CN116113611A - 包括玻璃片材的机动车辆后窗或角窗 - Google Patents

包括玻璃片材的机动车辆后窗或角窗 Download PDF

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Publication number
CN116113611A
CN116113611A CN202280006047.1A CN202280006047A CN116113611A CN 116113611 A CN116113611 A CN 116113611A CN 202280006047 A CN202280006047 A CN 202280006047A CN 116113611 A CN116113611 A CN 116113611A
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CN
China
Prior art keywords
motor vehicle
oxide
quarter window
transparent mineral
coating
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Pending
Application number
CN202280006047.1A
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English (en)
Inventor
J·雅玛尔特
K·查邦尼
J·巴查鲁什
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Saint Gobain Glass France SAS
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Saint Gobain Glass France SAS
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Filing date
Publication date
Application filed by Saint Gobain Glass France SAS filed Critical Saint Gobain Glass France SAS
Publication of CN116113611A publication Critical patent/CN116113611A/zh
Pending legal-status Critical Current

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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
    • C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
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    • C03C17/25—Oxides by deposition from the liquid phase
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Abstract

本发明涉及一种机动车辆的后窗或角窗(1，10)，包括第一玻璃片材(2)，其旨在位于车辆外侧的面在其至少一部分上涂覆有至少两个透明的矿物涂层(4，12)，该矿物涂层形成装饰，所述矿物涂层可相同或不同，所述至少两个矿物涂层在所述外侧面的至少一个区域(24，26，28)中叠加。

