CN108811492A - 机动车玻璃板 - Google Patents

机动车玻璃板 Download PDF

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CN108811492A
CN108811492A CN201880000890.2A CN201880000890A CN108811492A CN 108811492 A CN108811492 A CN 108811492A CN 201880000890 A CN201880000890 A CN 201880000890A CN 108811492 A CN108811492 A CN 108811492A
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tpe
sealing element
glass plate
metal insert
glass
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A.斯特里谢
C.克莱奥
B.格朗吉拉尔
F.皮鲁
O.勃朗
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Saint Gobain Glass France SAS
Compagnie de Saint Gobain SA
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Abstract

本发明涉及机动车玻璃板，其包括窗玻璃和热塑性弹性体密封件，所述密封件包含PP/TPE配混物，所述PP/TPE配混物包含38‑80wt％、优选40‑75wt％、特别是45‑70wt％的聚丙烯(PP)。

Description

机动车玻璃板
本发明涉及机动车玻璃板，特别是玻璃采光顶，其包括窗玻璃、热塑性弹性体密封件和任选地由所述热塑性弹性体密封件重叠注塑的金属嵌件。
在机动车玻璃板的工业领域(通常由于语言的误用而被称为汽车玻璃板)，术语“包封”表示围绕窗玻璃的周边将聚合物材料重叠注塑的方法或步骤。将含有聚合物材料或聚合物材料的前体的包封组合物以具有可变粘度的流体状态注入模具中，形成围绕窗玻璃的边缘的密封腔。在通过冷却或交联使该组合物硬化后，打开并移除模具，使得异型珠粒在窗玻璃的周边处与边缘并与窗玻璃的两个面中的至少一个面接触。
形成异型珠粒的硬化聚合物通常是能够在玻璃板和主体(body)之间起密封作用的弹性体。
最常用作制造机动车玻璃采光顶的包封材料的弹性体是通过反应注射成型(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，在其中它们反应形成三维交联网络。在RIM包封组合物中使用了两种类型的多异氰酸酯：芳族多异氰酸酯和脂族多异氰酸酯。已知芳族多异氰酸酯具有更高的反应性，它们可以有效地减少生产周期。它们也更便宜并且具有更好的耐溶剂性。
然而，聚氨酯的缺点是它们易受UV老化的影响，这可能导致暴露表面褪色、出现裂纹或脆化。
已经提出了若干种改善聚氨酯抗UV性的解决方案，包括开发特殊的催化剂、优化反应物之间的化学计量或加入UV稳定剂。
本发明提出了使用聚氨酯的替代解决方案以解决UV敏感性的这一问题。事实上已经证明，将某些热塑性聚合物、特别是热塑性弹性体(TPE) 用于包封机动车玻璃板构成了针对通过RIM获得的热固性弹性体在抗UV性方面的非常有利的替代品。
此外，TPE的使用提供了其他有利的优点：基于TPE的用于机动车玻璃板的密封件实际上是可回收的，而这对基于RIM聚氨酯的密封件而言并非如此；而且TPE的使用消除了与使用有毒的反应性挥发性单体(例如异氰酸酯)有关的问题。
因此，本发明涉及机动车玻璃板，其包括窗玻璃、热塑性弹性体密封件和任选地由所述热塑性弹性体密封件重叠注塑的金属嵌件，所述密封件包含PP/TPE配混物，所述PP/TPE配混物包含38-80wt％、优选40-75wt％、特别是45-70wt％的聚丙烯(PP)。
总的来说，所述密封件可包含至多5wt％、优选小于3wt％或甚至小于1wt％的偶联剂，例如功能性烷氧基硅烷。在一个具体实施方案中，所述密封件不含功能性烷氧基硅烷。
待包封的窗玻璃可以是由矿物玻璃制成的窗玻璃或由塑料制成的窗玻璃。它可以由单片玻璃或塑料制成，或者由两片或更多片玻璃或塑料形成的层压窗玻璃制成，所述两片或更多片玻璃或塑料通过通常称为层压夹层的物件而粘合在一起，所述层压夹层通常由聚(乙烯醇缩丁醛)(PVB)或聚(乙烯-乙酸乙烯酯)共聚物(EVA)构成。
所述一片或多片玻璃和层压夹层可以是着色的，但是窗玻璃整体保持一定的透明度，透光率(LT)优选为10-50％，特别是15-40％。
在本发明方法的一个优选实施方案中，所述窗玻璃是层压窗玻璃，其由两片通过层压夹层粘合在一起的矿物玻璃组成。
根据本发明的玻璃板优选是玻璃采光顶，这样的玻璃板特别暴露于UV光。窗玻璃的尺寸优选使得其周长至少等于1.0m，优选1.0-8.0m，特别是1.3-4.5m，理想是1.5-4.0m。
根据本发明的玻璃板可包括一个或多个由热塑性弹性体密封件重叠注塑的金属嵌件。金属嵌件可以起到机械增强和/或支撑的作用。证明所述金属嵌件，特别是具有大尺寸的金属嵌件对于复杂的汽车玻璃板，例如玻璃采光顶，特别是玻璃板天窗而言是必需的。汽车玻璃板还可以包括部分或完全引入包封中的其他组件，例如定位销或侧托架。
金属嵌件优选具有相当大的尺寸，例如接近窗玻璃的尺寸之一的长度，例如10cm-1.5m、特别是15cm-1.2m的长度。
因此与热塑性弹性体密封件接触的重叠注塑的金属嵌件的表面积可以是小于10cm2的接触表面积。然而，它优选是为几十平方厘米、或甚至几百平方厘米、特别是在10cm2-1000cm2的接触表面积。
