CN108811491A - 封装方法 - Google Patents

封装方法 Download PDF

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CN108811491A
CN108811491A CN201880000821.1A CN201880000821A CN108811491A CN 108811491 A CN108811491 A CN 108811491A CN 201880000821 A CN201880000821 A CN 201880000821A CN 108811491 A CN108811491 A CN 108811491A
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metal insert
tpe
elastomeric seal
weight
encapsulating
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A.斯特里谢
F.皮鲁
C.克莱奥
B.格朗吉拉尔
O.勃朗
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Saint Gobain Glass France SAS
Compagnie de Saint Gobain SA
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Abstract

本发明涉及一种用于制造复杂汽车窗玻璃的方法，该窗玻璃包含玻璃板，弹性体密封件和用弹性体密封件进行包覆成型的金属插件，该方法包括：‑将玻璃板的边缘和金属插件***封装模具中，该封装模具形成围绕该玻璃板边缘的密封腔室，‑通过注入包含熔融状态的聚丙烯(PP)/热塑性弹性体(TPE)配混物的封装组合物来填充该包含玻璃板边缘和金属插件的密封腔室，‑冷却该封装组合物以形成弹性体密封件，使金属插件集成在弹性体密封件中，‑使弹性体密封件脱模，在弹性体密封件中集成了金属插件，该方法的特征在于所述PP/TPE配混物包含30至80重量％，优选40至75重量％，特别是45至70重量％的聚丙烯(PP)，并且该金属插件在其整个可能将与封装组合物接触的表面上覆盖有聚丙烯涂层。

