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CN105814002B - 一种具较低可见光透射率低辐射涂层的涂层制品 - Google Patents

一种具较低可见光透射率低辐射涂层的涂层制品 Download PDF

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Publication number
CN105814002B
CN105814002B CN201380079929.1A CN201380079929A CN105814002B CN 105814002 B CN105814002 B CN 105814002B CN 201380079929 A CN201380079929 A CN 201380079929A CN 105814002 B CN105814002 B CN 105814002B
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CN
China
Prior art keywords
layer
coated article
silver
layer containing
contact
Prior art date
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Active
Application number
CN201380079929.1A
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English (en)
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CN105814002A (zh
Inventor
贝恩德·迪斯特尔多尔夫
安东·迪特里希
克里希纳·斯瓦米奈都
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.)
Guardian Europe SARL
Guardian Industries Corp
Guardian Glass LLC
Original Assignee
Centre Luxembourgeois de Recherches pour le Verre et la Ceramique CRVC SARL
Guardian Industries Corp
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Priority to CN201910356738.4A priority Critical patent/CN110104961B/zh
Publication of CN105814002A publication Critical patent/CN105814002A/zh
Application granted granted Critical
Publication of CN105814002B publication Critical patent/CN105814002B/zh
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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
    • E06B5/00—Doors, windows, or like closures for special purposes; Border constructions therefor
    • E06B5/10—Doors, windows, or like closures for special purposes; Border constructions therefor for protection against air-raid or other war-like action; for other protective purposes
    • E06B5/18—Doors, windows, or like closures for special purposes; Border constructions therefor for protection against air-raid or other war-like action; for other protective purposes against harmful radiation
    • 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
    • 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
    • B32B17/10201—Dielectric 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
    • B32B17/1022—Metallic 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
