CN112218757B - 用于获得包含玻璃板的材料的方法 - Google Patents

用于获得包含玻璃板的材料的方法 Download PDF

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CN112218757B
CN112218757B CN201980004262.6A CN201980004262A CN112218757B CN 112218757 B CN112218757 B CN 112218757B CN 201980004262 A CN201980004262 A CN 201980004262A CN 112218757 B CN112218757 B CN 112218757B
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coating
enamel
glass sheet
pigment
region
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CN112218757A (zh
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J.雅马尔
C.拉朗德
M.拉勒芒
W.克瓦尔
L.迪莫捷
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Saint Gobain Glass France SAS
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Saint Gobain Glass France SAS
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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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Abstract

本发明的主题是用于获得包括玻璃板的材料的方法,所述方法包括如下步骤:‑提供玻璃板,所述玻璃板包括至少部分地被基本上为矿物的第一涂层涂覆的第一面,所述第一面具有至少一个第一区域和至少一个第二区域,所述至少一个第一区域具有比所述第二区域更高的发射率,然后‑在所述第二区域的至少一部分上施加包含树脂的牺牲层,然后‑在至少550℃的温度下热处理所述经涂覆的玻璃板,在此步骤期间通过燃烧除去所述牺牲层。

Description

用于获得包含玻璃板的材料的方法
本发明涉及包含玻璃板,特别是装配玻璃的材料的领域。更具体地,本发明涉及使用高温热处理,例如弯曲和/或回火处理,并且使得获得在光学性能方面更好品质的产品成为可能的方法。
通常通过添加涂层,特别是矿物涂层,来功能化用于制造建筑物或运输车辆用装配玻璃的玻璃板。它们可以是例如旨在改善最终的装配玻璃的热性能的涂层,例如低发射率导电涂层,其将通过反射红外辐射并防止建筑物或车辆的热损失来改善隔热性,或者日光控制涂层,其将吸收和/或反射一部分日光辐射,并因此防止建筑物或车辆内部的热积聚。它们也可以是具有美学功能的涂层,例如搪瓷涂层,其使得例如将装配玻璃的装配密封件隐藏在车辆的车身开口中和保护它们免受紫外线辐射成为可能。它们也可以是具有导电功能的涂层,例如呈线形式的涂层,用于通过焦耳效应加热机动车辆的后窗玻璃。