Description

封装方法
本发明涉及一种用于制造复杂汽车窗玻璃，优选玻璃车顶的方法，该方法包括通过在含有大尺寸金属插件的封装模具中注入流化热塑性弹性体进行封装的步骤。
在汽车窗玻璃工业领域中，术语“封装”是指围绕玻璃板周边包覆成型聚合物材料的方法或步骤。含有聚合物材料或聚合物材料前体的封装组合物以或多或少粘性流体的状态注入到形成围绕玻璃板边缘的密封腔室的模具中。在通过冷却或交联固化该组合物之后，打开并移除模具，在玻璃板的周边留下与侧面以及与玻璃板的两个面中的至少一个接触的成型带。
形成成形带的固化聚合物通常是能够用作在窗玻璃和车厢之间的密封的弹性体。
最常用作为用于制造玻璃汽车车顶的封装材料的弹性体是通过注射-反应模塑(RIM)获得的聚氨酯。将前体、单体或低聚物，通常是多元醇和多异氰酸酯注入模具中，在那里它们进行反应以形成三维交联网络。
RIM封装特别适用于制造复杂的汽车窗玻璃，例如玻璃车顶，其不仅包括玻璃板和弹性体密封件，还包括起到机械增强作用的大尺寸金属插件。这些复杂的汽车窗玻璃还可以包括部分或完全被结合在封装中的其它部件，例如定心销或侧支架(side brackets)。
RIM封装组合物由于其非常高的流动性，甚至可以完美地填充模具腔室的难以到达的区域。此外，交联聚氨酯在金属插件表面上的粘附，通常受到通过电泳施加的涂料的防腐蚀保护，是优异的。
使用热塑性聚合物(特别地热塑性弹性体(TPE))以封装汽车窗玻璃构成了通过RIM获得的热固性弹性体的非常有益的替代。
基于TPE的汽车窗玻璃的密封件事实上是可回收的，而基于聚氨酯RIM的密封件则不是最终情况。此外，TPE的使用消除了与使用挥发性反应性和毒性单体如异氰酸酯相关的问题。
由热塑性弹性体制造密封件已经成功地用于封装简单的和具有相对适中尺寸的汽车窗玻璃，例如后侧窗。
对于具有更大尺寸的汽车窗玻璃的封装，特别地对于汽车窗玻璃，例如车顶，其包含具有机械增强作用的包覆成型(surmoulé)的金属插件，TPE的使用仍然存在问题，并且直到现在也没有被设想用在工业规模上。
当使用基于TPE的封装组合物用于制造具有大尺寸插件的复杂窗玻璃的密封件时，本领域技术人员面临的技术问题之一是获得TPE在金属插件表面上的不充分粘附。这些金属插件，例如长度为几十厘米的型材，通常涂有通过电泳沉积的涂料。该涂料通常由热固性阳离子聚合物组成，对热塑性聚合物不具有特别的亲和力。在***件和热塑性密封件之间的不足粘附性可体现为部分或完全脱层然后是玻璃完整性损失。
本发明基于这样的想法：通过使用预先涂有聚丙烯层的插件并使用TPE和聚丙烯的配混物(TPE/PP配混物)作为热塑性弹性体材料来改善TPE密封件和插件之间的粘附性。热注入的TPE/PP配混物充分软化插件的聚丙烯，使得两种组分的聚丙烯链可以相互渗透并形成牢固的粘合。
因此，本申请涉及一种用于制造复杂汽车窗玻璃的方法，该窗玻璃包含玻璃板，弹性体密封件和用弹性体密封件进行包覆成型(surmoulé)的金属插件，包括：
-将玻璃板的边缘和金属插件***封装模具中，该封装模具形成围绕该玻璃板边缘的密封腔室，
-通过注入包含熔融状态的聚丙烯(PP)/热塑性弹性体(TPE)配混物的封装组合物来填充该包含玻璃板边缘和金属插件的密封腔室，
-冷却该封装组合物以形成弹性体密封件，使金属插件集成在弹性体密封件中，
-弹性体密封件的脱模，在弹性体密封件中集成了金属插件，
该方法的特征在于所述PP/TPE配混物包含30至80重量％，优选40至75重量％，特别是45至70重量％的聚丙烯(PP)，并且该金属插件在其整个可能将与封装组合物接触的表面上覆盖有聚丙烯涂层。
待封装的玻璃板可以是由无机玻璃或塑料制成的玻璃板。它可以由单一玻璃或塑料片材构成，或者由两个或多个玻璃或塑料片材形成，它们借助于通常称为层压中间层的物体相互粘合，该层压中间层通常由聚乙烯醇缩丁醛(PVB)或聚(乙烯-乙酸乙烯酯共聚物)(EVA)构成。
所述一个或多个玻璃片材和层压中间层可以是着色的，而玻璃在其整体中保持一定的透明度，具有的透光率(TL)优选在10-50％之间，特别是在15-40％之间。
在本发明方法的一个优选实施方案中，所述玻璃板是由两个通过层压中间层彼此粘合的无机玻璃片材组成的层压玻璃板。
如在引言中所解释的，本发明的方法特别适用于具有足够大尺寸的，可用于复杂的窗玻璃(例如汽车玻璃车顶)的玻璃板。
玻璃板的尺寸优选使得其周长至少等于1米，优选地在1.0米-8.0米之间，特别是在1.3米-4.5米之间，理想地在1.5米-4.0米之间。
在注入封装组合物之前在封装模具中引入的金属插件优选地具有足够大的尺寸，例如接近玻璃板尺寸之一的长度，例如长度在10cm-1.5m之间，特别是在15至1.2m之间。
可能将与封装组合物接触的金属插件的表面典型地是几十平方厘米，甚至几百平方厘米，特别是10平方厘米至1000平方厘米的面积。本发明的方法当然可以用于具有小于10cm2的接触面积的较小尺寸的***件，但是其有用性将是较小的，因为在***件的表面和包覆成型的密封件之间的可能脱层(导致玻璃的完整性损失)是很小可能性的。
术语“热塑性弹性体(TPE)”是指具有刚性(或硬)域和柔性(或软)域的非均相聚合物材料。这些材料在包括环境温度的有限温度范围内具有弹性行为，并且在高于刚性区域的软化温度的温度下具有塑性行为，因此可以被用作为热塑性聚合物。
热塑性弹性体是已知的，它们的命名和分类在ISO 18064中定义。
用于本发明方法的热塑性弹性体优选地选自下列聚合物：
-未硫化的乙烯-丙烯-二烯单体(EPDM)橡胶，
-部分硫化的乙烯-丙烯-二烯单体橡胶(EPDM)，和
-热塑性苯乙烯弹性体(TPE-S)，如聚(苯乙烯-b-丁二烯-b-苯乙烯)嵌段共聚物(SBS)，聚(苯乙烯-b-(乙烯-丁烯)-b-苯乙烯)嵌段共聚物(SEBS)和聚(苯乙烯-b-(乙烯-丙烯)-b-苯乙烯)嵌段共聚物(SEPS)。
当这些TPE与聚丙烯共混时，所得TPE/PP配混物也具有热塑性弹性体性能，即在包括环境温度(20℃)的某一温度范围内的弹性行为，和超出该温度范围的热塑性行为。
聚丙烯不仅改善了包覆成型的密封件和金属插件之间的粘附性，而且还有利地增加了所获得的密封件的肖氏A硬度。
除TPE/PP配混物外，在本发明方法中使用的封装组合物还含有一种或多种添加剂，其主要功能是降低热封装组合物的粘度，降低所得最终材料的成本，和/或提高所得最终材料的物理或化学稳定性。
降低成本的添加剂是例如矿物填料，例如白垩，高岭土，滑石，氧化锌和炭黑。相对于封装组合物的总重量，它们可以以通常1至15重量％，优选2至10重量％的量存在。这种矿物填料的存在增加了所形成的密封件的肖氏A硬度。
油，优选矿物油，用作为加工助剂并允许降低玻璃化转变温度并使热封装组合物流化。相对于封装组合物的总重量，它们例如以10至50重量％，优选20至45重量％的比例存在。它们的存在对最终密封件的硬度几乎没有影响。
最后，抗氧化剂或抗紫外线稳定剂也可以少量存在，通常小于1重量％。
然而，这些添加剂的总量不应超过约30至35重量％的上限，并且封装组合物优选包含35至65重量％，优选45至60重量％，特别是50至57重量％的PP/TPE配混物，相对于封装组合物的总重量。
含有PP/TPE配混物和添加剂(矿物油/矿物填料/稳定剂)的即用型封装组合物可从TEKNOR APEX，EXXON，KRAIBURG，MCPP，MULTIBASE公司商购获得。
封装组合物优选在170℃至260℃之间，特别是在170℃至220℃之间的温度下，在15巴至120巴之间，优选在15巴至80巴之间的压力下被注入。
封装组合物的“硬化”通过模具和封装材料的简单冷却(主动或被动，优选主动)来完成。换句话说，固化步骤不包括用于封装组合物的化学交联的加热步骤。
密封件的脱模有利地在完全冷却至室温之前进行，例如在40至120℃的温度下进行。
包覆成型的金属插件可以是任何金属材料。它们优选由钢制成。它们可以任选地覆盖有有机或无机的表面涂层，例如通过电泳沉积的涂料，其有效地保护它们免受腐蚀。
因此，金属插件的聚丙烯涂层可以与金属表面直接接触，或者可以被沉积在通过电泳沉积的涂料层上。聚丙烯涂层的厚度有利地在0.1-5mm之间，优选在0.5-4mm之间，特别是在1-3mm之间，这些范围(fourchettes)不包括通过电泳沉积的可能的涂料层的厚度。聚丙烯涂层可以例如以粉末涂料的形式进行沉积，其在热的作用下变成薄膜。
聚丙烯涂层有利地由至少95重量％，优选至少98重量％，理想地100重量％的聚丙烯构成。特别优选不含矿物填料。

