CN104039732B - 提供有包括四个金属功能层的具有热性质的堆叠体的基材 - Google Patents

提供有包括四个金属功能层的具有热性质的堆叠体的基材 Download PDF

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CN104039732B
CN104039732B CN201380005544.0A CN201380005544A CN104039732B CN 104039732 B CN104039732 B CN 104039732B CN 201380005544 A CN201380005544 A CN 201380005544A CN 104039732 B CN104039732 B CN 104039732B
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CN104039732A (zh
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E.桑德尔-沙多纳尔
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Saint Gobain Glass France SAS
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    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10Optical coatings produced by application to, or surface treatment of, optical elements
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    • G02B1/113Anti-reflection coatings using inorganic layer materials only
    • G02B1/115Multilayers
    • G02B1/116Multilayers including electrically conducting layers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B60VEHICLES IN GENERAL
    • B60JWINDOWS, WINDSCREENS, NON-FIXED ROOFS, DOORS, OR SIMILAR DEVICES FOR VEHICLES; REMOVABLE EXTERNAL PROTECTIVE COVERINGS SPECIALLY ADAPTED FOR VEHICLES
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    • EFIXED CONSTRUCTIONS
    • E06DOORS, WINDOWS, SHUTTERS, OR ROLLER BLINDS IN GENERAL; LADDERS
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    • E06B3/00Window sashes, door leaves, or like elements for closing wall or like openings; Layout of fixed or moving closures, e.g. windows in wall or like openings; Features of rigidly-mounted outer frames relating to the mounting of wing frames
    • E06B3/66Units comprising two or more parallel glass or like panes permanently secured together
    • E06B3/67Units 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
