CN101395000A - 被提供有热性能的叠层的基材 - Google Patents

被提供有热性能的叠层的基材 Download PDF

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CN101395000A
CN101395000A CNA2007800077976A CN200780007797A CN101395000A CN 101395000 A CN101395000 A CN 101395000A CN A2007800077976 A CNA2007800077976 A CN A2007800077976A CN 200780007797 A CN200780007797 A CN 200780007797A CN 101395000 A CN101395000 A CN 101395000A
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layer
base material
coating
lower floor
lamination
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CN101395000B (zh
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P·鲁特勒
N·纳多德
E·马丁
L·拉布劳斯
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Saint Gobain Glass France SAS
Compagnie de Saint Gobain SA
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    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06Layered 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
    • B32B17/10Layered 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
    • B32B17/10005Layered 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
    • B32B17/10009Layered 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 number, the constitution or treatment of glass sheets
    • B32B17/10036Layered 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 number, the constitution or treatment of glass sheets comprising two outer glass sheets
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    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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    • B32B17/06Layered 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06Layered 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
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    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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    • B32B17/10005Layered 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
    • B32B17/10165Functional features of the laminated safety glass or glazing
    • B32B17/10174Coatings of a metallic or dielectric material on a constituent layer of glass or polymer
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    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06Layered 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
