CN101784589A - 粘结热塑性弹性体部件至玻璃板的方法 - Google Patents
粘结热塑性弹性体部件至玻璃板的方法 Download PDFInfo
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Abstract
本发明涉及利用一种或多种异氰酸酯基底胶和硅烷基底胶,把由热塑性弹性体(TPE)材料形成的弹性部件粘结到玻璃板的方法,特别地,所述热塑性弹性体材料是苯乙烯-乙烯-丁烯-苯乙烯(SEBS)共聚物和热塑性聚氨酯(TPU)材料的共混物。
Description
背景技术
本发明涉及将弹性部件,例如边缘成型体(peripheral molding),粘合至玻璃板。
近些年来,在汽车玻璃行业中,常见的实践是生产“包边(encapsulated)”车辆窗;换句话说,弹性部件在车辆窗的全部或一部分边缘周围延伸的车辆窗。许多材料已经用来形成这种弹性部件,并且不同的方法已经被用来模塑这种弹性部件。其中最常见的是利用反应注塑成型法(RIM)来模塑的多组分聚氨酯(PU)材料和利用注射模塑法模塑的聚氯乙烯(PVC)。粘合这些材料到玻璃上是存在问题的,并且已经发现必须利用助粘材料,也称为底胶,来增加聚合物材料和玻璃板之间的粘结强度和粘结耐久性。
对于PU和PVC,已经发现各自都适用于不同的应用。然而,在可能的情况下,因为PVC就材料成本而言本质上更加低廉,所以对于包边目的有利的是使用PVC。另一方面,一般来说,PU材料和玻璃形成更强的粘合。随着对制造“环境友好”材料的车辆的不断增加的重视,其中“环境友好”材料即可以有利地回收/重复使用的材料,PVC因为在不合理处理时对环境产生危害而受到批评。因此,人们正加强寻找可以在车辆窗包边中替代PVC的材料。寻找这样的替代材料时要考虑的很多其它性能是(1)成本,(2)强力粘结到玻璃的能力,和(3)为了密封目的提供好的压缩变定的能力。
热塑性弹性体(TPE)材料,包括与各种其他的聚合物材料共混的SEBS或者SBS聚合物,的使用已经在包边和相关应用的专利文献中有所描述,例如:
U.S.专利No.7056971描述了一种本身被描述为透氧的热塑弹性体,其通过将该TPE与液体聚异丁烯油增塑剂以不使被增塑的弹性体发粘的量熔融共混,而得到阻隔氧气的性能。
U.S.专利No.7026028描述了一种多层模塑品,其包含主体部分和至少部分覆盖该主体部分的表层,该主体部分包含交联的弹性体组合物,和该表层包含热塑性弹性体(TPE)。据描述,所述主体部分的TPE赋予表层良好的耐候性。
U.S.专利No.7015284描述了一种热塑性弹性体组合物,其可以重叠模塑到硬基底上,例如塑料或金属表面。所述组合物,当模塑时,据描述是无味、抗刮擦和可着色的。
U.S.专利No.6984688描述了一种与聚丙烯共混且不含填充材料的增塑的氢化TPE嵌段共聚物,其具有乙烯基芳族单体和共轭二烯单体的嵌段(HSBC),据描述其提供一种用于制品的可注塑组合物,其中所述制品需要具有与拉伸强度、撕裂强度、柔软性和雾度相关的特定性能,而且必须的是模塑制品的上述所有性能和物理尺寸在制品浸没在沸腾的水中一小时后基本保持不变。
U.S.专利No.6846571描述了一种据描述适用于汽车地板覆盖应用的聚合物共混物。所述聚合物共混物据描述可加工成片材,其可以回收使用并且其可以展示出低光泽和类似硫化橡胶的触感。这种聚合物共混物据描述还展示出良好的花纹保持性(grain retention)、耐磨性和热及紫外光稳定性。
U.S.专利No.6399696描述了一种热塑性弹性体组合物,据描述其有优良的密封性能并且其防止气体例如挥发性低分子量组分的生成,同时由这种材料制成的模塑制品由于使用了超高分子量聚乙烯的细颗粒而不发粘。