Description

包括玻璃片材的机动车辆后窗或角窗
本发明涉及用于包括玻璃片材的机动车辆的后窗或角窗的领域。
本发明的目的是提出具有吸引人的装饰的机动车辆后窗或角窗，所述装饰特别是仅从车辆外部可见的装饰。
为此目的，本发明的目标是一种机动车辆后窗或角窗，该后窗或角窗包括第一玻璃片材，该第一玻璃片材的旨在位于车辆外侧的面在其至少一部分上涂覆有至少两个形成装饰的透明矿物涂层，该至少两个透明矿物涂层可相同或不同，所述至少两个矿物涂层在所述外侧面的至少一个区域上叠加。
本发明的另一个目的是获得这种机动车辆的后窗或角窗的方法，包括在玻璃片材的面的至少一部分上连续沉积至少两个形成装饰的透明矿物涂层，该至少两个透明矿物涂层可相同或不同，所述至少两个矿物涂层在所述外侧面的至少一个区域上叠加。
本发明的另一个目的是一种包括至少一个根据本发明的后窗或角窗的机动车辆。
存在至少两个形成装饰的叠加的矿物涂层使得可以赋予不寻常的光学性质，而不会对车辆乘客的光和热舒适性具有有害影响。更特别地，装饰可以以良好的对比度对车辆外部的人可见，而对车辆的乘客不可见。
在本文的其余部分中，后窗或角窗将被简称为“装配玻璃”。
根据本发明的装配玻璃优选地是弯曲的，以便匹配车辆的曲率。
因此，在装配玻璃的内侧面和装配玻璃的外侧面之间有区别，所述装配玻璃的内侧面旨在位于车辆的内侧，所述装配玻璃的内侧面为凹面，所述装配玻璃的外侧面旨在位于车辆的外侧，所述配玻璃的外侧面为凸面。
根据第一实施方案，装配玻璃是层合的，即，它进一步包括附加玻璃片材，该附加玻璃片材通过热塑性层合中间层、特别是基于聚乙烯醇缩醛的热塑性层合中间层，粘合地结合到第一玻璃片材上。在这种情况下，每个玻璃片材具有面向车辆内部的内侧面和面向车辆外部的外侧面。
在该实施方案中，第一玻璃片材旨在位于车辆的外侧上。然后，第一玻璃片材的涂覆有所述至少两个透明矿物涂层的面旨在位于车辆的外侧。该面在本领域中通常被称为“面1”。这样，装饰对于车辆外部的人是可见的，但对于乘客舱的乘客是不可见的。
根据第二实施方案，装配玻璃是单片的，即，其仅包括单个玻璃片材，在此情况下包括第一玻璃片材。在这种情况下，第一玻璃片材通常由钢化玻璃制成，以便满足安全方面的规章要求。以类似于在层合装配玻璃的情况下所描述的方式，涂覆有透明矿物涂层的面是面1(旨在位于车辆外部)。
第一玻璃片材可以是平的或弯曲的。第一玻璃片材在沉积涂层时通常是平的，并且随后是弯曲的。
第一玻璃片材的玻璃通常是钠钙硅玻璃，但是也可使用其它玻璃，例如硼硅酸盐或铝硅酸盐。第一玻璃片材优选通过浮法获得，即通过由以下组成的方法获得：将熔融玻璃浇注到熔融锡浴上。
第一玻璃片材优选由有色玻璃制成。
其优选具有在2％至75％之间，特别地在5％至60％之间，或甚至大于30％的透光率，由此可以确保装饰的良好对比度，并因此确保装饰的良好的可见度，但仅在外侧。
为此，玻璃优选包含以下着色元素，其含量以重量计如下所定义：Fe2O3(全铁)为1.2-2.3％，特别是1.5-2.2％，CoO为50-400ppm，特别是200-350ppm，Se为0-35ppm，特别是10-30ppm。氧化还原优选在0.1至0.4之间，特别在0.2至0.3之间。氧化还原是亚铁含量(表示为FeO)与全铁含量(表示为Fe2O3)的重量比。
根据另一个实施方案，玻璃优选包含作为其唯一着色元素的氧化铁，以如下定义的重量含量：Fe2O3(全铁)为0.1-1.1％，特别是0.5-1.0％。氧化还原优选在0.1和0.4之间。
在本文中，透光率是考虑光源D65和CIE-1931标准观察者来表示的。理应在没有任何涂层的情况下测量玻璃片材的透光率。
第一玻璃片材优选具有包括在0.7至19mm，特别是1至10mm，特别是2至6mm，甚至2至4mm范围内的厚度。