    • B32B17/10Layered 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
    • B32B17/10005Layered 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
    • B32B17/1055Layered 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
    • B32B17/10761Layered 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
    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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    • B32B17/06Layered 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
    • B32B17/10Layered 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
    • B32B17/10005Layered 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
    • B32B17/1055Layered 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
    • B32B17/10788Layered 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 ethylene vinylacetate
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36Surface 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
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
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    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36Surface 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
    • C03C17/3602Surface 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
    • C03C17/3626Surface 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
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36Surface 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
    • C03C17/3602Surface 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
    • C03C17/3639Multilayers containing at least two functional metal layers
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36Surface 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
    • C03C17/3602Surface 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
    • C03C17/3652Surface 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 coating stack containing at least one sacrificial layer to protect the metal from oxidation
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36Surface 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
    • C03C17/3602Surface 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
    • C03C17/3657Surface 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
    • C03C17/366Low-emissivity or solar control coatings
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36Surface 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
    • C03C17/3602Surface 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
    • C03C17/3668Surface 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 electrical properties
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
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    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36Surface 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
    • C03C17/3602Surface 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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    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract

本发明涉及一种基材(10),被提供有一种薄层叠层,该叠层包含具有在红外和/或日光范围反射性能的n个功能层(40、80)的交替排列,以及(n+1)个涂层(20、60、200),其中n是整数,≥2,所述涂层由多个介电层(24、26;64、66;104)组成,让每个功能层(40)位于2个涂层(20、60、100)之间,至少2个功能层(40、80)每个沉积在润湿层(30、70)上,润湿层本身分别直接沉积到下层涂层(20、60)上。本发明基材的特征在于,2个下层涂层(20、60)每个包含至少一个介电层(24、64)和至少一个非结晶平滑层(26、66),构成该(平滑)层的材料不同于每个涂层内所述介电层的材料,所述平滑层(26)与所述下层润湿层(30)相接触。本发明的特征还在于,由于这2个下层涂层(20、60)厚度不相同,故让总厚度小于其他下层涂层(60、20)的下层涂层(20、60)的平滑层(26、66)的厚度小于或等于所述其他下层涂层(60、20)的平滑层(66、26)的厚度。

Description

被提供有热性能的叠层的基材
本发明涉及透明基材,尤其是由刚性无机材料如玻璃制成的那些,所述基材覆盖有薄层叠层,该薄层的叠层包含至少2个能作用于日光和/或长波长的红外线的金属型功能层。
本发明更具体地说涉及此种基材用于制造热绝缘和/或防晒保护玻璃(vitrage)的用途。这样的玻璃可用于装备建筑物或车辆,尤其着眼于减少由建筑物和车辆车厢内日益增长的玻璃表面的使用所带来的空调负荷和/或过度晒热(被称作“日光控制”玻璃)和/或减少能量朝外部的散失(被称作“低-发射”玻璃)。
这样的玻璃另外还可集成为具有特殊功能的玻璃,例如,发热玻璃或电致变色玻璃。
赋予基材此类性能的一种公知类型的叠层由至少2个具有在红外和/或日光范围的反射性能的基于银或含银金属合金的金属功能层组成。
每个金属功能层以结晶形式沉积在润湿层上,后者也是结晶的并且促使沉积在它上面的金属层的恰当的结晶取向。
每个功能层被置于2个由金属氧化物或氮化物类的介电材料制成的涂层之间。该叠层通常由采用真空技术,例如,任选地磁场辅助的阴极喷镀(pulvérisation cathodique),实施的一系列沉积操作来获得。还可提供1个,或甚至2个,非常薄的膜,被称为“阻隔涂层”,这个或这些涂层直接置于每个银基金属功能层的下面、上面或每一侧,当后面可能的对沉积物的热处理时,该下层涂层(revêtement sous-jacent)作为粘结层(revêtement d’accrochage)、成核层和/或保护层,和如果置于银基层上面的层在氧或氮气的存在下通过阴极喷镀进行沉积和/或如果叠层在沉积后经受热处理时,该上层涂层作为保护层或“牺牲层”以防止银受到损坏。
譬如,此类型具有2个银基层的叠层,可从欧洲专利申请EP-0638528得知。
再有,从欧洲专利申请No.EP 803 481已知一种直接接触基材、用在基于氧化锌的润湿层下层、基于锌-锡的混合氧化物的无定形层。
原来,当此种无定形层不是直接沉积到基材上去,而是被插入到下层介电层与润湿层之间时,它可以改性介电层与位于其上的润湿层之间的界面并从而显著改善润湿层的结晶,同时也显著改善金属功能层的结晶。
然而,在具有多个功能层的叠层中,将这样一种无定形层并入到在功能层下面的并备有至少一个位于该无定形层下面的每个涂层中,并不能在每种情况下都达到功能层所希望的结晶改进并从而达到整个叠层电阻率的所希望的改进。