    • E06B3/6715Units 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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Abstract

本发明涉及基材(10),尤其透明玻璃基材,其被提供有包含四个金属功能层(40,80,120,160),尤其基于银或含银金属合金的功能层,和五个抗反射涂层(20,60,100,140,180)的交替更迭的薄层堆叠体,每个抗反射涂层包含至少一个抗反射层,使得每个金属功能层(40,80,120,160)被设置在两个抗反射涂层(20,60,100,140,180)之间,特征在于从该基材开始的第二、第三和第四金属功能层(80,120,160)的厚度是基本上相同的,其中一个层的厚度与前面的层的厚度的比率为0.9至1.1,包括端值,和第一金属功能层(40)的厚度是第二金属功能层(80)的厚度的大约一半,其中第二金属层的厚度与第一金属功能层(40)的厚度的比率为1.9至2.2,包括端值。

Description

提供有包括四个金属功能层的具有热性质的堆叠体的基材
本发明涉及透明基材,尤其由刚性无机材料如玻璃制成的透明基材,所述基材用包含数个可以作用于长波长的日光辐射和/或红外辐射的功能层的薄层堆叠体涂覆。
本发明更特别地涉及基材,尤其透明玻璃基材,其被提供有薄层堆叠体包含“n”个金属功能层,尤其基于银或对含银金属合金的功能层,和“(n+1)”个抗反射涂层的交替更迭,其中n为整数=4,使得每个功能层被设置在两个抗反射涂层之间。每个涂层包含至少一个抗反射层,每个涂层优选由多个层组成,其至少一个层,甚至其每个层是抗反射层。
本发明更特别地涉及这种基材用于制备隔热和/或防晒窗玻璃的用途。这种窗玻璃可以等同地用于装备建筑物和交通工具,尤其为了降低空调负载和/或防止过度的过加热(被称为"日照控制"窗玻璃)和/或降低由于在建筑物和交通工具的客舱中日益增加使用玻璃化表面所引起的消散到外界的能量的量(被称为"低辐射性"窗玻璃)。
这些基材特别地可以被集成到电子装置中和该堆叠体这时可以充当用于传导电流的电极(照明装置、显示装置、伏打面板、电致变色窗玻璃等等)或可以被集成到具有特定功能性的窗玻璃中,如,例如加热窗玻璃,特别地交通工具的加热风挡。
具有四个金属功能层的堆叠体是已知的。
在这种类型堆叠体中,每个功能层被设置在两个抗反射涂层之间,每个抗反射涂层通常包含数个抗反射层,每个抗反射层由氮化物类型,尤其氮化硅或者氮化铝和/或氧化物类型材料制成。从光学角度来看,围绕该功能层的这些涂层的目的是使这种功能层“抗反射”。
然而非常薄的阻隔涂层有时被插入在一或每个抗反射涂层和相邻的功能层之间:在基材方向上被设置在功能层下方的阻隔涂层和被设置在与基材相对的侧上的功能层上方的阻隔涂层(其在沉积上面抗反射涂层期间和在任选的弯曲和/或淬火类型的高温热处理期间保护这种层不经受可能的退化)。
具有四个功能层的堆叠体从现有技术,例如从国际专利申请WO2005/051858是已知的。
在该文件中介绍的具有四个功能层的堆叠体中,所有的功能层的厚度基本上是相同的,即最靠近该基材的第一功能层的厚度基本上与第二功能层的厚度相同,第二功能层的厚度基本上与第三功能层的厚度相同,甚至当存在第四功能层时,第三功能层的厚度基本上与第四功能层的厚度相同。例如参看上述文件的实施例24。
然而,看起来申请WO2005/051858的实施例24的双层窗玻璃的结构不是完全地令人满意的,因为即使它的光透射十分高(58.0%),它的光反射十分低(12.2%)和它的能量传递十分低,它的太阳因子(其在本质上高于能量传递)引起不是令人满意的选择性;而且,由于在LAB体系中的a*的值是非常负的,在透射中的颜色不再是令人满意的。
看起来将优选的是,在双层窗玻璃中获得更高的光透射(大约60%),仍然十分低的光反射(大约12%)和更低的太阳因子(大约26%),以能够获得大约2.3的高选择性;看起来还将优选的是,从外部和从内部都获得更中性的反射颜色(在蓝-绿色中),并且该反射颜色随着观察角度改变很小。
本发明的一个目的是提供具有这些特征的堆叠体。
另一个目的是提供具有非常低的薄层电阻(résistance par carré)的堆叠体以特别使得集成了这种堆叠体的窗玻璃能显示出高能量反射和/或非常低的辐射率和/或能通过在两个电连接至该堆叠体的母线之间施加电流而被加热,以及高光透射和相对中性的颜色,特别地在双层窗玻璃结构中或在层压结构中,并且使得这些性质优选在一个(或多个)弯曲和/或淬火和/或退火类型的高温热处理之后而获得,甚至使得这些性质保持在限定的范围内,无论该堆叠体是否经受一个(或多个)这种热处理。
