379,040; 4,861,669; 4,898,789; 4,898,790; 4,900,633; 4,920,006; 4,938,857; 5,328,768; and 5,492,750.
  • one or both of the dielectric layers 28 and/or 34 can comprise one or more films of anti-reflective materials and/or dielectric materials, such as but not limited to metal oxides, oxides of metal alloys, nitrides, oxynitrides, or mixtures thereof.
  • the dielectric layers can be transparent to visible light.
  • suitable metal oxides include, but are not limited to, oxides of titanium, hafnium, zirconium, niobium, zinc, bismuth, lead, indium, tin, and mixtures thereof. These metal oxides can have small amounts of other materials (e.g., dopants), such as manganese in bismuth oxide, indium-tin oxide, etc.
  • oxides of metal alloys or metal mixtures can be used, such as oxides containing zinc and tin (e.g., zinc stannate), oxides of indium-tin alloys, silicon nitrides, silicon aluminum nitrides, oxynitrides, or aluminum nitrides.
  • doped metal oxides or doped metal alloy oxides such as but not limited to antimony or indium doped tin oxides or nickel or boron doped silicon oxides or tin doped zinc oxides, can be used.
  • the dielectric layers 28 , 34 can be substantially single phase films, such as a metal alloy oxide film, e.g., zinc stannate, or can be a mixture of phases composed of zinc and tin oxides, or can be composed of a plurality of metal oxide films, such as but not limited to those disclosed in U.S. Pat. Nos. 5,821,001; 4,898,789; and 4,898,790, or can be doped metal oxide films or doped metal alloy oxides films.
  • a metal alloy oxide film e.g., zinc stannate
  • a mixture of phases composed of zinc and tin oxides or can be composed of a plurality of metal oxide films, such as but not limited to those disclosed in U.S. Pat. Nos. 5,821,001; 4,898,789; and 4,898,790, or can be doped metal oxide films or doped metal alloy oxides films.
  • the first dielectric layer 28 can have a total thickness of less than or equal to 500 ⁇ , e.g., less than or equal to 400 ⁇ , e.g., less than or equal to 280 ⁇ .
  • the metal alloy oxide film 28 can have a thickness in the range of 100 ⁇ to 500 ⁇ , such as 150 ⁇ to 400 ⁇ , e.g., 200 ⁇ , to 400 ⁇ .
  • the reflective layer 30 be an IR reflective metal, such as but not limited to gold, copper, silver, or mixtures, alloys, or combinations thereof, and can have a thickness in the range of 50 ⁇ to 200 ⁇ , such as 75 ⁇ to 150 ⁇ , e.g., 100 ⁇ .
  • the IR reflective layer 30 comprises silver.
  • the metal alloy oxide films 28 , 34 can each include a zinc/tin alloy oxide.
  • the zinc/tin alloy can comprise zinc and tin in proportions of 10 wt. % to 90 wt. % zinc and 90 wt. % to 10 wt. % tin.
  • One suitable metal alloy oxide for use in the invention is zinc stannate.
  • zinc stannate is meant a composition of Zn x Sn 1 ⁇ x O 2 ⁇ x (Formula 1), where x varies in the range of greater than 0 to less than 1. For instance the number x can be greater than 0 and can be any fraction or decimal between greater than 0 up to the number 1.
  • a zinc stannate containing film has one or more of the forms of Formula 1 in a predominant amount in the film.
  • the metal oxide film can include a zinc-containing film, such as zinc oxide.
  • the zinc oxide film can include other materials to improve the sputtering characteristics of the associated cathode, e.g., the zinc oxide can contain 0 to 20 wt. % tin, e.g., 0 to 15 wt. % tin, e.g., 0 to 10 wt. % tin.
  • the primer film 32 can be an oxygen capturing material, such as titanium, that can be sacrificial during the deposition process to prevent degradation or oxidation of the reflective layer 30 during a sputtering process.
  • the oxygen capturing material can be chosen to oxidize before the material of the reflective layer 30 .
  • the hybrid coating 14 further includes a protective coating or topcoat 18 to assist in providing protection against mechanical and chemical attack.
