CN107429046A - 屋顶隔膜以及生产屋顶隔膜的方法 - Google Patents

屋顶隔膜以及生产屋顶隔膜的方法 Download PDF

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CN107429046A
CN107429046A CN201680011500.2A CN201680011500A CN107429046A CN 107429046 A CN107429046 A CN 107429046A CN 201680011500 A CN201680011500 A CN 201680011500A CN 107429046 A CN107429046 A CN 107429046A
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tpu
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帕斯卡·玛丽亚·休伯特·皮埃尔·泰杰森
卡洛琳·米特雷纳
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Abstract

本发明涉及包含阻隔膜的屋顶隔膜，所述阻隔膜由包含热塑性聚氨酯(TPU)和热塑性聚醚酯(TPEE)的聚合物组合物组成。

Description

屋顶隔膜以及生产屋顶隔膜的方法
本发明涉及屋顶隔膜和生产屋顶隔膜的方法。屋顶隔膜和生产屋顶隔膜的方法从EP-A-1100844中是已知的。
屋顶隔膜通常被应用在斜屋顶处，在屋顶覆盖物的下方，例如在瓷砖、板岩等的下方。这样的屋顶隔膜是防止水渗透到建筑物内的阻隔物，例如来自屋顶覆盖物中的泄漏的水、由被吹过瓷砖的间隙的细雪熔化而形成的水或者起因于由瓢泼大雨而引起的水渗透。然而，由于片材具有足够的水蒸汽渗透性(也表示为湿蒸汽透过率)，所以倾向于积聚在建筑物中的湿度被释放，使得室内条件变得足够干燥以确保在建筑物中生活或工作的人的身体健康，并避免在建筑物的木结构中腐烂，例如在屋顶结构的木梁中。
一般来说，屋顶隔膜包含一层绒头织物和一层阻隔膜或者两层绒头织物和阻隔膜，其中阻隔膜位于两层绒头织物之间。EP-A-1100844的屋顶隔膜的阻隔膜由包含共聚醚酯的聚合物组合物组成。
包含共聚醚酯的聚合物组合物的阻隔膜的优点包括可以生产低厚度的膜。对于通过挤出涂布和通过层压生产的两种屋顶隔膜来说，这是有价值的。此外，共聚醚酯具有良好的热稳定性，这是非常重要的，因为屋顶隔膜可能经受高温，在被应用于瓷砖下方时尤其如此。在屋顶处应用后，片材偶尔会被暴露几个月，最多四个月是屋顶建筑工人通常所接受的在应用屋顶覆盖物之前对阳光的紫外线照射的时期。另外，在应用覆盖物后，暴露可能会继续，因为在屋顶覆盖物中存在开口，这使阳光射线穿过。共聚醚酯的一个缺点就是耐UV性低。这可以通过添加UV稳定剂和/或UV吸收剂(例如EP-A-1100844中所公开的)来解决，但是特别是UV稳定剂是昂贵的，并且仍然需要进一步改善的耐UV性。
此外，包含共聚醚酯的聚合物组合物的膜是滑溜的。因为通常以朝向建筑物外部的方式来应用屋顶隔膜的阻隔膜的层，所以建筑物施工者经常不得不行走在膜上。如果膜是光滑的，这可能会导致安全方面的问题。
阻隔膜也可以由包含热塑性聚氨酯的聚合物组合物组成。热塑性聚氨酯的优点包括：采用合适的UV稳定剂和/或UV吸收剂时能够获得非常高水平的耐UV性，并且表面的摩擦系数高，提供低的滑溜性。热塑性聚氨酯的一大缺点是粘度低。由于粘度低，无法生产具有低厚度的阻隔膜，这使得膜从成本方面看没有吸引力。