本发明一个主题在它的最广泛的意义上因此是基材,尤其透明玻璃基材,其被提供有包含四个金属功能层(尤其基于银或含银金属合金的功能层)和五个抗反射涂层的薄层堆叠体的交替更迭(alternance),每个抗反射涂层包含至少一个抗反射层,使得每个金属功能层被设置在两个抗反射涂层之间,值得注意的是从该基材开始的第二、第三和第四金属功能层的厚度是基本上相同的,其中一个层的厚度与前面的层的厚度的比率为0.9至1.1,包括端值,和第一金属功能层的厚度是第二金属功能层的厚度的大约一半,其中第二金属层的厚度与第一金属功能层的厚度的比率为1.9至2.2,包括端值。
每个位于在两个金属功能层之间的抗反射涂层具有十分相近的光学厚度。每个位于两个金属功能层之间的抗反射涂层优选具有165nm至181nm(包括端值)的光学厚度,以促进获得在蓝-绿色中的反射颜色。考虑到在第一金属功能层的厚度和其它金属功能层的厚度之间的不平衡,这更是令人惊奇的。
措辞“在蓝-绿色中的颜色”在本发明意义上应该理解为在Lab颜色测量体系中,a*为0至-6。
优选,每个位于两个金属功能层之间的抗反射涂层仅仅由一个或多个抗反射层组成。优选,因此在该介电涂层中不存在吸收层,以便不降低光透射。
第一金属功能层的厚度优选为所有的其它金属功能层的厚度的大约一半,其中第二、第三和第四金属功能层的厚度的平均值与第一金属功能层的厚度的比率为1.9至2.5,包括端值。这种规则允许促进获得在蓝-绿色中的外部反射颜色。
术语"次序(rang)"在本发明意义上理解为表示每个功能层从该基材开始的整数编号:最靠近基材的功能层是次序1的功能层或第一功能层,更远离基材的下一个功能层是次序2的功能层或第二功能层,等等。
措辞“一个层的厚度与前面的层的厚度的比率”因此应该理解为表示所讨论层的厚度与直接地下面次序的层的厚度的比率。
每个功能层的厚度优选为6至20nm,包括端值,以获得足够高的光透射。
从基材开始的第一金属功能层的厚度e40(nm)优选使得:5.5≤e40≤11(nm),优选6≤e40≤10。
从基材开始的第二金属功能层(次序2的金属功能层)的厚度e80(nm)优选使得:11≤e80≤22(nm),优选12≤e80≤20。
从基材开始的第三金属功能层(次序3的金属功能层)的厚度e120(nm)优选使得:11≤e120≤22(nm),优选12≤e120≤20。
从基材开始的第四金属功能层(次序4的金属功能层)的厚度e160(nm)优选使得:11≤e160≤22(nm),优选12≤e160≤20。
对于金属功能层的这些厚度范围是其中获得最好结果的范围:高的在双层窗玻璃中的光透射,低的光反射和较低的太阳因子,以能够获得高选择性,具有从外部看和从内部看是中性的在蓝-绿色中的反射颜色。
在一个优选的变型中,四个金属功能层的总厚度为30至70nm,包括端值,甚至这种总厚度为35至65nm。
重要的是,在这里注意到:在该四个功能层的厚度的分配中的特定分布与在该堆叠体的所有层(考虑了抗反射层)的厚度的分配中的分布是不相同的。
除非另作说明,否则在本文件中提到的厚度是物理或实际厚度(不是光学厚度)。
措辞“光学厚度”在本发明的意义中通常理解为,该层的物理(或者实际)厚度乘以它通常在550nm测量的折光指数的乘积。
措辞“总光学厚度”在本发明的意义中理解为所考虑的层的所有光学厚度的总和,其中每个光学厚度如上面解释地是该层的物理(或者实际)厚度乘以它通常在550nm测量的折光指数的乘积。
因此,与第一金属功能层下邻的第一抗反射涂层(次序1的抗反射涂层)的总光学厚度由这种涂层的所有介电层的光学厚度的总和构成,所述介电层被设置在基材和第一金属功能层之间,或者在基材和第一金属层的下阻隔涂层(如果这种下阻隔涂层存在的话)之间。
同样地,与第四金属功能层上邻的最后抗反射涂层(次序5的抗反射涂层)的总光学厚度由这种涂层的所有介电层的光学厚度的总和构成,所述介电层被设置在第四金属功能层的上方,在与基材相对的侧上,或者在第四金属功能层的上阻隔涂层(如果这种上阻隔涂层存在的话)的上方。
与金属功能层上邻的并与后面的金属功能层(远离基材)下邻的中间抗反射涂层(次序2、3和4的抗反射涂层)的总光学厚度由这种涂层的介电层的所有光学厚度的总和构成,所述介电层被设置在这两个金属功能层之间,在金属功能层的上阻隔涂层(如果它存在)的上方并且在后面的金属功能层的下阻隔涂层(如果它存在)的下方。