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    • B32B17/10229—Metallic layers sandwiched by dielectric layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
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    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
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    • 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
    • C03C17/001—General methods for coating; Devices therefor
    • C03C17/002—General methods for coating; Devices therefor for flat glass, e.g. float glass
    • 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
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    • C03C17/3429—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating
    • C03C17/3435—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating comprising a nitride, oxynitride, boronitride or carbonitride
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    • 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
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    • 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
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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
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    • 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
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    • 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
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    • 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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    • 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
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    • 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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    • C03C17/3636—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 silicon, hydrogenated silicon or a silicide
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    • 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
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    • 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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    • 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
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    • 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
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    • C—CHEMISTRY; METALLURGY
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    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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    • E06B3/6715—Units comprising two or more parallel glass or like panes permanently secured together characterised by additional arrangements or devices for heat or sound insulation or for controlled passage of light specially adapted for increased thermal insulation or for controlled passage of light
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    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
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    • Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
    • Y10T428/2495—Thickness [relative or absolute]
    • Y10T428/24967—Absolute thicknesses specified

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • General Physics & Mathematics (AREA)
  • Structural Engineering (AREA)
  • Civil Engineering (AREA)
  • Toxicology (AREA)
  • Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Inorganic Chemistry (AREA)
  • Surface Treatment Of Glass (AREA)
  • Laminated Bodies (AREA)
  • Securing Of Glass Panes Or The Like (AREA)

Abstract

本发明涉及一种含有低辐射(low‑E)涂层的涂层制品。在示例性实施例中，低辐射涂层被配置在基片(例如，玻璃基片)上，并包括：至少第一和第二红外(IR)反射层(例如，银基层)，通过接触层(例如，基于镍铬的层)和含有类似氮化硅材料的介质层被隔开。在示例性实施例中，涂层制品具有较低的可见光透射率(例如，不超过60％，更优选是约55％以下，且最优选是约50％以下)。

Description

一种具较低可见光透射率低辐射涂层的涂层制品
本发明涉及一种涂层制品，包括低辐射(low-E)涂层。在一些实施例中，低辐射涂层被配置在基片上(例如，玻璃基片)，并包括：至少第一和第二红外(IR)反射层(例如，银基层)，通过接触层(例如，基于镍铬的层)和含有类似氮化硅材料的介质层被隔开。在一些示例性实施例中，涂层制品(例如，单片形式和/或以绝缘玻璃窗单元形式)具有较低的可见光透射率(例如，不超过60％，更优选是约55％以下，且最优选是约50％以下)。在示例性实施例中，涂层制品可被热处理(例如，热回火和/或热弯曲)，并被设计成热处理(HT)时基本上热稳定，由于热处理其ΔE*值(玻璃侧反射)不超过5.0，且更优选是不超过4.5。根据本发明的示例性实施例的涂层制品可用于绝缘玻璃(IG)窗单元、车窗、其他类型的窗、或任何其他合适的应用。
发明背景
涂层制品在现有技术中被应用于窗，例如绝缘玻璃(IG)窗单元，车窗，和/或类似等。通常在一些情况下，将涂层制品热处理(例如，热回火，热弯曲和/或热强化)从而目的在于回火、弯曲、或类似等。涂层的热处理(HT)通常需要使用至少580摄氏度的温度，更优选是至少约600摄氏度，甚至更优选是至少620摄氏度。该高温(例如，5-10分钟以上)经常会使涂层分裂和/或恶化，或是以不可预知的方式改变。因此，最好是涂层能够承受这样的热处理(例如，热回火)，如果需要的话，以一种不会明显损害涂层的预知方式。