因此,本发明的目的是弥补现有技术的缺点,开发出具有上面描述的那些类型功能层的新型叠层,该叠层具有改进的电阻率,电阻率比具有相当功能层和涂层厚度的类似叠层更低,所述叠层经受或不经受一次(或多次)弯曲、钢化和退火类的高温热处理,如果它经受一次(或多次)种此类处理,则其光学品质和机械完整性仍将保持不变。
因此,本发明的目的,就其最广的公认意义而言,是一种基材,尤其是透明玻璃基材,其被提供有薄层叠层,该叠层包含具有在红外和/或日光范围反射性能的n个功能层的交替排列,尤其是基于银或含银金属合金的金属功能层,以及(n+1)个涂层,其中n是整数,≥2,所述涂层包括多个介电层,以便让每个功能层位于2个涂层之间,至少2个功能层每个沉积在润湿层上,润湿层本身分别直接沉积到下层涂层上,特征在于,2个下层涂层每个包含至少一个介电层和至少一个非结晶平滑层,该平滑层的材料不同于每个涂层内所述介电层的材料,所述平滑层与所述上层润湿层相接触,特征还在于,这2个下层涂层厚度各不相同,总厚度小于其他下层涂层的下层涂层的平滑层的厚度小于或等于上述其他下层涂层的平滑层的厚度。
于是,本发明在于提供位于润湿层下方的非结晶平滑层,为了使位于该润湿层上面的功能层的恰当生长,该平滑层与润湿层直接接触或者通过下阻隔涂层(revêtement de sous-blocage)的介质。
平滑层的结晶学外观必定区别于润湿层,因为平滑层是非结晶的,而润湿层基本上是结晶的;因此,从这一角度看它们不可能被混淆。
然而,现已发现,在具有多个功能层的叠层中,重要的是要考虑下层涂层的厚度以便计算存在于这些下层涂层中的平滑层的厚度。
于是,本发明在于提供:较薄下层涂层的平滑层的厚度不得大于较厚下层涂层的平滑层的厚度。
本发明适用于涂层,该涂层在功能层下面,,不论功能层在叠层中的位置如何;然而,优选的是,在同一个薄层叠层中,所有包含平滑层的下层涂层都符合本发明的定义。
就本发明的意义而言,当提到层或涂层(包含一个或多个层)的沉积是直接在另一沉积层之下或直接在其上实施时,指的是在这两个沉积层之间不得有其他层插入。
平滑层优选地是基于氧化物的;因此,它们不是金属的。
平滑层在以下意义上被称作为“非结晶的”:它们可以是完全无定形或者部分无定形,因此是部分结晶的,但它们在其整个厚度不能是完全结晶的。
此种平滑层的优点能获得稍微粗糙的、与直接在上面的润湿层之间的界面。此种低粗糙度界面还可用透射电镜进一步看出。
再者,润湿层具有较好质地,另外还具有更明显的优选的结晶取向。
因此,每个平滑层由不同于直接位于其上方的润湿层的材料组成,从结晶学和化学计量的角度都不同。
本发明不仅仅适用于叠层,该叠层仅包括2个位于3个涂层之间的功能层,上述涂层中2个涂层是下层涂层。它也适用于叠层,该叠层包含3个与4个涂层交替排列的功能层,其中上述涂层中的3个是下层涂层,或者包含4个与5个涂层交替排列的功能层,其中上述涂层中的4个是下层涂层。
就这些具有多个功能层的叠层而言,至少1个功能层,优选每个功能层,被直接置于至少一个下层阻隔涂层上面和/或直接置于至少一个上层阻隔涂层的下面。
在具有2个功能层的叠层的情况下,甚至在其他情况下也是,所述包含平滑层的下层涂层当中的最薄涂层,优选地最靠近基材,甚至与基材接触,不论直接地抑或通过“接触层”介质,例如,基于二氧化钛(TiO2)。
在具有多于2个功能层的叠层的情况下,离基材最远的下层涂层是2个相邻下层涂层中的较薄层。
优选地是,至少一个平滑层,甚至所有平滑层,是氧化物层,尤其是混合氧化物层,它们基于下列金属中的一种之一或多种的氧化物:Sn、Si、Ti、Zr、Hf、Zn、Ga、In,更确切地说,是在低温沉积的基于锌和锡的混合氧化物的层或铟锡混合氧化物(ITO)的层。
平滑层的指数优选地小于2.2。
优选地是,另外,至少一个平滑层,甚至所有平滑层,是具有非化学计量氧含量的氧化物层,更具体地说,基于亚化学计量的以锑掺杂的锌和锡的混合氧化物(SnZnOx:Sb,x是数字)层。
另外,该(或每个)平滑层优选地具有介于0.1~30nm的几何厚度,更优选0.2~10nm,特别是对于2个当中较薄的那个。
在优选的实施方案中,至少一个阻隔涂层基于Ni或Ti或基于镍基合金,尤其是基于NiCr合金。
另外,至少1个,优选地每个,相对于功能层为下层润湿层优选地基于氧化锌;这些润湿层尤其可基于铝-掺杂的氧化锌。
每个润湿层的几何厚度优选介于2~30nm,更优选介于3~20nm。
而且,至少1个,优选每个,在所述下层涂层内与平滑层相邻的介电层,特别是直接在平滑层下面的介电层,优选基于氮化物,尤其是氮化硅和/或氮化铝。
该氮化物基介电层的指数优选地小于2.2。
本发明玻璃至少包括载有本发明的叠层的基材,任选地与至少1个其他基材的组合。每个基材可以是透明或着色的。其中至少一个基材尤其可由本体-着色的玻璃制成。着色类型的选择将取决于该玻璃一旦制造完成后所要求的透光率(niveau de transmission lumineuse)和/或色度学外观。
因此,就用于装配车辆的玻璃来说,某些标准规定,挡风玻璃应具有约75%的透光率TL,而其他标准则要求约65%的透光率TL;例如侧窗或天窗则不要求这样的透光率水平。例如,可使用的着色玻璃是,对于4mm厚度的而言,在光源D65下,具有65%~95%的TL,40%~80%的透能率TE,470nm~525nm的主透射波长的玻璃,与0.4%~6%的透射纯度的结合,这可在色度体系(L,a*,b*)中通过分别介于-9~0之间和-8~+2之间的透射a*和b*值“表示(traduire)”。