装配玻璃的制造经常使用在高温,高于550℃下的热处理,特别是弯曲和/或回火处理,旨在机械增强装配玻璃或赋予其所希望的形状。这些处理在加热设备例如炉中进行,在其中玻璃板通过对流和辐射来加热。
发明人已能够证明,当取决于区域以不同的方式涂覆玻璃板时,在某些条件下可能出现光学缺陷。发明人能够观察到,这些光学缺陷源于玻璃板在不同区域中经受的温度可能相差几十度的事实。被反射红外辐射的低发射率涂层覆盖的区域具有小于较大发射率的区域的升温趋势,并且该差异也可能由于在装配玻璃的某些区域中存在吸收红外辐射的涂层而加剧,例如不透明的搪瓷涂层。在某些区域中,反射红外辐射的涂层和吸收红外辐射的涂层的叠加存在也已证明是有问题的。同样地,被吸收红外辐射的涂层例如不透明的搪瓷涂层覆盖的区域具有比未涂覆的区域经受更高温度的趋势。
本发明的目的是消除这些缺点。为此目的,本发明的一个主题是用于获得包含玻璃板的材料的方法,所述方法包括如下步骤:
- 提供玻璃板,所述玻璃板包括至少部分地被基本上为矿物的第一涂层涂覆的第一面,所述第一面具有至少一个第一区域和至少一个第二区域,所述至少一个第一区域具有比所述第二区域更高的发射率,然后
- 在所述第二区域的至少一部分上施加包含树脂的牺牲层,然后
- 在至少550℃的温度下热处理所述经涂覆的玻璃板,在此步骤期间通过燃烧除去所述牺牲层。
所述玻璃板在热处理步骤之前优选是平的。玻璃通常为钠钙玻璃,但是也可以使用其他玻璃,例如硼硅酸盐或铝硅酸盐。所述玻璃板优选通过浮法工艺,即通过将熔融的玻璃倾倒在熔融的锡浴上的方法获得。
所述玻璃板可以是透明的或着色的,例如绿色、蓝色、灰色或青铜色。根据最终的装配玻璃的用途进行选择。在例如机动车辆后窗玻璃的情况下,玻璃的光透射率优选为至少30%;然后玻璃板优选包含0.5重量%至1.2重量%的氧化铁(以Fe2O3的形式表示)含量。在机动车辆挡风玻璃的情况下,所述装配玻璃的光透射率通常为至少70%;然后玻璃板优选包含0.1重量%至0.9重量%的氧化铁含量。
所述玻璃板的厚度优选为0.7至19mm,特别是1至10mm,尤其是2至6mm,或者甚至是2至4mm。玻璃板的表面积优选为至少1 m²。
表述“基本上为矿物的”被理解为表示涂层包含至少50重量%的矿物化合物,优选至少60%,特别是70%,或者甚至80%。根据一个实施方案,所述涂层可以是完全矿物的,任选地除了可能的有机杂质之外。根据另一实施方案,所述涂层包含有机化合物,例如溶剂或介质,所述有机化合物将最迟在热处理步骤期间,任选地在热处理步骤之前,例如在干燥或预烧步骤期间被除去。
本发明的第一方面
根据本发明的第一方面,第一涂层是导电的。这种类型的涂层固有地具有低发射率,可能在热处理步骤期间扰乱加热过程。
第一涂层优选包含至少一种金属,特别是银,或包含至少一种透明的导电氧化物。
在本发明的第一方面的第一优选实施方案中,第一涂层是透明的,并且优选覆盖玻璃板表面积的至少80%,或者甚至90%。这种类型的涂层特别地具有改善装配玻璃的隔热性的作用。
然后,第一涂层优选包含至少一层透明的导电氧化物(TCO)层。所述透明的导电氧化物优选选自混合的铟锡氧化物(ITO)、掺杂的氧化锡,特别是掺杂氟或锑的氧化锡,掺杂的氧化锌,特别是掺杂铝或镓的氧化锌。这些氧化物都是透明且导电的,因此具有低发射率。所述透明的导电氧化物层或每层透明的导电氧化物层的侧面优选有介电层,特别是基于氧化物、氮化物和/或氧氮化物,特别是硅、锡、锌或钛的氧化物、氮化物和/或氧氮化物。透明的导电氧化物的总物理厚度优选为30至200nm,特别是40至150nm。
替代地,第一涂层可以包括至少一层银薄层,所述银薄层或每层银薄层的侧面有介电层。