  • the topcoat 18 includes a first topcoat layer 40 , a second topcoat layer 42 , and a third topcoat layer 44 .
  • the topcoat 18 of the invention is a multi-layer structure.
  • the topcoat 18 has much fewer layers.
  • the first topcoat layer 40 can have a low refractive index
  • the second topcoat layer 42 can have a high refractive index
  • the third topcoat layer 44 can have a low refractive index.
  • low refractive index is meant a material having a refractive index less than that of the “high refractive index” material. That is, the terms “low” and “high” can be relative terms with respect to the materials chosen for the topcoat layers.
  • the “low refractive index” material can have a refractive index of 2 or less. Examples of some suitable materials include, but are not limited to, oxides comprising aluminum, silicon, yttrium, tin, or mixtures or combinations thereof.
  • the “high refractive index” material has a refractive index greater than that of the low refractive index material.
  • the high refractive index material can have a refractive index of greater than 2.
  • suitable materials include, but are not limited to, oxides comprising titanium, zirconium, niobium, bismuth, tungsten, zinc, tin, or mixtures or combinations thereof.
  • the first topcoat layer 40 comprises silica
  • the second topcoat layer 42 comprises zinc oxide
  • the third topcoat layer 44 comprises silica.
  • some of the topcoat layers can include small amounts of other materials, e.g., dopants, for example provided to increase the conductivity of the cathode from which they are deposited.
  • the adjacent low and high index materials can have a refractive index difference of at least 0.2.
  • refractive index difference is meant the difference between the refractive indices of two adjacent topcoat layers.
  • the refractive index difference can be in the range of 0.2 to 1, such as 0.2 to 0.6, such as 0.4.
  • the first topcoat layer 40 can comprise a high refractive index material
  • the second topcoat 42 can comprise a low refractive index material
  • the optional third topcoat layer 44 can comprise a high refractive index material.
  • One or more of the topcoat layers can include a dopant to increase the conductivity of the cathode from which they are deposited.
  • one or more of the topcoat layers can comprise silica doped with aluminum, e.g., 0.1 wt. % to 25 wt. % aluminum, such as 5 wt. % to 20 wt. % aluminum, such as 10 wt. % to 20 wt. % aluminum, such as 10 wt. % aluminum.
  • one or more of the topcoat layers can comprise zinc oxide doped with tin, e.g., 1 wt. % to 15 wt. % tin, such as 2 wt. % to 10 wt. % tin, such as 5 wt. % tin.
  • the topcoat layers 40 , 42 , and 44 can be of any desired thickness.
  • the first topcoat layer 40 and second topcoat layer 42 can have a thickness of about 1 quarter wave optical thickness (i.e., 1 QWOT) with respect to a reference wavelength of 550 nanometers and the third topcoat layer 44 can have a QWOT less than 1.
  • the “optical thickness” of a material is defined as the thickness of the material divided by the refractive index of the material.
  • 1 quarter wave optical thickness (QWOT) of a material having a refractive index of 2 with respect to a reference wavelength of 550 nm would be 0.25 ⁇ (550 nm ⁇ 2), which equals 68.75 nm.
  • 0.33 QWOT of a material having a refractive index of 1.75 with respect to a reference wavelength of 550 nm would be equivalent to 0.33 ⁇ [0.25 ⁇ (550 nm ⁇ 1.75)] or 25.93 nm.
  • a material with an index of refraction of 2.2 and a thickness of 50 nm would be equivalent to [(50 nm ⁇ 550 nm) ⁇ 2.2] ⁇ 0.25 or 0.8 QWOT based on a wavelength of 550 nm.
  • the quarter wave optical thickness of two materials may be the same, the actual physical thickness of the layers may be different due to the differing refractive indices of the materials.
  • the QWOT values are those defined with respect to a reference wavelength of 550 nm.
  • the first topcoat layer 40 can have a QWOT in the range of 0.1 to 1, such as 0.5 to 0.6.
  • the second topcoat layer 42 can have a QWOT in the range of 0.5 to 1.5, such as 1 to 1.5, such as 1.2 to 1.4.
  • the third topcoat layer 44 can have a QWOT in the range of 0.5 to 1, such as 0.6 to 0.8.