就用于装配在建筑物上的玻璃来说,对于“低-透射的”应用,该玻璃优选地具有至少75%或更高的透光率TL,以及对于“日光控制”应用至少40%或更高的透光率TL
本发明的玻璃可具有层压结构,尤其结合了至少2个玻璃型刚性基材与至少1个热塑性聚合物片材的玻璃,从而具有以下类型的结构:玻璃/薄层叠层/1个或多个片材/玻璃。该聚合物尤其可基于聚乙烯醇缩丁醛(PVB)、乙烯/醋酸乙烯(EVA)、聚对苯二甲酸乙二醇酯(PET)或聚氯乙烯(PVC)。
该玻璃还可具有所谓不对称的层压玻璃结构,它结合了玻璃型刚性基材与至少一个具有吸能性质的聚氨酯型聚合物片材,任选地结合另一层具有“自愈”性能的聚合物。有关此类型玻璃的进一步细节可参见,尤其是专利EP-0 132 198、EP-0 131 523、EP-0 389 354。
因此,该玻璃具有以下类型的结构:玻璃/薄层叠层/聚合物片材。
本发明玻璃能经受热处理而对薄层叠层没有损害。因此,任选地它们进行弯曲和/或钢化处理。
该玻璃,当由备有叠层的单一基材组成时,可接受弯曲和/或钢化处理。这时,它被称作“单块(monolithique)”玻璃。当该玻璃被弯曲,尤其是为了制造车窗时,薄层叠层优选地位于至少部分地非平面的面上。
该玻璃也可以是多(层)玻璃,尤其是双层玻璃,至少该载有叠层的基材可以被弯曲和/或钢化。在多层玻璃结构中优选的是,该叠层被置于面朝气体-充填空间的位置。在层压结构中,载有叠层的基材优选地与聚合物片材接触。
当该玻璃是整块或呈双层玻璃或层压玻璃型的多层玻璃时,至少该载有叠层的基材可由弯曲或钢化玻璃制成,该基材可在叠层沉积之前或之后进行弯曲或钢化处理。
在一种实施方案中,该玻璃被提供能对所述叠层提供电能的手段。
本发明还涉及一种制造本发明的基材的方法,它包括采用阴极喷镀类真空技术(任选地由磁场辅助)在其基材上沉积薄层叠层,随后对被覆盖的基材实施弯曲/钢化或退火等类型热处理,而不会损害其光学和/或力学品质。
然而,并不排除叠层的1个或多个第一层可以利用其他技术进行沉积,例如,采用高温热解型热分解技术。
本发明的细节和优点特征通过以下借助于附图示出的非限制性实施例将变得更清楚。
图1示出了单功能层的叠层(有或没有平滑层)的薄层电阻在热处理前随着设置在下面的介电层厚度的变化,该叠层被提供有上阻隔单层涂层;
图2示出了与图1所示相同的单功能层的叠层(有或没有平滑层)的薄层电阻在热处理后随着位于其下的介电层的厚度的变化;
图3示出单功能层的叠层的薄层电阻在热处理前随着平滑层的厚度的变化,其中该叠层被提供有单层阻隔涂层;
图4示出与图3所示相同的单功能层的叠层的薄层电阻在热处理后随着平滑层厚度的变化;
图5示出了本发明的双功能层的叠层,每个功能层被提供有上阻隔覆盖层但没有下阻隔涂层;
图6示出具有2个本发明功能层的叠层,每个功能层被提供有下阻隔涂层但没有罩面阻隔涂层;
图7示出具有2个本发明功能层的叠层,每个功能层被提供有下阻隔涂层并被提供有上阻隔涂层;
图8示出具有3个本发明功能层的叠层,每个功能层被提供有下阻隔涂层但没有上阻隔涂层;以及
图9示出具有4个本发明功能层的叠层,每个功能层被提供有下阻隔涂层但没有上阻隔涂层。
在示出的多层叠层的示意图中,为更容易理解,不同材料的厚度并未严格按照比例示出。
另外,在下面的所有实施例中,薄层叠层被沉积在由钠钙玻璃制成的基材10上,基材厚度为2mm,除非另行明确指出。
在对基材施加的热处理所有情况下,热处理是在约660℃温度进行约5min的退火处理,以及随后在室温(约20℃)的冷却。
图1~4的目的是说明平滑层在叠层中的存在的重要性。
然而,被用于获得这些图的叠层不是本发明的叠层,因为它们是具有以下类型单功能层的叠层:
基材/Si3N4/SnZnOx:Sb/ZnO/Ag/Ti/ZnO/Si3N4
         可变/可变/8nm/10nm/2nm/8nm/20nm
在图1和2中,曲线C1和C11说明了当叠层未被提供有平滑层时分别在热处理之前(BHT)和之后(AHT),叠层的薄层电阻(Ω)随与基材接触的氮化硅(e Si3N4)基的介电层厚度的变化。
曲线C2和C12说明了当叠层被提供有6nm厚的由SnZnOx:Sb(x代表非零的数字)制成的平滑层时,分别在热处理之前和之后,叠层的薄层电阻(Ω)随与基材接触的氮化硅(e Si3N4)基的介电层厚度的变化。
曲线C3和C13说明了当叠层被提供有20nm厚的基于SnZnOx:Sb的平滑层时,分别在热处理之前和之后,叠层的薄层电阻(Ω)随与基材接触的氮化硅(e Si3N4)基的介电层厚度的变化。
正如在图1和2中看到的,对于与基材接触的介电层的相同厚度(例如,20nm),当叠层包含介于与基材接触的氮化硅基的介电层与和在银Ag基功能层下面的氧化锌ZnO基的润湿层之间的SnZnOx:Sb基平滑层时,叠层的薄层电阻总是较低—因而较好—对于曲线C2、C3、C12和C13;而且,对于20nm的平滑层厚度(曲线C3和C13),叠层的薄层电阻总是较低。
业已证实,由混合氧化物制成的平滑层沿其整个厚度都是无定形的,而润湿层和金属功能层则沿它们的整个厚度都是结晶的。