U.S.专利No.5221782描述了一种热塑性树脂组合物,其含有在特定化合物例如作为交联剂的二氢芳族化合物或其聚合物和多官能单体的存在下通过动态热处理热塑性树脂和橡胶状物质制备的部分交联的产物,并进一步加入了软化剂和/或无机填料。
U.S.专利No.5149736描述了苯乙烯-乙烯-丁烯-苯乙烯三嵌段共聚物-油组合物,其据描述是耐热的和不可熔的。所述组合物据描述在升高的温度在压力下是可模塑的。
寻找到热塑性弹性体(TPE)材料,其如同PU粘结到玻璃,但却具有PVC的较低成本,具有良好的密封性能并且其满足车辆制造商对此类材料的其他苛刻标准,将是有利的。
发明概述
本发明涉及利用一种或多种异氰酸酯基底胶(isocyanate-based primer)和硅烷基底胶(silane-based primer),把由TPE材料,特别是苯乙烯-乙烯-丁烯-苯乙烯(SEBS)共聚物和热塑性聚氨酯(TPU)材料的共混物,形成的部件粘结到玻璃板的方法。通过利用本发明的材料,甚至在气候老化后,也可以实现超过TPE材料的内聚强度的粘结强度。
发明详述
本发明涉及热塑性弹性体(TPE)材料,其含有苯乙烯-乙烯-丁烯-苯乙烯(SEBS)共聚物和热塑性聚氨酯(TPU)的共混物,其通过借助常规的注射模塑法把SEBS/TPU模塑到基底的边缘或通过把由本发明的SEBS/TPU材料制成的预先形成的弹性部件粘结到玻璃基底的边缘,而被粘结到玻璃基底上。虽然本发明的SEBS/TPU材料在不对玻璃表面进行特定处理或在使用单一底胶的条件下展示出一定水平的对玻璃基底的粘合,但一些车辆生产商需要通过单独的SEBS/TPU材料或通过使用单一助粘(adhesion-promoting)底胶不能满足的粘合水平。
为了显著增加本发明的SEBS/TPU材料和玻璃基底之间的粘合的强度和耐久性,已经发现两种助粘底胶材料的混合物或分步施加多于一种助粘底胶材料是非常有效的。更加具体地,且优选地在对将要施加所述底胶材料的玻璃基底的表面进行彻底清洁后,把硅烷基底胶和异氰酸酯基底胶的混合物通过任何常规方式施加到玻璃基底边缘的至少一部分上。
可选择地,可能希望的是,同样在首先优选清洁玻璃后,最开始通过任何常规的施加方法把硅烷基底胶施加到玻璃基底的边缘,然后在规定的时间段内,同样通过任何常规施加方法,施加异氰酸酯基底胶,手工地或者自动地。
合适的硅烷基底胶的例子包括:Betaseal 43518TM(Dow Automotive),GC20TM(YH America),和Glasgrip 7780TM(Ashland Chemical Co.)。
合适的异氰酸酯基底胶的例子包括:Betaseal 43520ATM(Dow Automotive),Sika 206G+PTM(Sika),和PC3TM(YH America)。
而且,已经发现加热玻璃基底到预定的温度提高了粘结强度和耐久性。为了最大化粘结强度和耐久性,所述玻璃应该被加热到100°F到300°F,优先地,150°F和250°F之间的温度。
利用前述的底胶体系,在SEBS/TPU材料和玻璃基底之间形成的粘结的强度已经被发现高于SEBS/TPU材料本身的强度,所述强度依赖于所述材料的硬度,其典型地在50ShoreA和90ShoreA之间。在典型车辆将会经历的环境条件下,粘结耐久性通常预期最低为10年。对于上述的10年时间,所述SEBS/TPU材料本身也不应发生将被例如所述典型车辆的拥有者注意到的程度的变色或者其它物理外观退化。
所述SEBS/TPU材料提供了在其性能(例如作为形成车辆天窗(sunroof)上的封条的材料)和成本之间的良好平衡。优选本发明的SEBS/TPU材料的压缩变定,即材料可容忍并且仍然恢复到其原来结构的弹性变形的量,在20%-40%的范围,优选20%-30%,其将在天窗密封应用等等中提供良好的密封能力。同时,希望在每重量单位基础上所述SEBS/TPU材料的成本尽可能接近PVC的成本。