在本实施方案的上下文中,第一涂层优选通过溅射,特别是磁控溅射,或通过化学气相沉积(CVD)来沉积。
在本发明的第一方面的第二优选实施方案中,第一涂层是不透明的,并且优选地覆盖玻璃板表面积的最多20%,特别是1%至10%,或者甚至1%至5%。第一涂层优选呈导电迹线形式,并且特别地用作加热线或天线线,例如在机动车辆后窗玻璃上。
在此情况下的第一涂层优选包括银浆迹线(silver paste track),特别是由银浆迹线组成。所述迹线通常以穿过玻璃板的线和位于玻璃板边缘上的更宽的母线的形式定位。
在该第二实施方案的上下文中,优选地通过流体组合物的丝网印刷来沉积第一涂层,所述流体组合物包含金属颗粒,特别是银颗粒,玻璃料和有机介质。后者在此方法的热处理步骤期间被除去,这使得固结涂层成为可能。在该烧制处理之后,获得的涂层基本上由被玻璃粘合剂粘合的银颗粒组成。
在潮湿状态,银浆优选包含65重量%至75重量%的银。基于银浆的涂层的厚度优选地在潮湿状态下为20至100μm,或在烧制后为10至50μm。
在本发明的第一方面的上下文中,玻璃板的第一面优选地在至少一部分上被基本上为矿物的第二涂层涂覆。
所述第二涂层有利地是含有颜料,特别是黑色颜料的搪瓷。第二涂层优选为不透明的。
这样的涂层和如上所述的第一涂层在玻璃板的同一面上的同时存在加剧了前述的问题。搪瓷,特别是不透明搪瓷,且尤其是当其为黑色时,特别大地吸收红外辐射,而第一涂层当其导电时反射红外辐射。这导致一方面被第一涂层涂覆的区域和另一方面被第二涂层涂覆的区域,或者甚至在必要时,被第一和第二涂层二者覆盖的区域,或者没有被第一和第二涂层中的任一所覆盖的区域之间大的温度差。
优选地通过流体搪瓷组合物的丝网印刷来沉积搪瓷涂层,所述流体搪瓷组合物包含玻璃料、颜料和有机介质。后者在此方法的热处理步骤期间被除去,这使得固结搪瓷涂层成为可能。因此在烧制之后,搪瓷涂层在玻璃状基质中包含颜料。
所述玻璃料或玻璃状基质优选基于铋和/或锌的硼硅酸盐。所述颜料优选地包含一种或多种选自如下的氧化物:铬、铜、铁、锰、钴、镍的氧化物。它们可以,例如,是铜和/或铁的铬酸盐。在热处理步骤之后,搪瓷涂层的厚度优选为5至50μm,特别是10至40μm。
优选地,第一和第二涂层中的一个部分地覆盖另一个。下面描述几种变体。
根据第一变体,第一涂层是导电的,并且覆盖第二涂层的一部分,第二涂层为含有颜料的搪瓷。优选地,第一涂层包含银浆迹线(特别是根据以上所描述的“第二实施方案”)。前述的对于这些涂层的优选特征在此显然是可适用的。经涂覆的面随后具有第一区域,所述第一区域是没有被银浆迹线涂覆的搪瓷区域,该第一区域具有比被银浆迹线涂覆的第二区域更高的发射率。
在此变体中,可以观察到:在搪瓷被银浆所覆盖的区域中,银浆的存在极大地降低了搪瓷的烧制功效,使得搪瓷在烧制后具有浅灰色色调。还观察到机械弱化,某些情况下导致在热处理之后的冷却期间或者甚至在将电连接器焊接至银浆的操作之后,玻璃板破裂。
优选将在此变体中获得的材料整合至机动车辆后窗玻璃中,第一涂层为包括穿过玻璃板的加热线和位于玻璃板的两个相对侧上的母线的银浆迹线,所述母线沉积在位于玻璃板的周边的搪瓷涂层(特别是黑色搪瓷涂层)上。在此,玻璃板的第一面在使用位置上旨在与车辆的内部接触,并且搪瓷的存在尤其使得从车辆的外侧隐藏母线成为可能。在此,热处理优选为弯曲处理,特别是弯曲-回火处理。在某些情况下,将弯曲玻璃板层压至第二玻璃板,使得涂覆有银浆迹线的第一面与车辆的内部(面4)接触。