  • the hybrid coating 14 can include a functional coating 16 having a first dielectric layer 28 comprising a first film comprising a zinc and tin alloy, e.g., zinc stannate, having a QWOT in the range of 0.1 to 1, such as 0.2 to 0.7.
  • the first dielectric layer 28 can also include a second film formed over the first film.
  • the second film comprises zinc oxide.
  • the zinc-oxide second film can be doped with another material, such as 1 wt. % to 10 wt. % tin, such as 2 wt. % to 7 wt. % tin, such as 5 wt. % tin.
  • the first film can have a thickness in the range of 0.05 QWOT to 0.5 QWOT, such as 0.1 QWOT to 0.15 QWOT.
  • a second dielectric film can be formed over the first film.
  • the second film can comprise a zinc-tin alloy, such as zinc stannate, and can have a thickness in the range of 0.1 to 1.5 QWOT, such as 0.2 to 1 QWOT.
  • the exemplary hybrid coating 14 further includes a topcoat 18 having a first topcoat layer comprising silica having a thickness in the range of 0.5 QWOT to 1.5 QWOT, such as 0.8 QWOT to 1.3 QWOT, such as 0.9 QWOT to 1.2 QWOT, such as 1 QWOT.
  • the second topcoat layer 42 can comprise tin oxide and can have a thickness in the range of 0.05 QWOT to 1.5 QWOT, such as 0.08 QWOT to 1.3 QWOT, such as 0.09 QWOT to 1.2 QWOT, such as 1 QWOT.
  • the third topcoat layer 44 can comprise silica and can have a thickness in the range of 0.1 QWOT to 1 QWOT, such as 0.2 QWOT to 0.9 QWOT, such as 0.3 QWOT to 0.8 QWOT, such as 0.4 QWOT to 0.8 QWOT, such as 0.5 QWOT to 0.8 QWOT, such as 0.6 QWOT to 0.8 QWOT, such as 0.7 QWOT.
  • a laminated article 50 is shown in FIG. 2 .
  • the coated substrate 12 can be laminated to another substrate 52 by a conventional adhesive layer 54 .
  • the substrate 52 can be of any of the materials described above with respect to substrate 12 and can be the same or different than substrate 12 .
  • the adhesive layer 54 can include one or more plastic or polymeric materials, such as polyvinyl butyral, plasticized polyvinyl chloride, or multi-layered thermoplastic materials including polyethylene terephthalate. Suitable adhesive materials are described in U.S. Pat. Nos. 4,287,107 and 3,762,988.
  • the adhesive layer 54 is typically polyvinyl butyral having a thickness in the range of 0.5 mm to 1 mm.
  • the functional coating 16 can be the same as described above. However, the outermost topcoat layer 44 (shown in FIG. 1 ) can be eliminated for the laminated article 50 .
  • This Example illustrates the solar reflectivity of a single silver layer solar control coating with a topcoat of the invention and without a topcoat of the invention.
  • Table 1 shows the layer structure of a solar control coating having a single silver infrared reflective layer.
  • the first dielectric layer comprises two dielectric films ( 1 and 2 ).
  • the first dielectric film (film 1 ) comprises zinc stannate while the second dielectric film (film 2 ) comprises a tin doped zinc oxide.
  • the tin is due to the fact that the sputtering cathode from which the layer is deposited includes some time to improve the sputtering characteristics of the zinc cathode.
  • the second dielectric film is primarily zinc oxide, some tin from the cathode can also be present, such as incorporated into the zinc oxide structure or as tin oxide.
  • the second dielectric layer comprises two dielectric films ( 5 and 6 ).
  • the first dielectric film (film 5 ) comprises a tin doped zinc oxide while the second dielectric film (film 6 ) comprises zinc stannate.
  • TABLE 1 Film Material Thickness (nm) QWOT 1 Zn 2 SnO 4 41.67 0.62341 2 Sn:ZnO 4 8.00 0.11514 3 Ag 9.42 0.00792 4 TiO 2 2.00 0.03577 5 Sn:ZnO 4 8.00 0.11514 6 Zn 2 SnO 4 26.79 0.4008
  • Table 2 shows the structure of a similar coating but also incorporates a topcoat (films 7 , 8 and 9 ) of the invention.