虽然不希望被任何理论束缚,但本发明人相信,当结合所述硅烷基和异氰酸酯基助粘底胶材料时,所述硅烷基底胶,当被直接施加到玻璃基底表面上时,充当偶联剂来提供对玻璃的粘结。所述异氰酸酯基底胶材料然后形成所述硅烷材料和所述SEBS/TPU材料之间的连接物。如前面提到的,无论这两种底胶材料是被混合还是以分步方式分开施加,这种功能看起来都是存在的。
如前面提到的,本发明的范围包括将所述SEBS/TPU材料原位模塑到玻璃基底上以及将由SEBS/TPU材料预先形成的弹性部件粘结到玻璃基底上。
虽然对于本发明可以使用任何常规的注射模塑方法,但是一种优选的方法涉及把玻璃片或者由玻璃片形成的车辆玻璃放置到制造成在模具中精确地安置玻璃的第一半模(mold half)中,所述半模包括具有与玻璃板的边缘的至少一部分重合的区域,该区域构成当注入到模具中时能接收可流动形式的本发明的SEBS/TPU材料的模腔的一半。优选地,在放置到第一半模中之前,底胶的混合物或多个底胶层,已经被预先施加到玻璃边缘的指定区域。典型地,使第二互补半模紧密接触第一半模,形成模腔,该模腔呈将被粘结到玻璃基底的弹性部件轮廓的形式。足量的液体SEBS/TPU材料被注入以充满所述模腔,并在这种情况下与玻璃板的边缘发生粘结接触。冷却足够的时间后,可以从模具中移出已准备好用于使用/储存/运输形式的其上模塑有固化的SEBS/TPU部件的玻璃基底。
还可以通过例如挤出方法预先形成期望型材形式的弹性部件,所述型材然后可以通过手工或自动方式被粘结到玻璃基底上。典型地,理想地将是在使玻璃基底和预先形成的弹性部件发生粘结接触之前,把所述硅烷基/异氰酸酯基底胶施加到玻璃基底或者预先形成的弹性部件上。对于本发明的一些应用可能还期望使用其他粘合剂。在一个优选的方法中,利用夹具或固定装置来在精确位置接收玻璃基底并且与其邻近在所述夹具/固定装置内,形成用来接收所述预先形成的弹性部件的沟槽。应用压力和/或加热有助于弹性部件和玻璃基底的粘合。在这点上,通过原位模塑或粘合预先形成的弹性部件制造的产品理想地是基本相同的。
适合本发明使用的苯乙烯-乙烯-丁烯-苯乙烯共聚物包括,例如,各种苯乙烯嵌段共聚物。
适合本发明使用的热塑性聚氨酯材料包括,例如,EllastolanTM(BASF)和PellathaneTM(DOW Automotive)。如前所述,如果以分步方式分别施加硅烷基底胶材料和异氰酸酯基材料,则异氰酸酯基底胶应该在相对短的时间段内施加在硅烷底胶上。典型地,该时间间隔是在2秒到10分钟之间。优选地,该时间间隔是在2秒到2分钟之间。最优选地,各个底胶层的施加之间的时间间隔是在2秒到60秒之间。
实施例
对比实施例1-6是Pilkington绿色汽车玻璃的1英寸×6英寸片,在其边缘的一部分附件已经施加了陶瓷瓷釉(ceramic enamel)JM 355Frit。所有的样品都先预加热到200°F的温度。对于对比实施例1和4,然后在存在所述陶瓷烧结料(ceramic frit)的区域中,将Dow Betaseal和Lord Chemical487A/B底胶的混合物施加到所述玻璃上。然后把121-75M 1004热塑性硫化产品TPV材料模塑到存在所述底胶混合物的玻璃的边缘部分上。然后使样品固化30分钟。
关于对比实施例1和4描述的相同工艺被用于对比实施例2和5,不同的是Betaseal和487A/B底胶被分别施加,而不是作为混合物,和模塑到玻璃上的聚合物材料是SEBS材料,即Vichem SevreneTM 3570-80-8843。