根据第二变体,第二涂层是含有颜料的搪瓷,并且部分地覆盖导电的第一涂层。所述第一涂层优选包含至少一种透明的导电氧化物(特别是根据前文所描述的“第一实施方案”)。前述的对于这些涂层的优选特征在此显然是可适用的。经涂覆的面然后具有为搪瓷区域的第一区域,该第一区域具有比第二区域更高的发射率,所述第二区域是仅被导电涂层涂覆的区域。
优选将此变体中获得的材料整合至机动车辆车顶或机动车辆车顶板中,搪瓷优选为黑色搪瓷,位于玻璃板的第一面的周边,并且沉积在导电涂层上,所述导电涂层包含导电氧化物,位于整个所述第一面上。在仅被第一涂层涂覆的区域中,通过第一涂层的低发射率特性降低了加热功效,而在第一涂层被搪瓷覆盖的区域中,红外辐射被搪瓷吸收提供了相反的作用。这导致两个区域之间非常高的温度梯度,产生光学畸变,或者甚至在极端情况下产生物理变形。在使用位置,玻璃板的第一面位于与机动车辆内部接触的位置。
本发明的第二方面
根据本发明的第二方面,第一涂层是含有颜料,特别是黑色颜料的搪瓷。第一涂层优选为不透明的。其优选呈位于玻璃板的周边的条状物的形式。此条状物优选覆盖玻璃板表面积的3%至20%。
搪瓷,特别是不透明搪瓷,并且特别是当其为黑色时,的确比裸露的玻璃更多地吸收红外辐射。这导致一方面被搪瓷覆盖的区域(第一区域)和另一方面没有被搪瓷覆盖的玻璃的区域(第二区域)之间大的温度差。
在搪瓷区域附近,这些差异可能产生光学畸变,有时称为“灼伤线(burn lines)”。当畸变位于靠近被称作“相机区域”的区域(光学传感器必须通过所述区域捕捉光或图像)时,这些畸变尤其是麻烦的。此情况例如是,配备有传感器和/或相机的挡风玻璃,例如雨或光传感器,或驾驶辅助相机。这些传感器或相机位于车辆内部,例如在后视镜固定至挡风玻璃的区域中。为了隐藏并且保护用于固定后视镜的粘合剂,搪瓷涂层通常位于此区域中,但是此搪瓷区域必须布置有小的非搪瓷透射窗,以使得光能够到达传感器。然后,本发明使得减少或者甚至除去相机区域中的光学畸变成为可能。
根据本发明的此方面获得的材料优选为层压装配玻璃,特别是用于机动车辆挡风玻璃的层压装配玻璃,其包括借助于热塑性中间层粘合结合的两块玻璃板,沉积在所述装配玻璃的面2或面4上的搪瓷涂层,特别是呈包含至少一个非搪瓷透射窗的周边条状物的形式的。
优选地通过流体搪瓷组合物的丝网印刷来沉积所述搪瓷涂层,所述流体搪瓷组合物包含玻璃料、颜料和有机介质。后者在此方法的热处理步骤期间被除去,其根据情况将为预烧处理或弯曲处理。因此在烧制之后,搪瓷涂层在玻璃状基质中包含颜料。
所述玻璃料或玻璃状基质优选基于铋和/或锌的硼硅酸盐。所述颜料优选地包含一种或多种选自如下的氧化物:铬、铜、铁、锰、钴、镍的氧化物。它们可以,例如,是铜和/或铁的铬酸盐。在热处理步骤之后,搪瓷涂层的厚度优选为5至50μm,特别是10至40μm
牺牲层
牺牲层包含树脂。下面给出的涉及牺牲层的细节当然适用于以上所描述的本发明的所有方面、实施方案和变体中。
牺牲层中树脂的含量特别为至少10重量%,或至少20%,或者甚至至少30%。其可以为例如至少50重量%,特别是60%,或者甚至至少70%或80%,或者甚至还为90%或95%。
所述树脂可以起到各种作用。在某些情况下,它可能起着热作用,在热处理期间其燃烧使得可以通过释放的热量补偿玻璃板的区域在发射率方面的差异,并因此使加热均匀化。 替代地或另外地,它可以用作粘合剂,将能够运用这种热补偿功能的化合物(通过它们的在热处理期间的燃烧,或通过它们的吸收或反射特别是红外辐射的性质)临时固定至玻璃板的表面。
在第一实施方案中,牺牲层由树脂组成。在此情况下,树脂在热处理期间的燃烧将使得能够均匀热处理。