此外,当提到层的垂直定位状态(例如在...下方/在...上方)时,它总是考虑该载体基材在底部被水平地放置,在它上方具有堆叠体。当规定层被直接地沉积在另一个层上时,这表示不能存在一个(或多个)被插在这两个层之间的层。功能层的次序在这里总是从携带该堆叠体的基材(在堆叠体被沉积其面上的基材)开始并且通过参考相同性质的层进行界定。
在本发明的一个特定的变型中,每一个抗反射涂层包含至少一个基于氮化硅(任选地借助于至少一种其它元素,如铝进行掺杂)的抗反射层。这对于使薄层堆叠体弯曲/淬火或对于可弯曲的/可淬火的薄层堆叠体是特别有利的。
在本发明的另一个特定的变型中,与功能层下邻的每个抗反射涂层的最后层是抗反射润湿层,其基于结晶氧化物,尤其基于氧化锌,任选地借助于至少一种其它元素,如铝进行掺杂,以促进获得结晶功能层。
本发明此外涉及包括至少一个根据本发明的基材(任选地与至少一个其它基材结合)的窗玻璃,尤其双层窗玻璃或三层窗玻璃类型的多层窗玻璃或层压窗玻璃,特别地包含用于该薄层堆叠体的电连接的工具(以允许制备加热层压窗玻璃)的层压窗玻璃,所述携带该堆叠体的基材可以进行弯曲和/或淬火。
该窗玻璃的每个基材可以是透亮的或着色的。至少一个基材尤其可以用本体着色玻璃制成。着色类型的选择将取决于对于该窗玻璃(一旦已经完成它的制备)来说希望的光透射的水平和/或比色外观。
根据本发明的窗玻璃可以具有层压结构,尤其通过至少一个热塑性聚合物片材使至少两个玻璃类型的刚性基材结合,以便具有以下类型的结构:玻璃/薄层堆叠体/片材(一个或多个)/玻璃。该聚合物尤其可以基于聚乙烯醇缩丁醛(PVB),乙烯-醋酸乙烯酯(EVA),聚对苯二酸亚乙酯(PET)或聚氯乙烯(PVC)。
该窗玻璃这时可以具有以下类型的结构:玻璃/薄层堆叠体/聚合物片材(一个或多个)/玻璃。
根据本发明的窗玻璃可以经受热处理而不伤害该薄层堆叠体。它因此任选地进行弯曲和/或淬火。
该窗玻璃可以进行弯曲和/或淬火,当它由提供有该堆叠体的单一基材构成时。这时它是"单片"窗玻璃。如果该窗玻璃进行弯曲,尤其为了构成用于交通工具的窗玻璃,该薄层堆叠体优选在为至少部分非平坦的面上。
该窗玻璃还可以是多层窗玻璃,尤其双层窗玻璃,至少该携带堆叠体的基材可以进行弯曲和/或淬火。优选地在多层窗玻璃构造中该堆叠体进行设置以便面对中间充气腔侧。在层压结构中,携带该堆叠体的基材可以与聚合物片材接触。
该窗玻璃还可以是由三个被充气腔成对地分开的玻璃片材组成的三层窗玻璃。在三层窗玻璃结构中,携带该堆叠体的基材可以在面2上和/或在面5上,当考虑日光的入射方向以它们的编号提高的顺序穿过所述面时。
当窗玻璃是单片窗玻璃或双层窗玻璃、三层窗玻璃类型的多层窗玻璃或层压窗玻璃时,至少携带堆叠体的基材可以由经弯曲或淬火的玻璃制成,这种基材可以在沉积该堆叠体之前或之后进行弯曲或淬火。
本发明还涉及根据本发明的基材用于制备具有高能量反射窗玻璃和/或具有非常低辐射率的窗玻璃和/或具有通过焦耳效应加热的透明涂层的加热窗玻璃的用途。
本发明还涉及根据本发明的基材用于制备电致变色窗玻璃的或照明装置的或显示装置的或光伏面板的透明电极的用途。
根据本发明的基材可以特别地用于制备具有高能量反射的基材和/或具有非常低辐射率的基材和/或加热窗玻璃的加热透明涂层。
根据本发明的基材可以,特别地,用于制备电致变色窗玻璃(这种窗玻璃是单片窗玻璃或是双层窗玻璃或三层窗玻璃类型的多层窗玻璃或层压窗玻璃)的或照明装置的或显示屏的或光伏面板的透明电极。(术语"透明的"在这里应该理解为表示"非-不透明的")。
根据本发明的堆叠体允许获得用堆叠体涂覆的基材,并且其具有高光透射(>55%,甚至>60%),低的光反射(<14%),高太阳因子和不是非常明显的的反射颜色(在LAB体系中具有接近于零的a*和b*值)而且反射颜色根据观察角度改变很小。
根据本发明的堆叠体因此允许获得大于2.1的高选择性。
本发明的细节和有利特征将从以下非限制性实施例显露出来,该实施例借助于附图进行说明:
-附图1举例说明根据本发明的具有四个金属功能层的堆叠体的结构的实例;
-附图2举例说明对于实施例1在LAB体系中的从外部(“外”)和从内部(“内”)观察到的反射颜色根据角度的变化,
-附图3举例说明对于实施例2在LAB体系中的从外部(“外”)和从内部(“内”)观察到的反射颜色根据角度的变化,
-附图4举例说明对于实施例3在LAB体系中的从外部(“外”)和从内部(“内”)观察到的反射颜色根据角度的变化;