术语“热塑性弹性体(TPE)”表示包含刚性(或硬)域和柔性(或软)域的非均相聚合物材料。这些材料在包括室温在内的受限温度范围内表现出弹性体性能，并且在高于刚性域的软化点的温度下它们采取塑性性能并因此可以用作热塑性聚合物。
热塑性弹性体是已知的并且它们的命名和分类被定义在标准ISO 18064中。
用于根据本发明的方法的热塑性弹性体优选选自下列聚合物：
-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(EPDM)橡胶，和
-苯乙烯热塑性弹性体(TPE-S)，例如聚(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与聚丙烯混合时，所得的TPE/PP配混物还具有热塑性弹性体性质，即在包括室温(20℃)在内的一定温度范围内的弹性性能以及超出该温度范围的热塑性性能。
聚丙烯还有利地增加所得密封件的肖氏A硬度。
根据本发明的玻璃板具有非常好的抗UV辐射性，从而使得根据标准ISO 11664、在使用天候老化仪(WoM)1000小时来实施老化1000小时后、根据标准SAE J1960所定义的条件测得的颜色变化ΔE*小于1。因此，本发明还涉及包含PP/TPE配混物的包封密封件改善机动车玻璃板的抗UV辐射性的用途，所述PP/TPE配混物包含38-80wt％、优选40-75wt％、特别是45-70wt％的PP。
本申请还涉及制造机动车玻璃板的方法，所述玻璃板包括窗玻璃、弹性体密封件和任选地由弹性体密封件重叠注塑的金属嵌件，所述方法包括：
-将窗玻璃和任选的金属嵌件的边缘***包封模具中，形成围绕所述窗玻璃的边缘的密封腔，
-通过注入包含熔融状态的聚丙烯(PP)/热塑性弹性体(TPE)配混物的包封组合物来填充包括窗玻璃和任选的金属嵌件的边缘的密封腔，
-冷却所述包封组合物，以形成其中引入所述金属嵌件的弹性体密封件，
-使其中引入所述金属嵌件的弹性体密封件脱模，
所述方法的特征在于，所述PP/TPE配混物包含38-80wt％、优选40-75wt％、特别是45-70wt％的聚丙烯(PP)。
除TPE/PP配混物外，用于根据本发明的汽车玻璃板的包封组合物可包含一种或多种添加剂，其主要功能是降低包封组合物的高温粘度，促进组合物与窗玻璃的粘合，降低所得最终材料的成本，和/或增加所得最终材料的物理或化学稳定性。
为了促进密封件和窗玻璃之间的粘合，相对于包封组合物的总重量，包封组合物通常可包含至多5wt％、优选小于3wt％、或甚至小于1wt％的偶联剂，例如功能性烷氧基硅烷。在一个具体实施方案中，所述密封件不含功能性烷氧基硅烷。
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。相对于包封组合物的总重量，它们可以以典型地1-15％、优选2-10wt％的量存在。所述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，用作应用助剂并且可以降低玻璃化转变温度并增加热包封组合物的流动性。它们例如以相对于包封组合物的总重量的10-50wt％、优选20-45wt％的比例存在。它们的存在对最终密封件的硬度的影响很小。
最后，抗氧化剂或抗UV稳定剂也可以少量存在，通常小于1wt％。
然而，所述添加剂的总量不得超过约30-35wt％的上限，并且相对于包封组合物的总重量，包封组合物优选包含35-65wt％、优选45-60wt％、特别是50-57wt％的PP/TPE配混物。
含有PP/TPE配混物和添加剂(矿物油/矿物填料/稳定剂)的即用型包封组合物可从TEKNOR APEX、EXXON、KRAIBURG、MCPP、MULTIBASE公司商购获得。
优选在170℃-260℃、特别是170℃-220℃的温度下，在15巴-120巴、优选15巴-80巴的压力下注入包封组合物。
包封组合物的“硬化”通过模具和包封材料的简单冷却(主动或被动的，优选主动的)而发生。换句话说，硬化步骤不包括用于包封组合物的化学交联的加热步骤。
密封件的脱膜有利地在完全冷却至室温之前，例如在40-120℃的温度下发生。
重叠注塑的金属嵌件可以由任何金属材料制成。它们优选由钢制成。它们可任选地覆盖有有效地保护它们免受腐蚀的有机或矿物表面涂层，例如阳离子电泳沉积的涂料层。
本发明通过以下非限制性实施例说明。
实施例
通过使用包含PP/TPE配混物的TPE将由矿物玻璃制成的窗玻璃包封而获得的根据本发明的汽车玻璃板(实施例1)包含38-80wt％的PP，以及通过使用一方面包含芳族多异氰酸酯(实施例2)、另一方面包含脂族多异氰酸酯(实施例3)的RIM包封组合物包封由矿物玻璃制成的窗玻璃获得的两个对比汽车玻璃板***(实施例2和实施例3)。
根据标准SAE J1960定义的条件、使用天候老化仪(WoM)1000小时对这三种玻璃板***进行加速老化循环。由于每种包封组合物包含相同量的炭黑填料，因此所得的包封密封件在老化之前都具有深黑色。为了测定UV老化对包封密封件的影响，通过根据标准ISO11664在D65灯下以2°的观察者角度在老化前和老化后的密封件上实施的L*a*b*颜色的测量来计算ΔE*的值。还基于由标准EN20105-A02：1994定义的灰度级谱来评估颜色的牢固性，其中值5对应于老化前的密封件的深黑色。结果示于下表中。
样品 包封材料 ΔE* 灰度级谱
实施例1 PP/TPE配混物 < 1 4-5
实施例2 芳族PU-RIM > 8 2
实施例3 脂族PU-RIM < 2 3
对比实施例2和对比实施例3中的玻璃板***显示其在老化后显著褪色，如通过高ΔE*值和/或灰度级谱中的低分数所示。相反，根据本发明的实施例1中的玻璃板受UV老化的影响非常少。