在一些情况下，涂层物品设计师试图将所需的可见光透射率、所需的颜色、低辐射(或辐射率)、以及低片电阻(Rs)相结合。低辐射(low-E)和低片电阻特性使该涂层制品阻挡大量的红外辐射，从而来减少车辆或建筑物内部不理想的热量。
美国专利No.7,521,096公开了一种低辐射涂层，在银基红外反射层之下使用氧化锌(ZnO)接触层，以及在底部的银(Ag)基红外反射层之上使用NiCrOx接触层，随后为中心氧化锡(SnO2)介质层，其内容被纳入此处作为参考。虽然银基红外反射层下面的氧化锌层提供良好的结构性能有助于银的增长，但是在一些情况下发现SnO2会降低涂层的化学性，环境及机械耐久性。此外，该厚的SnO2介质层被发现经热处理显示出微结晶和应力，其导致SnO2、ZnO和Ag之间的粗糙界面，从而可能引起耐久性的退化并影响透射的颜色。
美国专利No.5,557,462公开了一种具有SiN/NiCr/Ag/NiCr/SiN/NiCr/Ag/NiCr/SiN层堆栈的低辐射涂层。然而，“462专利”的涂层制品针对至少63％的高可见光透射率被设计。在“462专利的第3栏，第12-15行，指出可见光透射率低于70％(单片涂层制品)和低于63％(绝缘玻璃窗单元)都是不可取的。因此，“462专利直接背离了可见光透射率低于63％的涂层制品。此外，如美国专利No.8,173,263中仔细说明的，由于‘462专利的涂层制品在热处理时片电阻(RS)从约3-5上升至10，并产生雾霾，且玻璃侧反射ΔE*值不理想，超过5.0，因此不能被热处理。
因此，需要提供一种涂层，具有以下特性中一个或多个：(i)较低的可见光透射率，(ii)较好的耐久性，和(iii)热处理时较好的热稳定性，从而实现玻璃侧反射ΔE*值不超过5.0，更优选是不超过4.5。
在ASTM 2244-93以及Hunter等人的有关外观测量报告(The Measurement ofAppearance 2ndEd.Cptr.9，第162页及以下等内容中[John Wiley&Sons,1987]说明了本技术领域中的ΔE*(以及ΔE)，根据各种各种技术来确定该值。如本技术领域中所使用的，ΔE*(以及ΔE)是适当地表现热处理之后或由于热处理制品中的反射率和/或透射率中的变化(或不足之处)的方法。ΔE可通过"ab"技术被计算，或是通过Hunter技术(被指定使用下标的"H")。ΔE对应于Hunter Lab L,a,b标度(或是Lh,ah,bh)。相似的，ΔE*对应于CIE LAB标度L*,a*,b*。对于本发明的目的两者都十分实用并相同。例如，上述参考的Hunter等人的报告中，称为L*,a*,b*标度的直角坐标/标度技术(CIE LAB 1976)可被使用，其中，L*为(CIE 1976)明度单位；a*为(CIE 1976)红绿色单位；b*为(CIE 1976)黄蓝色单位，且L*oa*ob*o和L*1a*1b*1之间差距ΔE*为：ΔE*＝[(ΔL*)2+(Δa*)2+(Δb*)2]1/2，其中，ΔL*＝L*1–L*o；Δa*＝a*1–a*o；Δb*＝b*1–b*o。其中下标的"o"表示热处理之前的涂层(涂层制品)，下标的"1"表示热处理之后的涂层(涂层制品)，且使用的数字(e.g.,a*,b*,L*)由上述的(CIELAB 1976)L*,a*,b*坐标技术被计算。例如，当玻璃侧反射ΔE*值被测量时，然后玻璃侧反射a*,b*和L*值被测量。以相似的方法，ΔE可利用上述用于ΔE*的等式被计算，即，ΔE*＝[(ΔL*)2+(Δa*)2+(Δb*)2]1/2，使用Hunter Lab值ah,bh,Lh来替换a*,b*,L*。此外，当在本发明的范围内，转换成采用如上定义的相同概念ΔE*的任何其他技术被计算时，ΔE*的定量数值相同。
发明的示例性实施例概述
本发明涉及一种涂层制品，包括低辐射(low-E)涂层。在一些实施例中，低辐射涂层被配置在基片上(例如，玻璃基片)，并包括：至少第一和第二红外(IR)反射层(例如，银基层)，通过接触层(例如，基于镍铬的层)和含有类似氮化硅材料的介质层被隔开。在一些示例性实施例中，涂层制品具有较低的可见光透射率(例如，不超过60％，更优选是约55％以下，更优选是约50％以下)。在示例性实施例中，涂层制品可被热处理(例如，热回火和/或热弯曲)，并被设计成热处理(HT)时基本上热稳定，由于热处理其ΔE*值(玻璃侧反射)不超过5.0，且更优选是不超过4.5。该较低的ΔE*值示出经肉眼观察涂层制品在热处理(例如，热回火)之前和之后几乎具有相同的透射性和颜色特性。根据本发明的示例性实施例的涂层制品可用于绝缘玻璃(IG)窗单元、车窗、其他类型的窗、或任何其他合适的应用。
此外，在本发明的示例性实施例中，涂层包括含有氧化锆和/或氮氧化锆的层(例如，外层)。在示例性实施例中，该含有氧化锆和/或氮氧化锆的层比涂层中含有银的各红外反射层更薄。
优选是提供一种涂层制品，具有以下特性中一个、两个、或三个：(i)较低的可见光透射率，(ii)较好的耐久性，和(iii)热处理时的热稳定性，从而实现玻璃侧反射ΔE*值不超过5.0，更优选是不超过4.5。