在第二实施方案中,牺牲层由树脂和耐熔或可燃矿物化合物组成。在此情况下,所述树脂可用于将所述化合物临时固定至玻璃板表面。术语“可燃”矿物被理解为表示这些化合物在热处理期间能够燃烧。术语“耐熔”矿物被理解为表示这些化合物在热处理期间不熔化和不软化。在此情况下,在热处理期间除去树脂的范围内,通过燃烧除去牺牲层,从而不再有实际的牺牲层,但是耐熔矿物化合物或可燃矿物化合物燃烧的可能残留物保留在玻璃板的表面上,并且如果需要,可通过洗涤和/或刷拭操作来除去。
耐熔或可燃矿物化合物有利地是颜料(然后牺牲层特别地可与油漆相当),特别是吸收至少一部分红外辐射,并因此将提高热处理功效的颜料。在本实施方案的上下文中,牺牲层可以通过丝网印刷由有机介质(包含树脂和溶剂)和颜料(特别是黑色颜料)组成的组合物来沉积。
矿物化合物尤其是炭黑,吸收红外辐射的黑色颜料,其可以在热处理期间燃烧,任选地留下容易除去的灰烬。
在某些情况下,可以通过在至少550℃的温度下进行第一热处理除去树脂,在玻璃板的表面上留下一层耐熔矿物化合物,随后使玻璃板经受在至少550℃的温度下的第二热处理,随后通过洗涤和/或刷拭除去耐熔化合物。当绝对必须在最终热处理之前除去树脂时,这种实施方式可以证明是必要的。例如,当最终材料是在面2上包含搪瓷为第一涂层的层压装配玻璃时,在弯曲处理期间,此涂层与层压装配玻璃的内玻璃板的外表面接触。在这种构造中,树脂的燃烧优选发生在预烧搪瓷的预处理期间。随后,在弯曲的时候,仅保留一层耐熔化合物层,例如颜料。
与实施方式无关,可以使用各种树脂。
该树脂特别地可以选自丙烯酸树脂、环氧树脂、酸醇树脂、聚氨酯树脂,单独地或作为混合物,在水相或溶剂相中。这些各种聚合物的共聚物也可以使用。树脂可以在水相或溶剂相中,具有的固体含量通常为20重量%至80重量%,特别是30重量%至70重量%。
树脂可以为UV-可交连树脂,特别是基于(甲基)丙烯酸酯和任选地基于光引发剂;无溶剂的树脂,或任选在水相或溶剂相中的树脂。 如果在施加牺牲层和热处理之间不需要处理玻璃板,则树脂可以不是交联的。 否则,优选提供UV干燥步骤。
该树脂可以是胶乳,即呈水分散液或乳液形式。 干燥可以在空气或炉中进行,但是如果不需要在施加牺牲层和热处理之间处理玻璃板,则可以省略干燥步骤。
该树脂可以是热塑性树脂,例如热熔树脂或热塑性弹性体,例如SEBS(聚苯乙烯-b-聚(乙烯-丁烯)-b-聚苯乙烯)共聚物。
该树脂可以是搪瓷组合物的有机介质的树脂。
优选通过丝网印刷,数字印刷,辊涂,幕涂或喷涂来沉积牺牲层。
牺牲层沉积在第二区域的至少一部分上。 它可以沉积在整个第二区域上或每个第二区域上,或者甚至沉积在整个第一面上。 如果牺牲层不与某些区域不相容,则从工业的角度来看,后一种实施方案是优选的,因为它能够通过幕涂或辊涂技术进行全面沉积。否则,这些技术需要事先掩盖不欲覆盖的区域。 丝网印刷,数字印刷或其他移印的方法本身使得仅在给定区域上沉积牺牲层成为可能。 这些局部沉积技术可能是有用的,例如当本发明的目的是防止照相机区域中的光学畸变时,因为在这种情况下,通过根据本发明的方法仅影响玻璃板的小区域。
牺牲层的厚度优选为100nm至80μm,特别是1μm至30μm,或者甚至5μm至20μm。
热处理使得可以通过燃烧除去牺牲层。 如上所述,在该步骤期间除去了牺牲层的树脂,但是耐熔化合物可以保留在玻璃板的表面,然后可以通过洗涤和/或刷拭除去,任选地在第二热处理之后。
热处理特别是用于弯曲和/或回火玻璃板的处理。热处理使用的温度优选为600℃至750℃,特别为620℃至700℃。热回火处理进一步包括,强制和迅速冷却玻璃表面,例如使用空气喷嘴,以便产生表面压缩应力,其改善玻璃板的机械强度。