结果,平滑层的存在显著改善了具有相当的下层介电层厚度的叠层的薄层电阻,且此种改善,当平滑层厚度大时,甚至更大。
在图3和4中,曲线说明了,当叠层被提供有介于基材与基于SnZnOx:Sb的层之间的20nm氮化硅Si3N4基层时,分别在热处理之前(BHT)和之后(AHT),叠层的薄层电阻(Ω)随基于以锑掺杂的锌和锡氧化物(e SnZnOx:Sb)的平滑层厚度的变化。
还证实,由混合氧化物制成的平滑层沿其整个厚度都是无定形的,而润湿层和金属功能层则沿各自整个厚度都是结晶的。
正如还可从图3和4看出的,对于平滑层厚度介于>0与4nm之间,平滑层的存在显著改善了叠层的薄层电阻,且此种改善,当平滑层厚度大时,则更大。
类似的结论可以适用于被提供有下阻隔涂层但没有上阻隔涂层或者被提供有下阻隔涂层且上阻隔涂层的单功能层的叠层。
另外,为测量各层的粗糙度,进行了试验。
下表给出由X-射线反射测定法测定的并以纳米为单位表示的粗糙度(基材的粗糙度为约0.4):
表1
 
层                 厚度(nm)             粗糙度σ(nm)
Si3N4             28.5                    1.1玻璃              基材
SnO2              29.5                    0.8玻璃              基材
SnZnOx:Sb         32.0                    0.7玻璃              基材
SnZnOx:Sb         11.2                    0.8Si3N4             19.7                    0.5玻璃              基材
SnO2              10.4                    0.8Si3N4             19.3                    0.5玻璃              基材
正如从该表可以看出的,基于仅仅沉积在玻璃上的氮化硅Si3N4的层的粗糙度被提高,但包含基于铟锡氧化物SnInOx(ITO)的混合氧化物层的或者基于沉积在基于氮化硅的层上的锌锡混合氧化物SnZnOx:Sb的层的叠层的最终粗糙度较低。因此,基于混合氧化物的润湿层可以通过降低上述粗糙度来改善与润湿层之间的界面的粗糙度。
从上述结论出发,因此可以在基材10上沉积薄层叠层,它包含具有在红外和/或日光范围的反射性能的交替的n个功能层40、80、120、160,尤其是基于银或含银金属合金的金属功能层,以及(n+1)个涂层20、60、100、140、180,其中n是大于或等于2的整数,所述涂层包括多个介电层24、26;62、64、66;102、104、106、142、144、146、182、184,为了使每一个功能层40、80、120、140位于2个涂层20、60、100、140、180之间,至少2个功能层,优选每个功能层被沉积在润湿层30、70、110、150上,这些润湿层本身分别被直接沉积在下层涂层20、60、100、140上。
于是,基于上面的单功能层试验,进行了多个两功能层试验,但是不是全都满意。
基于图5所示的具有两功能层的叠层结构进行了2个实施例,编号1和2,其中每个功能层40、80被提供有上阻隔涂层45、85但没有下阻隔涂层。
下表2给出每个层的厚度,以纳米为单位:
表2
 
材料 实施例1 实施例2
104 Si3N4 20 20
102 ZnO 8 8
85 Ti 2 2
80 Ag2 10 10
70 ZnO 8 8
66 SnZnOx:Sb 20 6
64 Si3N4 40 52
62 ZnO 8 8
45 Ti 2 2
40 Ag1 10 10
30 ZnO 8 8
26 SnZnOx:Sb 6 20
24 Si3N4 20 6
于是,在本发明实施例1中,较薄下层涂层20的基于锑掺杂的锌锡氧化物SnZnOx:Sb的平滑层26的厚度小于较厚下层涂层60的基于锑掺杂的锌锡氧化物SnZnOx:Sb的平滑层66的厚度;然而在对比例2中,较薄下层涂层20的平滑层26的厚度则大于较厚下层涂层60的平滑层66的厚度。
获得的电阻率在下表3中给出:
表3
于是,本发明实施例1的电阻率好于实施例2的电阻率,不论热处理前还是热处理后。
在实施例2的情况中,在具有多个功能层的叠层中的加入平滑层却不可能达到实施例1情况中所获得的在功能层结晶上要求的改善,即使(而且这一点已经得到证实)平滑层是无定形并且润湿层是结晶的。
另一系列实施例,编号3,是根据图6所示的具有2个功能层的叠层结构进行的,其中每个功能层40、80被提供有下阻隔涂层35、75,但没有在图6中可看到的机械保护层200。
下表4给出每个层的厚度,以纳米为单位:
表4
 
材料 实施例3
104 Si3N4 27
102 ZnO 8
80 Ag2 10
75 Ti 2
70 ZnO 10
66 SnZnOx:Sb Y
64 Si3N4 65-Y
62 ZnO 8
40 Ag1 10
35 Ti 2
30 ZnO 7
26 SnZnOx:Sb X
24 Si3N4 23-X
在此基础上,进行6个实施例,编号3a~3f。
下表5给出每个实施例的X和Y值,以纳米为单位:
表5
 
实施例 类型 X Y
3a X<Y 2 6
3b X>Y 6 2
3c X<Y 2 10
3d X>Y 10 2
3e X<Y 2 4
3f X>Y 4 2
于是,在本发明实施例3a、3c和3e中,较薄下层涂层20的平滑层26的厚度小于较厚下层涂层60的平滑层66的厚度,而在对比例3b、3d和3f中,较薄下层涂层20的平滑层26的厚度则大于较厚下层涂层60的平滑层66的厚度。
这些实施例的电阻率、光学和能量特性在下表6中给出(光学和能量特性是在退火并插入到具有以下结构的层压玻璃中后被测定的:外部/2.1mm玻璃基材/0.25mm PVB/载有叠层的2.1mm玻璃基材;于是,该层的叠层位于表面3上,按相对于入射日光的方向编号):
表6
Figure A200780007797D0015092841QIETU
因此,本发明实施例3a、3c、3e的叠层电阻率(这里在热处理后测定)仍然分别低于对应对比例3b、3d、3f。
再有,在光源A下测定的透能率TE、透光率TL,在光源D65下测定的能量反射RE、光反射RL(D65),以及按照在这些层一侧的光源D65下测量的LAB色度体系中的反射光的颜色a*和b*值,在本发明实施例与对应对比例3b、3d、3f之间没有非常显著的变化。
通过热处理前测定的光学和能量特性与热处理后的这些同样特性相比,没有观察到任何退化。
其他试验是基于图7中所示的具有2个功能层的叠层结构实施的,其中每个功能层40、80被提供有下阻隔涂层35、75和上阻隔涂层45、85。
这些试验得出了类似的观测结果。
就具有2个功能层的结构而言,观察到,较薄下层涂层的平滑层优选地离基材最近,于是较厚下层涂层的平滑层便离基材最远。
另外,本发明可应用于具有3个功能层的叠层,例如,图8中所示叠层。
在该说明的结构中,每个功能层40、80、120被提供有下阻隔涂层35、75、115;然而,也可以在除了下阻隔涂层35、75、115之外另提供上阻隔涂层,或者在没有上述下阻隔层时提供上述上阻隔层。
再有,在该说明的结构中,每个下层涂层20、60、100包含根据本发明的平滑层26、66、106。
就具有3个功能层的结构而言,据发现,较薄下层涂层的平滑层优选地离基材最近,而较厚下层涂层的平滑层作为中心平滑层66,同时离基材106最远的层应比离基材最近的平滑层26厚并且其厚度又小于中心平滑层66的厚度。
在此种结构中,有可能仅提供2个平滑层,就是说仅提供2个对应于本发明的下层涂层。在此种情况下,所述2个下层涂层当中较薄涂层离基材最远。
另外,本发明可以应用于具有4个功能层的叠层,例如,图9所示叠层。
在所示结构中,每个功能层40、80、120、160被提供有下阻隔涂层35、75、115、155;然而,还可能除了下阻隔涂层35、75、115、155外另提供上阻隔涂层,或者在没有上述下阻隔层时提供上述上阻隔层。
另外,在所示结构中,每个下层涂层20、60、100、140包含本发明的平滑层26、66、106、146。
这种叠层可通过,例如,将基材10经过用于沉积具有2个功能层的叠层的装置2次来获得,正如从国际专利申请WO 2005/051858中已知,从而沉积:
-在第一次通过期间,层24~102,随后
-在第二次通过期间,层104~182,随后
-在沉积最后工序的装置中,层184和200。
在此种结构中,有可能仅提供2个平滑层,就是说仅提供2个对应于本发明的下层涂层。在此种情况中,所示2个下层涂层当中较薄涂层离基材最远。
上面通过实施例描述了本发明。应当理解的是,本领域技术人员能够进行各种不同的本发明替代方案,而不致偏离如权利要求定义的发明范围。

Claims (18)

1.基材(10),尤其是透明玻璃基材,其被提供有薄层的叠层,该叠层包含交替排列的具有在红外和/或日光范围反射性能的n个功能层(40、80),尤其是基于银或含银金属合金的金属功能层,以及(n+1)个涂层(20、60、100),其中n是≥2的整数,所述涂层包括多个介电层(24、26;64、66;104),以便使每个功能层(40、80)位于2个涂层(20、60、100)之间,其中至少2个功能层(40、80)中的每个沉积在润湿层(30、70)上,润湿层本身分别被直接沉积到下层涂层(20、60)上,特征在于,2个下层涂层(20、60)中的每个包含至少一个介电层(24、64)和至少一个非结晶的平滑层(26、66),构成平滑层的材料不同于每个涂层内所述介电层的材料,所述平滑层(26、66)与所述上层润湿层(30、70)相接触,特征还在于,这2个下层涂层(20、60)厚度各不相同,总厚度小于其他下层涂层(60、20)的下层涂层(20、60)的平滑层(26、66)的厚度小于或等于其他下层涂层(60、20)的平滑层(66、26)的厚度。
2.权利要求1的基材(10),其特征在于,叠层包含与3个涂层的交替排列的2个功能层。
3.权利要求1的基材(10),其特征在于,叠层包含与4个涂层的交替排列的3个功能层。
4.权利要求1的基材(10),其特征在于,叠层包含与5个涂层的交替排列的4个功能层。
5.以上权利要求中任何一项的基材(10),其特征在于,离基材最近的下层涂层是所述2个下层涂层(20、60)当中较薄的涂层。
6.权利要求3~5中任何一项的基材(10),其特征在于,离基材最远的下层涂层是所述2个相邻的下层涂层当中较薄的涂层。