在本发明的示例性实施例中，提供一种含有涂层的涂层制品，所述涂层由玻璃基片支撑，所述涂层包括：含有银的第一和第二红外(IR)反射层，所述第一红外反射层比所述第二红外反射层更靠近所述玻璃基片；含有镍铬的第一接触层，位于所述含有银的第一红外反射层之上并直接与其接触；含有氮化硅的介质层，位于所述含有镍铬的第一接触层之上并直接与其接触；含有镍铬的第二接触层，位于所述含有氮化硅的介质层之上并直接与其接触；所述含有银的第二红外反射层，位于所述含有镍铬的第二接触层之上并直接与其接触；含有镍铬的第三接触层，位于所述第二红外反射层之上并直接与其接触；另一个含有氮化硅的介质层，位于所述含有镍铬的第三接触层之上并直接与其接触；含有氧化锆的层，位于所述另一个含有氮化硅的介质层之上并直接与其接触，其中，所述含有银的第二红外反射层比所述含有银的第一红外反射层厚，其中，所述含有银的第一和第二红外反射层中的每一个比所述含有氧化锆的层至少厚两倍，且其中，所述涂层制品被单片测量的可见光透射率不超过60％。
附图简要说明
图1是示出根据本发明的示例性实施例的涂层制品的横截面图。
图2是示出根据本发明的示例性实施例的配置在绝缘玻璃窗单元中的图1的涂层制品的横截面图。
本发明示例性实施例的具体说明
在此所述的涂层制品，可用于类似绝缘玻璃窗单元，层压窗单元(例如，用于在车辆或建筑应用)、车辆窗、单片的建筑窗、住宅窗，和/或任何其他包括单个或多个玻璃基片的合适的窗应用中。
在本发明的一些示例性实施例中，该涂层包括双银堆栈。参考图1，例如，在本发明的一些实施例，提供了一种含有涂层的涂层制品，所述涂层由玻璃基支撑，包括：含有银或主要由银构成的第一红外(IR)反射层9和第二红外反射层19，第一红外反射层9比第二红外反射层19更靠近玻璃基片1；含有镍铬的第一接触层7，位于含有银的第一红外反射层9之下并直接与其接触，第二接触层11位于含有银的第一红外反射层9之上并直接与其接触；含有氮化硅的介质层14，位于含有镍铬的第一接触层11之上并直接与其接触；含有镍铬的第三接触层17，位于含有氮化硅的层14之上并直接与其接触；含有银的第二红外反射层19，位于含有镍铬的第二接触层17之上并直接与其接触；含有镍铬的第四接触层21，位于第二红外反射层19之上并直接与其接触，其中，含有银的第二红外反射层19与含有银的第一红外反射层9至少一样厚。在一些优选的实施例中发现，当含有银的第二红外反射层19比含有银的第一红外反射层9更厚时可实现令人惊讶的有益效果，更优选是，第二红外反射层19比含有银的第一红外反射层9至少厚(更优选是至少厚)。如图1所示，涂层包括三个含有氮化硅的介质层3、14和24。此外，涂层包括含有氧化锆和/或氮氧化锆的层(例如，外层)27。在一些实施例中，该含有氧化锆和/或氮氧化锆的层27比涂层中含有银的红外反射层9，19中的一个或两个更薄。在本发明的一些实施例中，含有银的各红外反射层9、19与含有氧化锆和/或氮氧化锆的层27相比，至少厚两倍，更优选是至少厚三倍。在本发明的一些示例性实施例中，涂层仅包括2个含有银或类似等的红外反射层9、19。
为了提高耐久性，以及光学和热学性能，并在热处理之前和之后避免较大的结构性转变，根据本发明的一些实施例的涂层制品具备含有氮化硅的中心介质层14和基于镍铬的下接触层7、17(相对于ZnO)。此外还发现使用金属或基本金属的镍铬(可能部分被氮化)来用于层7、11、17和/或21可提高化学、机械、和环境的耐久性(相比在银之下使用氧化锌的下接触层和/或在银之上使用高氧化的镍铬上接触层)。在此还发现，在非晶质状态下，溅射沉积含有氮化硅的层14，从而使半涂层和热处理状态下都为非晶质，可有助于涂层的整体稳定性。例如，美国专利No.7,521,096中的涂层，经1小时65摄氏度下的5％HCl将会被除去，然而图1中所示的涂层以及在此所述的示例将通过该HCl测试。在高温高湿的环境下，与两天曝光后的‘096专利中的涂层相比，十天曝光后的图1所示的涂层以及在此所述的示例则损害更少。对于那些用于“砖洗”的高腐蚀性化学物质，用于抗腐蚀的切边不需要在示例性实施例和层压示例中被执行。相似地，对于机械磨损测试、热循环及盐雾测试，在此所述的示例性涂层被发现比‘096专利更佳。此外，发现，使顶部银基红外反射层19比底部银基红外反射层9更厚时可提高涂层光学特性。由于ΔE*值相对较低，该涂层可以是半涂层或被热处理。例如，当涂层30位于绝缘玻璃窗单元的表面#2(如图2所示)时，由于热处理玻璃侧反射ΔE*值较低，示出在热处理(如热回火)之前和之后经肉眼观察几乎具有相同的透射率和颜色特征，因此作为半涂层或被热处理不会严重影响其光学特性。
在本发明的一些实施例中，如图1，热处理或非热处理的涂层制品具有多个红外反射层(例如，两个隔开的银基层)可实现小于或等于5.0的片电阻(RS)(更优选是小于或等于4.0，甚至更优选是小于或等于3.0)。“热处理”和“热处理”的术语表示加热到足够的温度，以实现玻璃制品的热回火、热弯曲、和/或热强化。该定义包括，例如，至少约580摄氏度的温度下在烤炉或加热炉中加热涂层制品，更优选是至少约600摄氏度，以足够的时间允许回火、弯曲、和/或热强化。在一些情况下，热处理可以是至少约4分钟或5分钟。在本发明的不同实施例中，涂层制品可被热处理或也可以不热处理。