第一玻璃片材(以及，在合适情况下附加玻璃片材)的横向尺寸将适应旨在将装配玻璃并入的车辆，更特别地，随着装配玻璃旨在安装在的车身开口的尺寸的变化而变化。第一装配玻璃(和/或附加玻璃片材)的表面积优选为至少0.5m2、特别是至少1m2。
第一玻璃片材优选地在玻璃片材面的5％至90％的表面积上，特别是在10％至80％的表面积上，基于所需的装饰，涂覆有透明矿物涂层。
第一玻璃片材或附加玻璃片材优选地涂覆有不透明层，所述不透明层特别地由搪瓷制成，典型地由黑色搪瓷制成，特别地布置在其周边处，例如以周边带的形式。这种层的目的通常是隐藏和保护用于在车身开口中安装装配玻璃的聚合物密封件免受紫外线辐射。
该不透明层优选通过丝网印刷或数字印刷来沉积。
在层合装配玻璃的情况下，不透明层优选沉积在附加玻璃片材上。
当不透明层和透明矿物涂层沉积在第一玻璃片材上时，它们可沉积在同一个面上或两个相对面上。涂层沉积的顺序是无关紧要的，但是当它们沉积在同一个面上时，优选首先沉积透明矿物涂层，然后沉积不透明层。
根据优选实施方案，低辐射涂层插入在第一玻璃片材和透明矿物涂层之间。在环境温度下测量的该涂层的标准辐射优选大于0.50，特别是0.30，并且甚至是0.20或0.10。
该涂层的折射率以及在适当的情况下其颜色可以影响装配玻璃的最终外观。
低辐射涂层优选是薄层的堆叠。薄层堆叠优选与第一玻璃片材接触。它优选覆盖第一玻璃片材的整个表面或至少90％的表面。
在本文中，“接触”旨在表示物理接触。表述“基于”优选地旨在表示以下事实：所讨论的层包括至少50％重量的所讨论的材料，特别是60％、或甚至70％并且甚至80％或90％重量的所讨论的材料。层甚至可基本上由这种材料组成或可由这种材料组成。“基本上由...组成”应理解为表示层可包含对其性质没有影响的杂质。术语“氧化物或“氮化物”不一定表示是化学计量的氧化物或氮化物。实际上，它们可以是亚化学计量、超化学计量或化学计量的。
堆叠优选包括至少一个基于氮化物的层。氮化物特别是选自铝、硅、锆、钛中的至少一种元素的氮化物。它可包括这些元素中的至少两种或三种的氮化物，例如氮化硅锆或氮化硅铝。基于氮化物的层优选是基于氮化硅的层，更特别地是基本上由氮化硅组成的层。当氮化硅层通过阴极溅射沉积时，它通常含有铝，因为通常的做法是用铝掺杂硅靶以加速沉积速率。
基于氮化物的层优选具有2至100nm，特别是5至80nm的物理厚度。
基于氮化物的层通常用于薄层的大量堆叠，因为它们具有有利的阻挡性质，由于它们防止堆叠中存在的其它层的氧化，特别是将在下面描述的功能层的氧化。
优选地，堆叠包括至少一个功能层，特别是导电功能层。功能层优选地包括在两个薄介电层之间，其中至少一个是基于氮化物的层。其它可能的介电层是例如氧化物或氮氧化物的层。
至少一个导电功能层有利地选自：
-金属层，特别是银、铌或金层，和
-透明导电氧化物的层，所述透明导电氧化物特别地选自铟锡氧化物、掺杂的锡氧化物(例如掺杂有氟或锑)、掺杂的锌氧化物(例如掺杂有铝或镓)。
这些层由于其低辐射而特别有价值，其赋予装配玻璃优异的绝热性质。在装备装配玻璃的机动车辆中，低辐射装配玻璃使得可以在热天气中向外反射部分太阳辐射，并因此限制所述车辆的乘客室的加热，并且在合适的情况下降低空调成本。相反，在寒冷的天气中，这些装配玻璃使得可以将热量保持在乘客室内，并因此减少所需的加热能量。
根据一个优选的实施方案，薄层的堆叠包括至少一个银层，特别是一个、两个、三个或甚至四个银层。银层的物理厚度，或者在合适的情况下银层的厚度总和，优选为2-50nm，特别为3-40nm。
根据另一优选的实施方案，薄层的堆叠包括至少一个铟和锡的氧化物的层。其物理厚度优选在30至200nm之间，特别是在40至150nm之间。