7.以上权利要求中任何一项的基材(10),其特征在于,至少一个平滑层(26、66),甚至所有平滑层(26、66),是氧化物层,尤其是基于下列金属中一种或多种的氧化物的混合氧化物:Sn、Si、Ti、Zr、Hf、Zn、Ga、In。
8.以上权利要求的基材(10),其特征在于,至少一个平滑层(26、66),甚至所有平滑层(26、66),是混合氧化物层,尤其是一种在低温沉积的基于锌和锡的混合氧化物的层或铟锡混合氧化物(ITO)的层。
9.以上权利要求中任何一项的基材(10),其特征在于,至少一个平滑层(26、66),甚至所有平滑层(26、66),是具有非化学计量的氧的氧化物层。
10.以上权利要求中任何一项的基材(10),其特征在于,该或每个平滑层(26、66)具有0.1~30nm,优选0.2~10nm之间的几何厚度。
11.以上权利要求中任何一项的基材(10),其特征在于,至少一个,优选每个功能层(40、80)被直接置于至少一个下层阻隔涂层(35、75)上和/或直接在至少一个上层阻隔涂层(45、85)下方。
12.以上权利要求的基材(10),其特征在于,至少一个阻隔涂层(35、45、75、85)基于Ni或Ti或基于镍基合金,尤其是基于NiCr合金。
13.以上权利要求中任何一项的基材(10),其特征在于,至少一个,优选每个在功能层(40、80)下方的润湿层(30、70)是基于氧化锌的。
14.以上权利要求中任何一项的基材(10),其特征在于,至少一个,优选每个在所述下层涂层(20、60)内与平滑层(26、66)相邻的介电层(24、64)基于氮化物,尤其是氮化硅和/或氮化铝。
15.包括至少一个以上权利要求中任何一项的基材(10)的玻璃,任选地与至少一个其他基材结合。
16.以上权利要求的玻璃,其以单块形式或作为双层玻璃或层压玻璃型多层玻璃进行安装,特征在于,至少载有该叠层的基材被弯曲或被钢化。
17.权利要求15或16的玻璃,其特征在于,它被提供有能给所述叠层提供电能的手段。
18.用于制造权利要求1~14中任何一项的基材(10)的方法,其特征在于,采用任选地磁场辅助的阴极喷镀类真空技术在其基材上沉积薄层的叠层,随后对所述基材实施弯曲、钢化或退火等类热处理,而不会损害其光学和/或力学品质。
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CN105050979A (zh) * 2012-11-19 2015-11-11 葛迪恩实业公司 具附加金属的含氧化锡层的低辐射涂层的涂层制品
US9796620B2 (en) 2012-11-19 2017-10-24 Guardian Glass, LLC Coated article with low-E coating including tin oxide inclusive layer(s) with additional metal(s)
TWI613069B (zh) * 2012-11-19 2018-02-01 加爾汀工業公司 具有低輻射塗層且該塗層包括具其他金屬之含氧化錫層的經塗覆物件
CN104973800A (zh) * 2014-04-08 2015-10-14 法国圣戈班玻璃厂 设有具备热学性能的叠层的基底
CN109311740A (zh) * 2016-04-19 2019-02-05 顶峰实业股份有限公司 涂覆的玻璃表面和用于涂覆玻璃基板的方法
CN109311740B (zh) * 2016-04-19 2022-01-11 顶峰实业股份有限公司 涂覆的玻璃表面和用于涂覆玻璃基板的方法

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WO2007101963A2 (fr) 2007-09-13
CA2644862C (fr) 2015-07-07
PT1993829T (pt) 2018-10-19
ES2682098T3 (es) 2018-09-18
KR101400421B1 (ko) 2014-05-26
BRPI0708421A2 (pt) 2011-05-31
KR20080101932A (ko) 2008-11-21
JP2009528973A (ja) 2009-08-13
EP1993829A2 (fr) 2008-11-26
FR2898122B1 (fr) 2008-12-05
BRPI0708421B1 (pt) 2018-03-20
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WO2007101963A3 (fr) 2008-01-31
US8420207B2 (en) 2013-04-16
EA017637B1 (ru) 2013-02-28
TR201811273T4 (tr) 2018-08-27
CN101395000B (zh) 2013-09-25
FR2898122A1 (fr) 2007-09-07
JP5491736B2 (ja) 2014-05-14
CA2644862A1 (fr) 2007-09-13

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