图1是根据本发明的非限制性示例实施例的涂层制品的侧横截面图。该涂层制品包括：基片1(例如，透明、绿色、青铜色、或蓝绿色的玻璃基片，厚度约为1.0-10.0毫米，更优选是厚度约为1.0-3.5毫米)；和低辐射涂层(或层系统)30，直接或间接地配置在基片1上。涂层(或层系统)30包括，例如：底部介质氮化硅层3，其可以是Si3N4，或是富硅型的氮化硅来减少灰霾，或是本发明的不同实施例中任何其他合适的化学计量氮化硅；下接触层7(其接触底部红外反射层9)；导电的优选是金属或基本金属的第一红外(IR)反射层9；上接触层11(其接触层9)；基于和/或含有氮化硅的介质层14；下接触层17(其接触红外反射层19)；导电的优选是金属或基本金属的第二红外反射层19；上接触层21(其接触层19)；氮化硅介质层24，其可以是Si3N4，富硅型来减少雾霾，或是本发明的不同实施例中任何其他合适的化学计量氮化硅；和含有类似氧化锆(例如ZrO2)和/或氮氧化锆材料的外层27。“接触”层11、7、17和21分别接触红外反射层(例如，银基层)。上述层3-27用来制备低辐射(即低辐射率)涂层30，配置在玻璃或塑料基片1上。在本发明的一些实施例中，层3-27可溅射沉积在基片1上，各层根据需要通过使用一个或多个目标在真空中被溅射沉积(溅射目标可以是陶瓷或金属)。金属或基本金属的层(例如，层7、9、11、17、19和21)可在含有氩气的氛围中被溅射，其中氮化层(例如，层3、7、11、14、17、21和24)可在含有氮氩混合气体的氛围中被溅射。在本发明的不同实施例中，接触层7、11、17和21可被氮化或也可以不被氮化。
在单片的情况下，如图1所示，涂层制品仅包括一个玻璃基片1。然而，在此所述的单片涂层制品可用于类似层压的汽车挡风玻璃、绝缘玻璃窗单元等装置中。用于绝缘玻璃窗单元时，绝缘玻璃窗单元可包括2个隔开的玻璃基片。示例性的绝缘玻璃窗单元被示出并说明，例如美国专利文件No.2004/0005467中所公开的内容，其被纳入此处作为参考。图2示出含有图1中所示的涂层玻璃基片1的示例性绝缘玻璃窗单元，通过隔离片、密封胶40或类似等被耦合到另一个玻璃基片2，其之间被定义有间隙。绝缘玻璃窗单元实施例中基片之间的间隙在一些情况下被填入气体，例如氩气(Ar)。示例性绝缘玻璃单元可包括一对被隔开的玻璃基片，厚度分别为3-4毫米，在示例性例子中，其中一个被涂有在此所述的涂层30，基片之间的间隔可约为5-30毫米，更优选是约为10-20毫米，且最优选是约为16毫米。在示例性例子中，低辐射涂层30可面对间隙配置在任一基片的内表面(虽然在图2中涂层被示出面对间隔位于基片1内部主要表面上，但是也可以是面对间隔位于基片2的内部主要表面上)。无论是基片1或基片2可以是建筑外墙的绝缘玻璃窗单元的最外层基片(例如，图2中基片1是最接近外墙的基片，且涂层30被配置在绝缘玻璃窗单元的表面#2上)。
在本发明的示例性实施例中，接触层7、11、17、21中的一个、两个、三个或四个可包括镍铬(任何合适的Ni对Cr比例)，可被氮化或是也可以不被氮化(NiCrNx)。在一些实施例中，含有镍铬的层7、11、17、21中的一个、两个、三个或四个为基本或完全非氧化的。在一些实施例中，层7、11、17和21可能都是金属镍铬或基本金属镍铬(尽管其他微量元素可能存在)。在一些实施例中，基于镍铬的层7、11、17、21中的一个、两个、三个或四个可含有0-10％的氧气，更优选是0-5％的氧气，最优选是0-2％的氧气(原子百分比)。在一些实施例中，层7、11、17、21中的一个、两个、三个或四个可含有0-20％的氮气，更优选是1-15％的氮气，最优选是约12％的氮气(原子百分比)。基于镍铬的层7、11、17和/或21可以或也可以不掺杂其他物质，如不锈钢、钼等。在此发现，在银基红外反射层9、19下使用基于镍铬的接触层7和/或17可提高涂层制品的耐久性(与使用氧化锌的层7和17相比)。
本发明的特定实施例中，介质层3、14、24可以是或包含氮化硅。氮化硅层3、14和24可位于其他物质之前，提高涂层制品的热处理性，并在选择性热处理期间保护其他层，例如热回火等。在本发明的不同实施例中，氮化硅层中3、14、24一个或多个可以是化学计量式(即，Si3N4)，或者富硅型氮化硅。例如，富硅型氮化硅层3和/或14中存在的自由硅，可使热处理过程中从玻璃基片1中向外迁移的类似钠(Na)的特定原子，在达到银和损害银之前经富硅型氮化硅层被更有效地制止。因此，在本发明的选择性示例实施例中，富硅型SixNy可减少热处理过程中对于银层的损害，使片电阻(Rs)减少或以符合要求的方式保持不变。此外，在本发明的选择性示例实施例中，层3、14和/或24中的富硅型SixNy可减少热处理过程中对于银和/或镍铬的损害(例如，氧化)。在一些实施例中，当使用富硅型氮化硅时，沉积的富硅型氮化硅层(3、14和/或24)可以是SixNy层特征，其中X/Y可以是0.76-1.5，更优选是0.8-1.4，且更优选是0.82-1.2。在本发明的示例性实施例中，在此所述的氮化硅层中的任何一个和/或所有可掺杂其他材料，如不锈钢或铝。例如，在本发明的示例性实施例中，在此所述的氮化硅层3、14、24中的任何一个和/或所有可选择性地包括约0-15％的铝，更优选是约1-10％的铝。在本发明的示例性实施例中，氮化硅层3、14、24可通过在氩气和氮气的氛围中溅射硅或硅铝目标被沉积。在一些情况下，也可在氮化硅层中提供少量的氧气。
红外线(IR)反射层19和9优选是基本或完全金属的和/或导电的，并可包括或基本上由银(Ag)、金、或任何其他合适的红外反射材料构成。红外反射层9和19使涂层具有低辐射和/或良好的太阳能控制特性。