为了在弯曲步骤期间，保护该或每个导电薄层(无论是金属的还是基于透明导电氧化物的)，这些层中的每一个优选地被至少两个介电层包围。介电层优选基于选自硅、铝、钛、锌、锆和锡中的至少一种元素的氧化物、氮化物和/或氧氮化物。
薄层堆叠的至少一部分可以通过各种已知技术沉积，例如化学气相沉积(CVD)，或者通过阴极溅射沉积，特别是磁场辅助的(磁控方法)。
薄层的堆叠优选通过阴极溅射，特别是磁控溅射来沉积。在该方法中，在高真空中靠近包含待沉积的化学元素的靶产生等离子体。通过轰击靶，等离子体的活性物质令所述元素剥落，所述元素沉积在玻璃片材上，形成所需的薄层。当层由从靶上剥落的元素与等离子体中所含气体之间的化学反应产生的材料制成时，该方法被称为“反应性方法。该方法的主要优点在于，通过使玻璃片材在各种靶下方连续运行，通常在同一设备中，可以在同一生产线上沉积非常复杂的层的堆叠。
上述实例具有导电和红外反射的性质，其具有用于提供加热功能(除霜、除雾)和/或热绝缘功能的用途。
当薄层的堆叠旨在提供加热功能时，必须提供电流供应。这尤其可以是通过在玻璃片材的两个相对边缘处在薄层的堆叠上丝网印刷来沉积的银膏的条。
透明矿物涂层使得可以局部地改变装配玻璃的光学性质，以便产生装饰。矿物涂层优选赋予着色外观，着色可源自(根据情况可为)干涉现象或源自来自层的透射中的颜色，这是由于例如着色物质的存在。在干涉的情况下，仅在某些观察角度下，例如在广角下，才可看到着色。
根据本发明，第一玻璃片材具有涂覆有至少两个相同或不同的形成装饰的透明矿物涂层的面，所述至少两个矿物涂层在所述涂覆的面的至少一个区域中叠加。
在某些区域中，装饰可以包括若干叠加厚度的相同性质的透明矿物涂层，或者甚至在其化学组成和其厚度方面相同。或者，装饰可由多个不同性质的透明矿物涂层形成，多个不同性质的透明矿物涂层特别具有不同的化学组成，在一些区域叠加。
在不存在涂覆有单一透明矿物涂层的装配玻璃区域的意义上，至少两个透明矿物涂层可精确地叠加。或者，至少两个透明矿物涂层可仅部分叠加。在这种情况下，装配玻璃的某些区域可仅用单一透明矿物涂层涂覆。
已经观察到，在叠加区域中，所获得的光学效果，特别是颜色，不同于在其中沉积单一矿物涂层的区域中所获得的。因此，通过连续地且任选地局部沉积两个涂层，或者甚至三个、四个或更多个涂层，可以获得高度变化的装饰。
例如，装饰可包括仅由第一透明矿物涂层形成的第一区域、仅由不同于第一的第二透明矿物涂层形成的第二区域、以及通过叠加第一涂层和第二涂层形成的第三区域。
每个透明涂层的透光率优选在40％和95％之间，特别是在50％和80％之间。
选择这种透射使得不会显著降低乘客室内的亮度，其中装饰仍然保持从外部清晰可见。
透明矿物涂层可通过具有比玻璃低的折射率而具有抗反射性质。在这种情况下，装饰将通过将该涂层与另一透明矿物涂层叠加而获得。
形成装饰的每个透明矿物涂层的物理厚度优选在20至250nm之间，特别地在50至200nm之间，或甚至在100至150nm之间。在此，这是最终产品的厚度，即在固化或烧结的任选步骤之后。在一些情况下，特别是当光学效果是由于干涉效应获得时，厚度的选择使得可以调节所获得的色调。
每个透明矿物涂层优选是基于氧化物的。这种涂层具有不使任选的插入的低辐射涂层劣化，并且特别是不过度影响其辐射性质的优点。
氧化物优选选自钛氧化物、硅氧化物、锆氧化物、锡氧化物、锌氧化物、铝氧化物、铟氧化物和过渡金属氧化物。过渡金属特别是铜、铁、钴、铬和锰。
由于存在着色物质，例如颜料或金属颗粒，例如金颗粒，透明矿物涂层可具有着色外观。
每个基于氧化物的透明矿物涂层有利地是溶胶-凝胶涂层，其为通过溶胶-凝胶法获得的涂层。
溶胶-凝胶法通常包括：
-形成“溶胶”，即含有至少一种待沉积氧化物前体的溶液，
-将该溶液施加到待涂覆的表面上，
-通过热处理使涂层固结或致密化。