当涂层之一是搪瓷或基于银浆时,搪瓷或银浆的烧制优选在该热处理期间进行。
当涂层之一是搪瓷时,在其间通过燃烧除去树脂的热处理也可以是用于预烧所述搪瓷的处理。然后,热处理优选地使用550℃至650℃,特别是560℃至600℃的温度。预烧处理对于发展某些搪瓷的不粘性能特别有用。在这种情况下,优选在热处理之后进行使玻璃板弯曲的处理。如上所述,当第一涂层是旨在放在层压装配玻璃的面2上的搪瓷时,该实施方案特别有价值,所述搪瓷在弯曲处理期间与层压装配玻璃的另一玻璃板接触。在这种情况下,牺牲层有利地包含树脂和耐熔颜料,在搪瓷预烧的处理期间除去树脂并留下颜料层,然后将其在弯曲后和层压前通过洗涤和/或刷拭除去。
在热处理步骤之后,该方法可以包括洗涤和/或刷拭的步骤。 该步骤使得能够除去由牺牲层的燃烧产生的可能的有机残余物,或者甚至当牺牲层包含它们时除去可能的矿物残余物(例如颜料)。
在热处理步骤之后,该方法可以进一步包括层压步骤,其中玻璃板通过热塑性中间层结合至另一玻璃板。
获得的材料可以是用于建筑物或运输车辆,特别是机动车辆的装配玻璃。 在后一种情况下,所述装配玻璃优选是机动车辆车顶,机动车辆车顶板,机动车辆后窗玻璃或机动车辆挡风玻璃。
机动车辆车顶或车顶板优选包括玻璃板,该玻璃板涂覆有搪瓷(特别是黑色搪瓷),该搪瓷位于玻璃板的第一面的周边,并沉积在包含透明导电氧化物的导电涂层上并位于整个第一面上。 第一面旨在与车辆的内部气氛接触,而相对面,或第二面,优选地通过热塑性中间层粘合结合至另一玻璃板。 玻璃板中的一个和/或另一个和/或热塑性中间层优选为着色的,使得装配玻璃的光透射率为最大40%,特别为30%。玻璃板优选为弯曲的。
机动车辆后窗玻璃优选地包括单个弯曲且回火的玻璃板,该玻璃板在旨在与车辆内部接触的面上包括作为第一涂层的银浆迹线,该银浆迹线包括穿过玻璃板的加热线和位于玻璃板的两个相对侧面上母线,所述母线沉积在位于玻璃板的周边的搪瓷涂层(特别是黑色搪瓷涂层)上。 搪瓷的存在尤其使得能够从车辆外侧隐藏母线。
机动车辆挡风玻璃优选地包括弯曲的层压装配玻璃,该弯曲的层压装配玻璃包括借助于热塑性中间层粘合结合的两个玻璃板,位于玻璃板之一的周边,特别是在装配玻璃的面 2或面4上的搪瓷涂层(特别是黑色搪瓷涂层)。 根据所使用的惯例,面2是旨在位于车辆外侧的玻璃板的内表面,因此该面与中间层接触,而面4是旨在位于车辆内侧的玻璃板的内表面。周边的搪瓷使得能够隐藏和保护密封件和粘合剂,粘合剂使装配玻璃能够附着至车身开口,或者使后视镜附着至装配玻璃。 优选地,挡风玻璃包括至少一个传感器,和周边的搪瓷条状物包括与所述传感器相对的非搪瓷的透射窗。
实施例
以下实施例以非限制性的方式阐述本发明。
实施例1
通过丝网印刷对玻璃板进行涂覆,首先在其整个第一面上涂覆黑色搪瓷涂层,然后在该搪瓷涂层的一半上涂覆基于银浆的涂层。 因此,玻璃板的经涂覆的面包括两个区域,第一区域(仅涂覆有搪瓷)的发射率高于第二区域(涂覆有搪瓷和银浆两者)。
然后通过将如此涂覆的玻璃板通过放置在加热到680℃温度的炉子中180秒的时间来热处理。 测量在第一区域(T1)和第二区域(T2)中的玻璃的温度变化(在与第一面相对的面上测量)。
在测试1A和1B中,牺牲层沉积在整个第一和第二区域上。 对于测试1A,牺牲层是一层基于丙烯酸酯的UV交联树脂的层,厚度约为10 µm,而对于测试1B,牺牲层是一层油漆的层,其包含约50%的环氧丙烯酸酯树脂和炭黑作为固体,干燥后的厚度约为5 µm。 在(比较)测试1C中,没有沉积牺牲层。