Claims (8)

1.一种用于制造复杂汽车窗玻璃的方法，该窗玻璃包含玻璃板，弹性体密封件和用弹性体密封件进行包覆成型的金属插件，该方法包括：
-将玻璃板的边缘和金属插件***封装模具中，该封装模具形成围绕该玻璃板边缘的密封腔室，
-通过注入包含熔融状态的聚丙烯(PP)/热塑性弹性体(TPE)配混物的封装组合物来填充该包含玻璃板边缘和金属插件的密封腔室，
-冷却该封装组合物以形成弹性体密封件，使金属插件集成在弹性体密封件中，
-使弹性体密封件脱模，在弹性体密封件中集成了金属插件，
该方法的特征在于所述PP/TPE配混物包含30至80重量％，优选40至75重量％，特别是45至70重量％的聚丙烯(PP)，并且该金属插件在其整个可能将与封装组合物接触的表面上覆盖有聚丙烯涂层。
2.根据权利要求1所述的方法，其特征在于，所述插件的可能将与所述封装组合物接触的表面为10cm2-1000cm2。
3.根据权利要求1或2的方法，其特征在于TPE选自
-未硫化的乙烯-丙烯-二烯单体(EPDM)橡胶，
-部分硫化的乙烯-丙烯-二烯单体橡胶(EPDM)，和
-热塑性苯乙烯弹性体(TPE-S)，如聚(苯乙烯-b-丁二烯-b-苯乙烯)嵌段共聚物(SBS)，聚(苯乙烯-b-(乙烯-丁烯)-b-苯乙烯)嵌段共聚物(SEBS)和聚(苯乙烯-b-(乙烯-丙烯)-b-苯乙烯)嵌段共聚物(SEPS)。
4.根据前述权利要求中任一项所述的方法，其特征在于，覆盖金属插件的聚丙烯涂层具有为0.1至5mm，优选为0.5至4mm，特别是1至3mm的厚度。
5.根据前述权利要求中任一项所述的方法，其特征在于，所述封装组合物还包含矿物填料，例如白垩，高岭土，滑石，氧化锌和炭黑，加工助剂如油，优选矿物油，或抗氧化剂或抗紫外线稳定剂。
6.根据前述权利要求中任一项的方法，其特征在于所述封装组合物包含35至65重量％，优选45至60重量％，特别是50至57重量％的PP/TPE配混物，相对于封装组合物的总重量。
7.根据前述权利要求中任一项所述的方法，其特征在于，所述封装组合物在170℃至260℃，优选在170℃至220℃的温度下，在15巴至120巴，最好在15巴至80巴的压力下被注入。
8.根据前述权利要求中任一项所述的方法，其特征在于，所述流体封装组合物的冷却步骤是通过封装模具的主动冷却进行的。
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