  • the topcoat comprises a first topcoat layer of silica that also includes a small portion of alumina.
  • the alumina is present due to the presence of aluminum in the silicon sputtering target.
  • the second topcoat layer comprises zinc oxide with a small portion of tin.
  • the third topcoat layer comprises silica with a small portion of alumina.
  • FIG. 3 shows the percent reflectance versus wavelength for the coating of Table 1 (curve 80 ) and of Table 2 (curve 82 ).
  • the reflectance values shown in FIG. 3 were calculated using FilmStar DESIGN software commercially available from FTG Software Associates of Princeton, N.J.
  • the hybrid coating of curve 82 has substantially better solar reflectance in the near infrared region of the spectrum than the coating of curve 80 without the topcoat of the invention.
  • the hybrid coating provides a region of enhanced solar infrared reflectance in the near solar infrared region adjacent the visible region of the electromagnetic spectrum. Such an enhanced infrared reflective region would not be expected simply from the addition of a multi-layer topcoat.
  • topcoat having low and high refractive index materials in accordance with the present invention appears to improve the solar control performance compared to a similar functional coating without the topcoat. Additionally, it is to be expected that the topcoat of the invention will provide improved mechanical and/or chemical durability compared to conventional thinner titania coatings of the known art.
  • This Example illustrates the effects of a topcoat on the invention of a functional coating having two silver infrared reflective metal layers.
  • a coating stack having two infrared reflective silver layers is set forth in Table 3.
  • Table 3 Film Material Thickness (nm)
  • Ag 10.95 0.00921 TiO 2 2.00 0.03577 10
  • the solar reflectivity of the coatings shown in Tables 3 and 4 is depicted in FIG. 4 .
  • the coating with the topcoat of the invention (curve 84 ) shows improved solar reflectivity in the near infrared region compared to the coating without the topcoat of the invention (curve 86 ).

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  • Laminated Bodies (AREA)
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US10/832,600 2004-04-27 2004-04-27 Hybrid coating stack Abandoned US20050238923A1 (en)

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Application Number Priority Date Filing Date Title
US10/832,600 US20050238923A1 (en) 2004-04-27 2004-04-27 Hybrid coating stack
JP2007510796A JP4768722B2 (ja) 2004-04-27 2005-04-19 ハイブリッド被覆積層体
PCT/US2005/013286 WO2005115940A1 (fr) 2004-04-27 2005-04-19 Empilement de revetements hybrides
ES05749344T ES2715210T3 (es) 2004-04-27 2005-04-19 Pila de recubrimiento híbrido
CA2563945A CA2563945C (fr) 2004-04-27 2005-04-19 Empilement de revetements hybrides
RU2006141646/03A RU2329979C1 (ru) 2004-04-27 2005-04-19 Гибридное многослойное покрытие
MXPA06012103A MXPA06012103A (es) 2004-04-27 2005-04-19 Pila de recubrimiento hibrida.
EP05749344.7A EP1742889B8 (fr) 2004-04-27 2005-04-19 Empilement de revetements hybrides
PL05749344T PL1742889T3 (pl) 2004-04-27 2005-04-19 Hybrydowy stos powłok
CN200580013433XA CN1946645B (zh) 2004-04-27 2005-04-19 杂化涂层叠层
US11/756,664 US7648768B2 (en) 2004-04-27 2007-06-01 Hybrid coating stack

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ES (1) ES2715210T3 (fr)
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US7648768B2 (en) 2010-01-19
US20070281184A1 (en) 2007-12-06
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ES2715210T3 (es) 2019-06-03
RU2329979C1 (ru) 2008-07-27
JP2007534603A (ja) 2007-11-29
CA2563945A1 (fr) 2005-12-08
JP4768722B2 (ja) 2011-09-07
CA2563945C (fr) 2010-10-12
CN1946645A (zh) 2007-04-11
EP1742889B1 (fr) 2018-12-26
EP1742889A1 (fr) 2007-01-17
EP1742889B8 (fr) 2019-05-22
MXPA06012103A (es) 2007-01-25
CN1946645B (zh) 2011-11-23

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