Claims (10)

1.机动车玻璃板，其包括窗玻璃和热塑性弹性体密封件，所述密封件包含PP/TPE配混物，所述PP/TPE配混物包含38-80wt％、优选40-75wt％、特别是45-70wt％的聚丙烯(PP)。
2.如权利要求1所述的玻璃板，其特征在于，它包括由热塑性弹性体密封件重叠注塑的金属嵌件、至少一个定位销或至少一个侧托架。
3.如权利要求1或权利要求2所述的玻璃板，其特征在于，所述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(EPDM)橡胶，和
-苯乙烯热塑性弹性体(TPE-S)，例如聚(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.如权利要求1-3中任一项所述的玻璃板，其特征在于，所述密封件包含至多5wt％、优选小于3wt％或甚至小于1wt％的偶联剂。
5.如权利要求1-4中任一项所述的玻璃板，其特征在于，所述密封件不含功能性烷氧基硅烷。
6.制造机动车玻璃板的方法，所述玻璃板包括窗玻璃、弹性体密封件和由所述弹性体密封件重叠注塑的金属嵌件，所述方法包括：
-将窗玻璃和金属嵌件的边缘***包封模具中，形成围绕所述窗玻璃的边缘的密封腔，
-通过注入包含熔融状态的聚丙烯(PP)/热塑性弹性体(TPE)配混物的包封组合物来填充包括窗玻璃和金属嵌件的边缘的密封腔，
-冷却所述包封组合物，以形成其中引入所述金属嵌件的弹性体密封件，
-使其中引入所述金属嵌件的弹性体密封件脱模，
所述方法的特征在于，所述PP/TPE配混物包含38-80wt％、优选40-75wt％、特别是45-70wt％的聚丙烯(PP)，并且其中所述金属嵌件在其可能与包封组合物接触的所有表面上覆盖有聚丙烯涂层。
7.如权利要求6所述的方法，其特征在于，所述包封组合物包含至多5wt％、优选小于3wt％或甚至小于1wt％的偶联剂。
8.如权利要求6或权利要求7所述的方法，其特征在于，所述密封件不含功能性烷氧基硅烷。
9.如权利要求6-8中任一项所述的方法，其特征在于，所述包封组合物另外包含矿物填料，例如白垩、高岭土、滑石、氧化锌和炭黑、施用助剂，例如油，优选矿物油、或抗氧化剂、或抗紫外线稳定剂。
10.如权利要求6-9中任一项所述的方法，其特征在于，相对于所述包封组合物的总重量，所述包封组合物包含35-65wt％、优选45wt％-60wt％、特别是50-57wt％的PP/TPE配混物。
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