图1显示了温度差T1-T2与加热时间(t,以秒表示)的函数关系。
结果表明,牺牲层使得能够大大减小温度差,该温度差的绝对值为最大10℃,而在没有牺牲层的情况下,该温度差可以高达80℃。
实施例2
通过溅射在玻璃板的整个第一面上涂覆基于TCO的低发射率涂层,该涂层包括一层混合的铟锡氧化物(ITO)的层,其侧面具有氧化硅和氮化物的薄层。 然后通过丝网印刷用黑色搪瓷涂层涂覆该低辐射率涂层的一半。
因此,玻璃板的经涂覆的面包括两个区域,第一区域(涂覆有搪瓷)的发射率高于第二区域(仅涂覆有低发射率涂层)。
然后通过将如此涂覆的玻璃板通过放置在加热到680℃温度的炉子中180秒的时间来热处理。 测量在第一区域(T1)和第二区域(T2)中的玻璃的温度变化(在与第一面相对的面上测量)。
在测试2A和2B中,在整个第一和第二区域上沉积了牺牲层(分别与测试1A和1B所使用的相同)。 在(比较)测试2C中,没有沉积牺牲层。
图2显示了温度差T1-T2与加热时间(t,以秒表示)的函数关系。
结果表明,牺牲层使得能够大大减小温度差,该温度差的绝对值为最大20℃,而在没有牺牲层的情况下,该温度差可以高达40℃。
实施例3
通过丝网印刷对玻璃板进行涂覆,首先在其整个第一面上涂覆黑色搪瓷涂层,然后在该搪瓷涂层的一半上涂覆基于银浆的涂层。 因此,玻璃板的经涂覆的面包括两个区域,第一区域(仅涂覆有搪瓷)的发射率高于第二区域(涂覆有搪瓷和银浆两者)。
然后通过将如此涂覆的玻璃板通过放置在加热到710℃温度的炉子中180秒的时间来热处理。 测量在第一区域(T1)和第二区域(T2)中的玻璃的温度变化(在与第一面相对的面上测量)。
在测试3A中,牺牲层通过丝网印刷沉积在第二区域上。
丝网印刷的组合物由有机介质和的黑色矿物颜料组成,所述黑色矿物颜料基于铜(37重量%),铁(17重量%)和锰(46重量%)的氧化物。 湿厚度为15μm。 在该实施例中,热处理使得能够通过燃烧树脂除去牺牲层,将颜料留在玻璃表面上。
在(比较)测试3B中,没有沉积牺牲层。
图3显示了温度差T1-T2与温度T1的函数关系。
结果表明,牺牲层使得能够大大减小温度差,在实施例3A的情况中该温度差的绝对值为最大6℃,而在没有牺牲层的情况下,该温度差可以高达大于70℃。
实施例4
将玻璃板通过丝网印刷在玻璃板的第一面的一部分上涂覆黑色搪瓷涂层。 因此,玻璃板的经涂覆的面包括两个区域,第一区域(涂覆有搪瓷)的发射率高于第二区域(未涂覆,因此为裸露的玻璃)。
接下来,为了模拟弯曲条件,将另一未涂覆的透明玻璃板放置在如此涂覆的玻璃板上,以制造层压挡风玻璃。 然后将组件通过放置在加热到710℃温度的炉子中180秒的时间来热处理。 使用位于两块玻璃板之间的热电偶测量第一区域(T1)和第二区域(T2)中的玻璃的温度变化。
在测试4A中,预先通过丝网印刷由有机介质和黑色颜料组成的组合物来涂覆未被搪瓷涂覆的区域(第二区域),该组合物与实施例3的上下文中使用的组合物相同。
在(比较)测试4B中,没有沉积牺牲层。
图4显示了温度差T1-T2与温度T1的函数关系。
结果表明,牺牲层使得能够在高温下大大减小温度差,因为在实施例4A的情况中该温度差的绝对值为最大15℃,而在没有牺牲层的情况下,该温度差可以高达大于35℃。当搪瓷的温度达到500℃时,相比于比较例4B的35℃,在实施例4A的情况下该温度差小于5℃。
实施例5