对比实施例3和6通过与对比实施例2和5相同的方法制备,除了模塑到施加底胶的玻璃样品边缘的材料是TPE材料,即GLS KratonTM G7820-9001-00。
根据本发明的实施例1和2根据与对比实施例2,3,5和6相同的方法制备,除了施加的第二底胶是Dow Betaseal和模塑到施加底胶的玻璃上的聚合物材料是SEBS/TPU TPE材料,即GLS LC 303-123之外。
为了测试如上所述制备的模塑上的聚合物材料对玻璃样品的粘合的强度和相关性能,在环境室温或72°F测试实施例1和对比实施例1-3,而在80℃(176°F)测试实施例2和对比实施例3-6。与样品结果对比的规格是:
初始剪切强度规格>0.5MPa&100%材料破裂
初始剥离强度规格>50N/25mm&100%材料破裂
热(80℃)剪切强度规格>0.2MPa&100%材料破裂
热(80℃)剥离强度规格>15N/25mm&100%材料破裂
拉伸试验在Instron Universal Test Machine 42.01上以200mm/min的拉伸速度实施。
如可从下面的表1中看出的那样,根据本发明的实施例1和2的本发明的SEBS/TPU材料,特别地结合本文其他地方描述的类型的底胶,满足或超过严格的OEM粘结规格和在性能上优于其他被测的聚合物材料/底胶体系。
表1:
Claims (12)
1.利用一种或多种异氰酸酯基底胶和硅烷基底胶,把弹性部件粘结到玻璃板的方法,所述弹性部件包含苯乙烯-乙烯-丁烯-苯乙烯(SEBS)共聚物和热塑性聚氨酯(TPU)材料的共混物。
2.如权利要求1所述的方法,其中所述玻璃板是车辆玻璃。
3.如权利要求2所述的方法,其中所述一种或多种底胶被施加到所述车辆玻璃的边缘的至少一部分上。
4.如权利要求3所述的方法,其中所述弹性部件通过注射模塑或反应注塑成型方法的一种被模塑到已经施加了所述一种或多种底胶的所述车辆玻璃的边缘的至少一部分上。
5.如权利要求3所述的方法,其中将要粘结的所述弹性部件通过模塑或挤出方法的一种被预先形成。
6.如权利要求3所述的方法,其中异氰酸酯基底胶被施加在所述车辆玻璃上先前施加的硅烷底胶上。
7.如权利要求3所述的方法,其中硅烷基底胶被施加到所述车辆玻璃的边缘的一部分上,并且在其后在2秒到10分钟的时间间隔内,将异氰酸酯基底胶施加在所述硅烷基底胶上。
8.如权利要求7所述的方法,其中施加所述硅烷基底胶和施加所述异氰酸酯基底胶之间的间隔时间在2秒和2分钟之间。
9.如权利要求8所述的方法,其中施加所述硅烷基底胶和施加所述异氰酸酯基底胶之间的间隔时间在2秒和10秒之间。
10.如权利要求3所述的方法,其中硅烷基底胶和异氰酸酯基底胶的混合物被施加到所述车辆玻璃的边缘的至少一部分上。
11.如权利要求5所述的方法,其中在把所述预先形成的弹性部件粘结到所述车辆玻璃上之前,将其上设置有一种或多种底胶的所述车辆玻璃预先加热到100°F(24℃)到300°F(135℃)的温度。
12.如权利要求1所述的方法,其中所述弹性部件和所述玻璃板之间的粘结强度至少等于所述弹性部件的材料的内聚强度。
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BRPI0813130A2 (pt) | 2015-02-18 |
EP2162487A1 (en) | 2010-03-17 |
WO2008156649A1 (en) | 2008-12-24 |
US20080319133A1 (en) | 2008-12-25 |
JP2010530325A (ja) | 2010-09-09 |
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