-附图5举例说明对于实施例4在LAB体系中的从外部(“外”)和从内部(“内”)观察到的反射颜色根据角度的变化;
-附图6举例说明对于国际专利申请WO2005/051858的实施例24在LAB体系中的从外部(“外”)和从内部(“内”)观察到的反射颜色根据角度的变化。
在附图1中,没有遵循在不同元素之间的比例以使得它们更容易观察;对于附图2至6,箭头指示从相对于外表面的法线0°(弯曲的起始)直至相对于外表面的法线70°的角度(沿着箭头的方向的弯曲的结束)获得的变化。
附图1举例说明了具有四个金属功能层40,80,120,160的堆叠体结构,这种结构被沉积在透明玻璃基材10上。
每个功能层40,80,120,160被设置在两个抗反射涂层20,60,100,140,180之间使得从基材开始的第一功能层40被设置在抗反射涂层20,60之间,第二功能层80被设置在抗反射涂层60,100之间,第三功能层120被设置在抗反射涂层100,140之间和第四功能层160被设置在抗反射涂层140和180之间。
这些抗反射涂层20,60,100,140,180每个包括至少一个介电抗反射层24,28;62,64,68;102,104,108;142,144,148;182,184。
任选地,一方面每个功能层40,80,120,160可以被沉积在被设置在与该功能层下邻的该抗反射涂层和该功能层之间的下阻隔涂层(未图示)上方,另一方面,每个功能层40,80,120,160可以被直接地沉积在设置在功能层和与该功能层上邻的抗反射涂层之间的上阻隔层涂层55,95,135,175的下方。
在该堆叠体的抗反射涂层的光学定义中不考虑这些阻隔涂层。
实施了第一系列四个实施例。这些实施例在下文从1至4进行编号。
对于这些实施例,该抗反射涂层20,60,100,140,180仅仅通过它们的光学厚度进行定义(同时考虑组成该抗反射涂层的抗反射材料的折光指数在550纳米进行测量,按照惯例)。
在下面表1总结了构成堆叠体的每个层或涂层根据它们相对于携带堆叠体(在表的底部的最后行)的基材的位置的厚度(纳米);第一栏的厚度的下标对应于附图1的标记。
实施例1 实施例2 实施例3 实施例4
e180 介电5 91 86 75 85
e160 Ag4 17.1 17.1 17.2 15.5
e140 介电4 181 178 176 175
e120 Ag3 15.7 15.8 13.3 17.1
e100 介电3 168 167 141 172
e80 Ag2 15.2 14.3 8.6 15.1
e60 介电2 175 165 118 165
e40 Ag1 7.7 6.7 6.2 9.5
e20 介电1 89 45 67 80
玻璃
表1
下面的表2总结了该功能层的厚度的比率:
实施例1 实施例2 实施例3 实施例4
e160/e120 1.09 1.08 1.30 0.91
e120/e80 1.03 1.10 1.55 1.13
e80/e40 1.98 2.13 1.39 1.60
((e80+e120+e160)/3)/e40 2.08 2.35 2.10 1.67
表2
表3对于这些实施例1至4总结了对于该携带该堆叠体的基材测量的主要光学特征,该基材被集成到具有以下结构的双层窗玻璃中:6毫米玻璃/15毫米中间充氩空间/6毫米玻璃,该堆叠体被设置在面2上(该窗玻璃的面1是该窗玻璃的最外部的面,按照惯例)。
实施例1 实施例2 实施例3 实施例4
TL % 60.0 59.8 59.9 61.7
a*T -8.4 -8.0 -7.2 -11.4
b*T 3.3 4.0 3.1 4.2
RL外 % 12.5 12.6 12.1 9.1
a*R外 -1.9 -3.7 -3.0 9.4
b*R外 -4.8 -9.2 -3.1 -12.4
a*R外-45° -1.0 -1.0 -1.3 12.1
b*R外-45° 3.2 -2.1 -1.9 -1.5
a*R外-60° -2.5 -1.5 -1.1 9.2
b*R外-60° 3.5 0.0 -1.8 1.2
RL内 % 14.0 14.1 16.1 11.0
a*R内 0.4 -0.7 -1.5 9.1
b*R内 -5.7 -5.3 -1.1 -10.3
FS % 26.4 26.4 28.3 26.6
表3
对于这种双层窗玻璃,
-TL指示:在可见光中的光透射(%),其按照标准光源A以10°观察器进行测量;
-a*T和b*T指示在LAB体系中的透射颜色a*和b*,其按照光源D65以10°观测器进行测量,并因此基本上垂直于窗玻璃进行测量;