还可在示出的涂层之下或之上提供其他层。因此，虽然层系统或涂层位于基片1“上”或由基片1(直接或间接地)“支撑”，但其他层也可配置在其之间。因此，例如，即使层3和基片1之间配置有其他层，图1中的涂层也可被视为位于基片1“上”或由基片1“支撑”。此外，在不脱离本发明实施例的整个思想范围下，在一些实施例中，示出的涂层中的特定层可被去除，且在本发明的其他实施例中，各种层之间可添加其他层，或是各种层可与分开部分之间添加的其他层断开。
在本发明的不同实施例中，层中可使用各种厚度和材料，以下示出针对图1实施例中的玻璃基片1上的层的示例性厚度和材料，从玻璃基片开始向外(物理厚度被列举)：
示例性材料/厚度；图1实施例
含有银的第二红外反射层19至少与含有银的第一红外反射层9一样厚。在一些优选的实施例中，发现可实现更惊人的有效结果，当含有银的第二红外反射层19比含有银的第一红外反射层9更厚时，更优选是，当第二红外反射层19比含有银的第一红外反射层9至少厚时(更优选是至少厚)。
在一些优选的实施例中，含有氧化锆和/或氮氧化锆的层27比涂层30中含有银的各红外反射层9、19更薄。在本发明的示例性实施例中，含有银的红外反射层9和19中的每一个比含有氧化锆和/或氮氧化锆的层27至少厚2倍，且更优选是至少厚3倍。
在示例性实施例中，中心基于氮化硅的层14，厚度大于其他基于氮化硅的层3和24中的每一个，优选是至少为更优选是至少为最优选是至少为此外，在一些示例性实施例中，氮化硅层3、14和24中的每一个，至少比氧化锆层27厚2倍，更优选是至少厚3倍，且最优选是厚4倍或5倍。
涂层30提供良好的耐久性，并与单个基于银的低辐射涂层相比，具有较低的玻璃侧和外侧可见光反射率。但是ΔE*值通常在4-5的范围内。涂层以及含有涂层的涂层制品可被设计为透射和反射中呈现出浅蓝色，但在选择性的热处理之后可变得略微中性。
在本发明的示例性实施例中，当涂层制品被单片测量时(选择性地热处理前和/或后)可具有以下的光学和太阳能特性。在此，片电阻(Rs)被涉及所有的红外反射层(例如，银层9、19)。应注意，“热处理前”表示被退火，但在所述的类似热回火的高温热处理之前。
光学/太阳能特性(单片–热处理前)
光学/太阳能特性(单片–热处理后)
从上面可以看出，热处理(例如，热回火)稍微增加了涂层制品的可见光透射率。
在本发明的示例性绝缘玻璃窗实施例中，涂层制品选择性地被热处理，从而在一定程度上充分回火，并被耦合至另一个玻璃基片来形成绝缘玻璃单元，在如图2所示的结构中可具有以下所述的光学/太阳能特性，(例如，两个玻璃片的厚度分别约为6毫米的透明玻璃，具有约为16毫米的间隙，其之间填充有90/10的氩气/空气)。在本发明的示例性实施例中，该绝缘玻璃窗单元可具有约20-55％的可见光透射率。
以下本发明的示例仅作为示例被提供，除了特别声明，其并不局限于此。
示例1-3
以下示例1-3通过将涂层溅射在6毫米厚的清楚/透明的玻璃基片上被制备，从而使图1中说明的层厚度大约具有以上表中“示例”栏中所示出的层厚度。
以下示出示例1-3的光学性能，针对如图1所示的单片涂层制品被测量。下表中所有的测量值为热处理前。请注意，“f”表示薄膜反射率，即，涂层制品的薄膜侧的反射率，而“g”表示玻璃侧反射率。
单片(热处理前)
从上面的示例可以看出，被单片测量的涂层制品具有理想的较低可见光透射率，并具有非常理想的玻璃侧反射颜色。特别是，单片的a*g(玻璃侧反射a*颜色)在约-1至-5的理想范围内，且b*g(玻璃侧反射b*颜色)在约-5至-10的理想范围内。此外，玻璃侧可见光反射率(RgY)较好，其低于10％，更优选是不超过9％。特别是如图2所示，当涂层制品被放置在绝缘玻璃窗单元中时都为理想的特性。
以下说明为热回火之后单片测量的涂层制品示例1-3的光学特性。
单片(热处理后)
从上面的示例可以看出，被单片测量的涂层制品具有理想的较低可见光透射率，并有相当理想的玻璃侧反射颜色。特别是，在示例2-3中单片的a*g(玻璃侧反射a*颜色)在约0至-2的理想范围内，且在示例2-3中b*g(玻璃侧反射b*颜色)在约-8至-12的理想范围内。此外，玻璃侧可见光反射率(RgY)较好，其低于10％。特别是如图2所示，当涂层制品被放置在绝缘玻璃窗单元中时都为理想的特性。
以下示出含有示例1-3中涂层制品的绝缘玻璃窗单元的光学特性，即，如图2所示，涂层制品被放置在绝缘玻璃窗单元中(位于绝缘玻璃窗单元的表面#2上，从而玻璃侧反射值自外侧被示出)。该值针对绝缘玻璃单元中所使用的非热处理涂层制品(即，没有被热回火)。
绝缘玻璃单元(非热处理)
虽然参照最实用和优选的实施例对本发明进行了说明，但是应理解，本发明并不局限于所述实施例，相反可进行各种修改和等效的配置，修改将由后附的权利要求范围定义。

Claims (23)

1.一种含有涂层的涂层制品，所述涂层由玻璃基片支撑，所述涂层包括：
含有银的第一和第二红外反射层，所述第一红外反射层比所述第二红外反射层更靠近所述玻璃基片；
含有镍铬的第一接触层，位于所述含有银的第一红外反射层之上并直接与其接触；
含有氮化硅的介质层，位于所述含有镍铬的第一接触层之上并直接与其接触；
含有镍铬的第二接触层，位于所述含有氮化硅的介质层之上并直接与其接触，