在比较测试5A中,将一层黑色搪瓷(潮湿厚度为约20μm)的层通过丝网印刷沉积在厚度为2.1mm的第一玻璃板上,所述黑色搪瓷在其中心具有未涂覆的150×130 mm² 的相机区域。在150℃下干燥2分钟后,将搪瓷在600℃预烧115秒,然后将第一玻璃板与厚度为2.1mm的第二玻璃板耦合,使得搪瓷面在第二玻璃板的该侧上,两个玻璃板通过如下维持距离:在它们之间放置提供几十微米空间的中间层粉末,通常为20至50μm。随后使组件经受在610℃下的弯曲处理340秒,然后将两个玻璃板分开、洗涤以除去中间层粉末,并且最终借助于聚乙烯醇缩丁醛(PVB)板层压。因此在获得的层压装配玻璃中,搪瓷层在面2上。
在根据本发明的测试5B中,在预烧处理之前,将牺牲层沉积在黑色搪瓷层和相机区域二者上。为此,在干燥黑色搪瓷之后,将与实施例3和4中所用的相同的由有机介质和黑色颜料组成的组合物,通过丝网印刷进行沉积。将湿厚度为6至8μm量级的该层在150℃下干燥2分钟。预烧处理使得能够通过燃烧有机介质除去牺牲层,将黑色颜料层留在玻璃板上。
然后使用ISRA Vision销售的Labscan机器,用1/2/0滤光器测量照相区域的光学畸变。在比较例5A的情况下,所测得的在相机区域中的最大水平畸变为584毫屈光度,在实施例5B的情况下,为160毫屈光度。
因此在预烧和弯曲期间牺牲层的存在使得能够很大程度地减小相机区域中的畸变。

Claims (19)

1.用于获得包括玻璃板的材料的方法,所述方法包括如下步骤:
- 提供玻璃板,所述玻璃板包括至少部分地被基本上为矿物的第一涂层涂覆的第一面,所述第一面具有至少一个第一区域和至少一个第二区域,所述至少一个第一区域具有比所述第二区域更高的发射率,然后
- 在所述第二区域的至少一部分上施加包含树脂的牺牲层,然后
- 在至少550℃的温度下热处理经涂覆的玻璃板,在此步骤期间通过燃烧除去所述牺牲层。
2.根据权利要求1所述的方法,其中所述第一涂层是导电的。
3.根据权利要求2所述的方法,其中所述第一涂层包含至少一种金属,或包含至少一种透明导电氧化物。
4.根据权利要求3所述的方法,其中所述至少一种金属是银。
5.根据权利要求1-4任一项所述的方法,其中所述第一面在至少一部分上被基本上为矿物的第二涂层涂覆。
6.根据权利要求5所述的方法,其中所述第二涂层为搪瓷,所述搪瓷含有颜料。
7.根据权利要求6所述的方法,其中所述颜料是黑色颜料。
8.根据权利要求5所述的方法,其中所述第一和第二涂层中的一个部分地覆盖另一个。
9.根据权利要求8所述的方法,其中所述第一涂层是导电的,并且覆盖所述第二涂层的一部分,所述第二涂层为含有颜料的搪瓷。
10.根据权利要求9所述的方法,其中所述第一涂层包含银浆迹线。
11.根据权利要求8所述的方法,其中所述第二涂层是含有颜料的搪瓷,并且部分地覆盖导电的第一涂层。
12.根据权利要求1所述的方法,其中所述第一涂层是搪瓷,所述搪瓷含有颜料。
13.根据权利要求12所述的方法,其中所述颜料是黑色颜料。
14.根据权利要求1-4中任一项所述的方法,其中所述牺牲层由树脂和耐熔的或可燃的矿物化合物组成。
15.根据权利要求14所述的方法,其中所述耐熔的或可燃的矿物化合物是颜料组成。
16.根据前述权利要求1-4中任一项所述的方法,其中热处理是用于弯曲和/或回火玻璃板的处理。
17.根据权利要求6至7或9至13中任一项所述的方法,其中所述热处理是用于预烧搪瓷的处理。
18.根据权利要求17所述的方法,其中在用于预烧搪瓷的处理之后进行用于弯曲玻璃板的处理。
19.根据权利要求1-4中任一项所述的方法,在热处理步骤之后,进一步包括层压步骤,其中将所述玻璃板通过热塑性中间层结合至另一玻璃板。
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