-RL外指示:在可见光中的光反射(%),其按照标准光源A以10°观测器从最外面(面1)的一侧进行测量;
-a*R外和b*R外指示在LAB体系中的反射颜色a*和b*,其按照光源D65以10°观测器从最外部面的一侧进行测量并因此基本上垂直于该窗玻璃进行测量;
-a*R外-45°和b*R外-45°指示在LAB体系中的反射颜色a*和b*,其按照光源D65以10°观测器从最外部面的一侧进行测量并基本上以相对于该窗玻璃的垂直的45°的角度进行测量;
-a*R外-60°和b*R外-60°指示在LAB体系中的反射颜色a*和b*,其按照光源D65以10°观测器从最外部面的一侧进行测量并基本上以相对于该窗玻璃的垂直的60°的角度进行测量;
-RL内指示该在可见光中的光反射(%),按照标准光源A以10°观测器从最内部面(面4)的一侧进行测量;
-a*R内和b*R内指示在LAB体系中的反射颜色a*和b*,按照标准光源D65以10°观测器从最内部面的一侧进行测量,并因此基本上垂直于该窗玻璃进行测量;
-FS指示太阳因子,即穿过该窗玻璃进入该房间的总能量相对于总入射太阳能的百分比,其根据标准EN 410进行计算。
对于根据本发明的实施例1和2,最远离该基材的三个功能层因此具有几乎相同的厚度:一方面,第四功能层的厚度e160与第三功能层的厚度e120的比率和,另一方面,第三功能层的厚度e120与第二功能层的厚度e80的比率是几乎相同的;这些比率为0.9至1.2,更精确地1.0至1.15。
对于根据本发明的这些实施例1和2,最靠近该基材的功能层具有为第二功能层的厚度e80的约一半甚至低于一半的厚度e40(参看表2的倒数第二行);第二功能层的厚度e80与第一功能层的厚度e40的比率为1.9至2.2。
对于根据本发明的这些实施例1和2,最靠近该基材的功能层具有的厚度e40为所有其它功能层的平均厚度的约一半,甚至低于一半(参看表2的最后行);这些比率为1.9至2.5,更精确地2.0至2.4。
对于不是根据本发明的实施例3,功能层的厚度在远离基材同时而逐步提高,其中一个功能层的厚度相对于前面功能层(在基材的方向上)的厚度比率为大约1.3至1.5。
对于不是根据本发明的实施例3,即使最靠近该基材的功能层具有的厚度e40为所有其它功能层的平均厚度(参看表2的最后行)的大约一半,最靠近该基材的功能层不具有为第二功能层的厚度e80的大约一半的厚度e40(参看表2的倒数第二行)。
对于不是根据本发明的实施例4,最远离该基材的三个功能层具有几乎相同的厚度:一方面,第四功能层的厚度e160与第三功能层的厚度e120的比率和,另一方面,第三功能层的厚度e120与第二功能层的厚度e80的比率是几乎相同的;这些比率为0.9至1.2。
对于不是根据本发明的实施例4,最靠近该基材的功能层具有的厚度e40的确小于第二功能层的厚度(参看表2的倒数第二行),但是第二功能层的厚度e80与第一功能层的厚度e40的比率低于1.9。
对于不是根据本发明的实施例4,最靠近基材的功能层具有的厚度比所有其它功能层的平均厚度的一半大许多(参看表2的最后行)。
对表3的研究显示,可以制备具有四个功能金属层的堆叠体,其在整个可见光区中具有低的并且平坦的光反射,在UV和红外线范围中非常急剧的倾斜度,其透射谱因此明显地接近理想方形-波带通谱,因此允许获得非常有利的大约60/26的选择性(TL/FS比率);这已经由实施例1和2得到的结果。
此外在外部侧上和在内部侧上的反射颜色被包括在蓝-绿色中,并且随着角度改变很小,如在分别地在用于实施例1和2的附图2和3中可以看见的那样。
在附图2中,可以发现,对于实施例1,表3的对于外部反射颜色的值(“外”,以实线形式),特别地在0°(即在法线)的外部反射颜色的值为a*R外=-1.9和b*R外=-4.8;这是实线曲线的起点。
在附图2中,可以发现,对于实施例1,表3的对于内部反射颜色的值(“内”,以虚线形式),特别地在0°(即在法线)的内部反射颜色的值为a*R外=0.4和b*R外=-5.7;这是虚线曲线的起点。
实施例3具有比实施例1和2更差的选择性,约60/28。此外,在该外部侧的和在该内部侧的反射颜色随着该角度改变很大,如可以在附图4中所见。
实施例4具有比实施例1和2稍微更好的选择性,约61/26,但是具有淡红的反射颜色,其随着角度改变很大,如可以在附图5中所见。
来自申请WO2005/051858的实施例24本身还是模拟分析的主题,使用与上面实施例1至4相同的数据处理工具。结果在附图6中进行举例说明。