前体特别包括其氧化物将被沉积的元素的盐。它们特别是有机金属化合物或硝酸盐、乙酸盐、氯化物等。作为有机金属化合物的实例，可提及例如醇盐，例如在硅氧化物层的情况下为四原硅酸盐(TEOS)，或在钛氧化物层的情况下为四异丙醇钛。
溶胶可以是部分含水的。它优选包含有机溶剂，例如醇，特别选自乙醇、异丙醇、丁醇和二醇或二醇衍生物，及其混合物。溶胶可进一步含有粘度调节剂，例如纤维素醚或聚丙烯酸酯。
优选地，每个透明矿物涂层是基于氧化物的，并且每个沉积步骤包括该氧化物的前体，特别是溶胶，的丝网印刷或数字印刷。数字印刷技术例如涉及喷墨打印技术。
在丝网印刷的情况下，将丝网印刷丝网放置在第一玻璃片材上，该丝网包括孔，所述孔中的一些孔被封闭，然后将组合物，特别是溶胶，沉积在丝网上，然后施加刮刀以迫使溶胶在其中丝网孔未被封闭的区域中通过丝网，从而形成湿溶胶-凝胶层。
在沉积之后，优选干燥湿涂层以除去溶剂，特别是在100-200℃的温度下。干燥步骤优选在每次沉积之后进行。
在一些情况下，所有透明矿物涂层可随后进行预固化处理，特别是在550至650℃的温度下。该处理在弯曲之前的附加步骤的情况下是特别有用的，例如为了制造层合的装配玻璃而与附加玻璃片材组装的步骤，或者沉积不透明层的步骤，特别是在与涂覆有透明矿物涂层的面相对的面上，需要在所述相对面上传送。
在沉积透明矿物涂层之后，优选弯曲第一玻璃片材以及在合适的情况下的附加玻璃片材。当至少一个透明矿物涂层是溶胶-凝胶层时，弯曲可引起该层的致密化和固结。
弯曲可以使用重力进行，例如(玻璃在其自身重量下变形)或通过压制，在典型地550-650℃的温度下进行。
根据第一实施方案，两个玻璃片材(第一玻璃片材和附加玻璃片材)分别弯曲。根据第二实施方案，第一玻璃片材和附加玻璃片材分别弯曲。
层合步骤可通过在高压釜中处理来进行，例如在110至160℃的温度下和在10至15巴的压力下。在高压釜处理之前，玻璃片材和层合中间层之间截留的空气可以通过压延或通过施加负压来消除。
附加的玻璃片材可由钠钙硅玻璃或硼硅酸盐或铝硅酸盐玻璃制成。它可由透明或有色玻璃制成。其厚度优选在0.5至4mm之间，特别是在1至3mm之间。
层合中间层优选包括至少一个聚乙烯醇缩醛片材，特别是聚乙烯醇缩丁醛(PVB)片材。其有利地由这种片材组成。层合中间层尤其通常不包括基于液晶的活性层。
如果需要，层合中间层可为有色的或无色的，以调节装配玻璃的光学或热性质。层合中间层可有利地具有消声性质，以便吸收空气传播的或结构传播的声音。为此，它可特别由三个聚合物片材组成，包括两个包围内部聚合物片材的“外部”PVB片材，该内部聚合物片材任选由PVB制成，具有硬度低于外部片材的硬度。
层合中间层还可具有热绝缘性质，特别是红外辐射反射性质。为此，它可包括具有低辐射的薄层的涂层，例如包含银薄层的涂层或具有不同折射率的交替介电层的涂层，沉积在由两个外部PVB片材包围的内部PET片材上。
层合中间层的厚度通常在0.3-1.5mm，特别是0.5-1mm的范围内。层合中间层在装配玻璃的边缘可以具有比在装配玻璃的中心的厚度更小的厚度，以便防止在使用平视显示器(HUD)的情况下形成重影。
实施例
以下示例性实施方案结合图1以非限制性方式示出了本发明。
图1示出了根据本发明的示例性装配玻璃1。
图2示出了根据本发明的另一示例性装配玻璃10。
装配玻璃1是由具有绿色色调的3.85mm厚的钠钙硅玻璃的玻璃片材2形成的机动车辆角窗。玻璃片材2的透光率为60％。
然后通过溶胶-凝胶溶液的丝网印刷沉积装饰(其在实施例中是基于三角形的)，形成两个叠加的涂层4。为此目的，对由Ferro以TLU0050编号出售的溶液进行两次连续的印刷，其中每次涂覆的湿厚度为14μm，并且中间干燥(150℃，2分钟)。
然后将玻璃片材2弯曲并在650℃回火180秒。装饰具有从车辆外部可见的反射外观。
装配玻璃10是由具有绿色色调的3.85mm厚的钠钙硅玻璃的玻璃片材2形成的机动车辆后窗。玻璃片材2的透光率为40％。