所述含有银的第二红外反射层，位于所述含有镍铬的第二接触层之上并直接与其接触；
含有镍铬的第三接触层，位于所述第二红外反射层之上并直接与其接触；
另一个含有氮化硅的介质层，位于所述含有镍铬的第三接触层之上并直接与其接触；
含有氧化锆的层，位于所述另一个含有氮化硅的介质层之上并直接与其接触，
其中，所述含有银的第二红外反射层比所述含有银的第一红外反射层厚；
其中，所述含有银的第一和第二红外反射层中的每一个比所述含有氧化锆的层至少厚两倍，且
其中所述涂层还包括含有NiCr的另一接触层，所述含有NiCr的另一接触层位于含有银的所述第一红外反射层之下并直接与其接触，并且其中所述含有NiCr的另一接触层位于所述第一红外反射层和含有氮化硅的最底部介质层之间并且直接与所述第一红外反射层和含有氮化硅的最底部介质层接触，所述含有氮化硅的最底部介质层直接与玻璃基片接触，
其中，所述涂层制品被单片测量的可见光透射率不超过60％。
2.根据权利要求1所述的涂层制品，其中，每个含有银的所述第一和第二红外反射层比所述含有氧化锆的层至少厚三倍。
3.根据权利要求1所述的涂层制品，其中，每个含有银的所述第一和第二红外反射层比所述含有氧化锆的层至少厚四倍。
4.根据上述权利要求中任何一项所述的涂层制品，其中，所述含有氧化锆的层进一步包括氮。
5.根据权利要求1-3中任一项所述的涂层制品，其中，所述含有银的第二红外反射层比所述含有银的第一红外反射层至少厚
6.根据权利要求1-3中任一项所述的涂层制品，其中，所述含有银的第二红外反射层比所述含有银的第一红外反射层至少厚
7.根据权利要求1-3中任一项所述的涂层制品，其中，所述含有银的第二红外反射层比所述含有银的第一红外反射层至少厚
8.根据权利要求1-3中任一项所述的涂层制品，其中，位于所述含有镍铬的第一接触层之上并直接与其接触的所述含有氮化硅的介质层为非晶质。
9.根据权利要求1-3中任一项所述的涂层制品，其中，所述含有镍铬的第一接触层为基本金属或金属，并含有不超过5％原子百分比的氧气。
10.根据权利要求1-3中任一项所述的涂层制品，其中，所述含有镍铬的第二接触层为基本金属或金属，并含有不超过5％原子百分比的氧气。
11.根据权利要求1-3中任一项所述的涂层制品，其中，所述含有镍铬的第三接触层为基本金属或金属，并含有不超过5％原子百分比的氧气。
12.根据权利要求1-3中任一项所述的涂层制品，其中，所述第一、第二和/或第三接触层进一步含有氮。
13.根据权利要求1-3中任一项所述的涂层制品，其中，所述涂层制品被单片测量的可见光透射率为20-60％。
14.根据权利要求1-3中任一项所述的涂层制品，其中，所述涂层制品没有被热回火，且被单片测量的可见光透射率为20-55％。
15.根据权利要求1-3中任一项所述的涂层制品，其中，所述涂层制品被热回火。
16.根据权利要求15所述的涂层制品，其中，所述涂层制品被热处理，且由于所述热处理，玻璃侧光反射ΔE*值不超过5.0。
17.根据权利要求16所述的涂层制品，其中，所述涂层制品被热处理，且由于所述热处理，玻璃侧光反射ΔE*值不超过4.5。
18.根据权利要求1-3中任一项所述的涂层制品，其中，所述含有银的第一红外反射层的厚度为且所述含有银的第二红外反射层的厚度为
19.根据权利要求1-3中任一项所述的涂层制品，其中，所述含有氧化锆的层的厚度为
20.根据权利要求1-3中任一项所述的涂层制品，其中，所述涂层具有小于或等于4.0欧姆/平方的片电阻Rs。
21.一种绝缘玻璃窗单元，包括上述权利要求中任何一项所述的涂层制品，以及被耦合至所述涂层制品的另一个玻璃基片。
22.一种含有涂层的涂层制品，所述涂层由玻璃基片支撑，所述涂层包括：
含有氮化硅的第一介质层，位于玻璃基片之上并直接与其接触；
含有NiCr的第一接触层，位于含有银的第一红外反射层之下并直接与其接触，并且其中所述含有NiCr的第一接触层位于所述第一红外反射层和含有氮化硅的第一介质层之间并且直接与所述第一红外反射层和含有氮化硅的第一介质层接触，所述含有氮化硅的第一介质层直接与玻璃基片接触；
含有银的第二红外反射层，位于所述含有氮化硅的第一介质层之上并且位于第一红外反射层之上，所述第一红外反射层比所述第二红外反射层更靠近所述玻璃基片；
第二接触层，位于所述含有银的第一红外反射层之上并直接与其接触；
含有氮化硅的第二介质层，位于所述第二接触层之上并直接与其接触；
第三接触层，位于所述含有氮化硅的第二介质层之上并直接与其接触；
所述含有银的第二红外反射层，位于所述第三接触层之上并直接与其接触；
第四接触层，位于所述第二红外反射层之上并直接与其接触；
含有氮化硅的第三介质层，位于所述第四接触层之上并直接与其接触；
含有氧化锆的层，位于所述含有氮化硅的第三介质层之上并直接与其接触，
其中，所述含有银的第二红外反射层比所述含有银的第一红外反射层厚；
其中，所述含有银的第一和第二红外反射层中的每一个比所述含有氧化锆的层至少厚两倍，且
其中，所述涂层制品被单片测量的可见光透射率不超过60％。
23.根据权利要求22所述的涂层制品，其特征在于，所述含有NiCr的第一接触层为金属或基本金属的并且含有不超过5％原子百分比的氧。
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