外部反射颜色和内部反射颜色随着角度改变很大。
对于下面的实施例5(其基于上面实施例2),薄层堆叠体被沉积在具有6mm厚度的由透亮的钠钙玻璃(由SAINT-GOBAIN销售)制成的基材上。
对于这种实施例,用于沉积所述层的条件,所述层已通过溅射(磁控管溅射)进行沉积,为以下:
使用的靶 沉积压力 气体 在550nm的指数
SiAlN Si:Al为92:8wt% 3.2×10-3mbar Ar/(Ar+N2)为55% 2.03
ZnO Zn:Al为98:2wt% 1.8×10-3mbar Ar/(Ar+O2)为63% 1.95
Ti Ti 2.5×10-3mbar Ar为100%
Ag Ag 3×10-3mbar Ar为100%
表4
在下面的表5总结了每个层的材料和厚度(纳米)和构成实施例5的堆叠体的层(根据它们相对于携带该堆叠体的基材的位置)的组成(在该表底部的最后行);第一和第二栏中的数字以及在最后栏中的下标对应于来自附图1的标记。
表5
与功能层40,80,120,160下邻的每个抗反射涂层20,60,100,140包含基于铝-掺杂的结晶氧化锌的最后润湿层28,68,108,148,并且其与在正上面沉积的功能层40,80,120,160接触。
每个抗反射涂层20,60,100,140,180包含具有平均指数的层24,64,104,144,184,其基于铝-掺杂的氮化硅(在这里被称为SiAlN,为了简化起见),虽然该层的真实性质实际上为如上面所解释的Si3N4:Al。
这些基于氮化硅的层对于在该热处理期间获得对氧的阻挡作用是重要的。
实施例5因此具有为可淬火的和可弯曲的附加优点。
已证实,这种实施例5实际上具有在上面表3中对于实施例2所指示的特征,具有测量误差和不确定性,和在附图3中指示的那些。
由于银层的大的总厚度(并因此获得的低的薄层电阻)以及优良的光学性质(特别地在可见光中的光透射),此外可以使用根据本发明的用堆叠体涂覆的基材以制备透明的电极基材。
这种透明的电极基材可以适合于有机电致发光装置,特别地通过用导电层(特别地,具有低于105Ω.cm的电阻率)和尤其基于氧化物的层代替一部分来自实施例5的氮化硅层184。这种层可以,例如,由氧化锡制成或基于氧化锌(其任选地用醛或镓掺杂),或基于混合氧化物和尤其基于氧化铟锡ITO,氧化铟锌IZO,氧化锡锌SnZnO(其任选地被掺杂(例如用Sb,F))。这种有机电致发光装置可以用于制备照明装置或显示装置(荧光屏)。
通常,该透明电极基材可以适合作为用于加热窗玻璃和特别地加热层压风挡的加热基材。它还可以适合作为用于任何电致变色窗玻璃,任何显示屏,或用于光电池和尤其用于透明光电池的正面或背面的透明电极基材。
本发明在上文中通过举例进行描述。理解的是,本领域的技术人员直接实施本发明的不同变型而无脱离如权利要求所定义的专利范围。

Claims (22)

1.基材(10),其被提供有包含四个金属功能层(40,80,120,160),和五个抗反射涂层(20,60,100,140,180)的交替更迭的薄层堆叠体,每个抗反射涂层包含至少一个抗反射层,使得每个金属功能层(40,80,120,160)被设置在两个抗反射涂层(20,60,100,140,180)之间,特征在于从该基材开始的第二、第三和第四金属功能层(80,120,160)的厚度是基本上相同的,其中一个层的厚度与前一个层的厚度的比率为0.9至1.1,包括端值,和第一金属功能层(40)的厚度是第二金属功能层(80)的厚度的大约一半,其中第二金属功能层的厚度与第一金属功能层(40)的厚度的比率为1.9至2.2,包括端值。
2.根据权利要求1的基材(10),特征在于该基材(10)为透明玻璃基材。
3.根据权利要求1的基材(10),特征在于金属功能层(40,80,120,160)是基于银或含银金属合金的功能层。
4.根据权利要求1的基材(10),特征在于每个位于两个金属功能层之间的抗反射涂层(60,100,140)具有165nm至181nm的光学厚度,包括端值。
5.根据权利要求1-4任一项的基材(10),特征在于第一金属功能层(40)的厚度为所有的其它金属功能层(80,120,160)的厚度的大约一半,其中第二、第三和第四金属功能层的厚度的平均值与第一金属功能层(40)的厚度的比率为1.9至2.5,包括端值。
6.根据权利要求1-4任一项的基材(10),特征在于从基材开始的第一金属功能层(40)的以nm计的厚度e40使得:以nm计,5.5≤e40≤11。