通过丝网印刷相同的溶胶-凝胶溶液(Ferro TLU0050)的连续步骤在玻璃片材2上形成装饰。在区域22中，沉积单个涂层12。在区域24中，叠加两个涂层12。在区域26中，叠加三个涂层12。在区域28中，叠加四个涂层12。在两个连续的沉积步骤之间进行中间干燥(150℃，2分钟)。各涂层的湿厚度为14μm。在650℃下回火和弯曲处理180秒后，每个涂层的厚度为约30至40nm。
叠加涂层使得可以产生具有不同外观的区域：区域22具有银色外观，区域24具有金色外观，区域26具有粉红外观，并且区域28具有蓝色外观。

Claims (15)

1.一种机动车辆的后窗或角窗(1，10)，包括第一玻璃片材(2)，该第一玻璃片材的旨在位于车辆外侧的面在其至少一部分上涂覆有至少两个形成装饰的透明矿物涂层(4，12)，该至少两个透明矿物涂层可相同或不同，所述至少两个矿物涂层叠加在所述外侧面的至少一个区域(24，26，28)中。
2.根据权利要求1所述的机动车辆的后窗或角窗(1，10)，进一步包括通过热塑性层合中间层、特别是基于聚乙烯醇缩醛的热塑性层合中间层粘合地结合至所述第一玻璃片材(2)的附加玻璃片材。
3.根据前述权利要求之一所述的机动车辆的后窗或角窗(1、10)，所述后窗或角窗是弯曲的，旨在位于所述车辆的外侧上的面是凸面。
4.根据前述权利要求之一所述的机动车辆的后窗或角窗(1、10)，其中所述第一玻璃片材(2)具有在2％和75％之间、特别地在5％和60％之间的透光率。
5.根据前述权利要求之一所述的机动车辆的后窗或角窗(1、10)，其中在所述第一玻璃片材(2)和所述透明矿物涂层(4、12)之间插入低辐射涂层。
6.根据前述权利要求之一所述的机动车辆的后窗或角窗(1、10)，使得在某些区域中，所述装饰包括若干叠加厚度的相同类型的透明矿物涂层。
7.根据前述权利要求之一所述的机动车辆的后窗或角窗(1、10)，使得所述装饰包括仅由第一透明矿物涂层形成的第一区域、仅由不同于所述第一透明矿物涂层的第二透明矿物涂层形成的第二区域、以及通过叠加所述第一透明矿物涂层和所述第二透明矿物涂层而形成的第三区域。
8.根据前述权利要求之一所述的机动车辆的后窗或角窗(1、10)，其中每个透明矿物涂层(4、12)的透光率在40％和95％之间，特别是在50％和80％之间。
9.根据前述权利要求之一所述的机动车辆的后窗或角窗(1、10)，其中形成装饰的每个透明矿物涂层(4、12)的物理厚度在20nm和250nm之间，特别地在50nm和200nm之间。
10.根据前述权利要求之一所述的机动车辆的后窗或角窗(1、10)，其中每个透明矿物涂层(4、12)是基于氧化物的。
11.根据前述权利要求所述的机动车辆的后窗或角窗(1、10)，其中每个透明矿物涂层(4、12)是溶胶-凝胶涂层。
12.根据权利要求10或11中任一项所述的机动车辆的后窗或角窗(1、10)，其中所述氧化物选自钛氧化物、硅氧化物、锆氧化物、锡氧化物、锌氧化物、铝氧化物、铟氧化物和过渡金属氧化物。
13.一种用于获得根据前述权利要求之一所述的机动车辆的后窗或角窗(1、10)的方法，包括在玻璃片材的面的至少一部分上连续沉积形成装饰的至少两个透明矿物涂层(4、12)，该至少两个透明矿物涂层(4、12)可相同或不同，所述至少两个矿物涂层叠加在所述外侧面的至少一个区域(24、26、28)中。
14.根据前述权利要求所述的方法，其中每个透明矿物涂层(4，12)是基于氧化物的，每个沉积步骤包括该氧化物的前体的丝网印刷或数字印刷，特别是溶胶的丝网印刷或数字印刷。
15.一种机动车辆，包括至少一个根据权利要求1至12中任一项所述的后窗或角窗。
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