7.根据权利要求1-4任一项的基材(10),特征在于从基材开始的第一金属功能层(40)的以nm计的厚度e40使得:以nm计,6≤e40≤10。
8.根据权利要求1-4任一项的基材(10),特征在于从基材开始的第二金属功能层(80)的以nm计的厚度e80使得:以nm计,11≤e80≤22。
9.根据权利要求1-4任一项的基材(10),特征在于从基材开始的第二金属功能层(80)的以nm计的厚度e80使得:以nm计,12≤e80≤20。
10.根据权利要求1-4任一项的基材(10),特征在于从基材开始的第三金属功能层(120)的以nm计的厚度e120使得:以nm计,11≤e120≤22。
11.根据权利要求1-4任一项的基材(10),特征在于从基材开始的第三金属功能层(120)的以nm计的厚度e120使得:以nm计,12≤e120≤20。
12.根据权利要求1-4任一项的基材(10),特征在于从基材开始的第四金属功能层(160)的以nm计的厚度e160使得:以nm计,11≤e160≤22。
13.根据权利要求1-4任一项的基材(10),特征在于从基材开始的第四金属功能层(160)的以nm计的厚度e160使得:以nm计,12≤e160≤20。
14.根据权利要求1-4任一项的基材(10),特征在于四个金属功能层(40,80,120,160)的总厚度为30至70nm,包括端值。
15.根据权利要求1-4任一项的基材(10),特征在于四个金属功能层(40,80,120,160)的总厚度为为35至65nm。
16.根据权利要求1-4任一项的基材(10),特征在于每一个抗反射涂层(20,60,100,140,180)包含至少一个基于氮化硅的抗反射层(24,64,104,144,184)。
17.根据权利要求1-4任一项的基材(10),特征在于与功能层(40,80,120,160)下邻的每个抗反射涂层的最后层是抗反射润湿层(28,68,108,148),其基于结晶氧化物。
18.根据权利要求17的基材(10),特征在于该抗反射润湿层(28,68,108,148)基于氧化锌。
19.包括至少一个根据权利要求1-18任一项的基材(10)的窗玻璃,该基材任选地与至少一个其它基材结合,该被提供有薄层堆叠体的基材可以进行弯曲和/或淬火。
20.根据权利要求19的窗玻璃,特征在于该窗玻璃是双层窗玻璃或三层窗玻璃类型的多层窗玻璃或层压窗玻璃。
21.根据权利要求19的窗玻璃,特征在于该层压窗玻璃是包含用于该薄层堆叠体的电连接的工具以允许获得加热层压窗玻璃的层压窗玻璃。
22.根据权利要求1-17任一项的基材的用途,用于获得加热窗玻璃的加热透明涂层或用于获得电致变色窗玻璃的或照明装置的或显示装置的或光伏面板的透明电极。
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MX364186B (es) 2019-04-16
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EP2804843B1 (fr) 2017-08-02
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PL2804843T3 (pl) 2018-01-31
EA201491381A1 (ru) 2014-10-30
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FR2985724B1 (fr) 2014-03-07
JP6231494B2 (ja) 2017-11-15
US20150004383A1 (en) 2015-01-01
KR20140124772A (ko) 2014-10-27
CA2858182A1 (fr) 2013-07-25
BR112014014359B1 (pt) 2020-12-29
CA2858182C (fr) 2021-05-04
ES2645615T3 (es) 2017-12-07
CN104039732A (zh) 2014-09-10
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BR112014014359A2 (pt) 2017-06-13
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