本发明的目标是提供不表现出这些缺点且仍然具有成本吸引力的屋顶隔膜。
该目标通过如下实现：提供包含聚合物组合物的阻隔膜的屋顶隔膜，该聚合物组合物包含共聚醚酯和热塑性聚氨酯。
令人惊奇的是，本发明的聚合物组合物可以被挤出成薄的阻隔膜，即使在高挤出速度下也是如此，类似于热塑性共聚醚酯的阻隔膜的挤出。
此外，根据本发明的屋顶隔膜的阻隔膜显示出非常高的耐UV性，类似于热塑性聚氨酯的阻隔膜的耐UV性。
此外，根据本发明的屋顶隔膜的阻隔膜显示出非常高的耐温性，类似于热塑性共聚醚酯弹性体的阻隔膜的耐高温性。
最后，由于TPU的价格相对较低，屋顶隔膜更具成本效益。这对于包含TPU的阻隔膜的屋顶隔膜来说不是这种情况，然而TPU不能被加工成具有低厚度的阻隔膜。
共聚醚酯(TPEE)合适地含有由衍生自至少一种亚烷基二醇和至少一种芳族二羧酸或其酯的重复单元构成的硬链段。作为“链段”的替代性术语，也可以使用术语“嵌段”。线性或脂环族亚烷基二醇通常含有2-6个C原子，优选地2-4个C原子。它们的例子包括乙二醇、丙二醇和丁二醇。优选地使用丙二醇或丁二醇，更优选1,4-丁二醇。合适的芳族二羧酸的例子包括对苯二甲酸、2,6-萘二羧酸，4,4'-联苯二羧酸或它们的组合。其优点是所得聚酯通常为半结晶的，熔点高于150℃，优选地高于175℃，更优选地高于190℃。硬链段可以任选地进一步含有少量衍生自其它二羧酸的单体，例如间苯二甲酸，其通常降低聚酯的熔点。其它二羧酸的含量优选地被限制在不超过10摩尔％，更优选地不超过5摩尔％，以确保共聚醚酯的其他性能、尤其结晶性能不受不利影响。硬链段优选由对苯二甲酸乙二醇酯、对苯二甲酸丙二醇酯以及特别是对苯二甲酸丁二醇酯作为重复单元构成。这些容易获得的单元的优点包括有利的结晶行为和高熔点，导致共聚醚酯具有良好加工性能、优异的耐热性和耐化学性以及良好的抗穿刺性。
组分(a)的共聚醚酯中的合适的脂族聚醚软链段是基本无定形且玻璃化转变温度(Tg)低于0℃的柔性聚醚。优选地，Tg低于-20℃，更优选地低于-40℃，最优选地低于-50℃。链段的摩尔质量可以在宽范围内变化，但优选地摩尔质量选自400至6000g/mol，更优选500至4000g/mol，最优选750至3000g/mol。合适的脂族聚醚包括衍生自2-6个C原子、优选2-4个C原子的环氧烷烃的聚(亚烷基氧)二醇或其组合。实例包括聚(亚乙基氧)二醇，聚(四亚甲基氧)二醇或聚(四氢呋喃)二醇，聚(亚新戊基氧-共聚-四亚甲基氧)二醇，聚(亚丙基氧)二醇和环氧乙烷封端的聚(亚丙基氧)二醇。如果共聚醚酯包含聚醚链段，如聚丙二醇链段、聚乙二醇链段和/或聚四氢呋喃链段，则获得本发明片材的高耐久性。聚四氢呋喃链段提供最好的耐久性，聚乙二醇链段提供高耐久性和高蒸汽渗透性的组合。
共聚醚酯可以进一步含有具有两个或更多个可以与酸或羟基反应的官能团的化合物，分别作为扩链剂或支化剂。合适的扩链剂的实例包括羰基双内酰胺、二异氰酸酯和双环氧化物。合适的支化剂包括例如偏苯三酸、偏苯三酸酐和三羟甲基丙烷。选择扩链剂或支化剂的量和类型，使得获得所期望的熔融粘度的嵌段共聚酯。一般来说，支化剂的量不会超过6.0当量每100摩尔呈现共聚醚酯的二羧酸。
共聚醚酯的实例和制备例如被描述于Handbook of Thermoplastics,ed.O.Olabishi,第17章,Marcel Dekker Inc.,New York 1997,ISBN 0-8247-9797-3中，Thermoplastic Elastomers,2nd Ed,第8章,Carl Hanser Verlag(1996),ISBN 1-56990-205-4中，Encyclopedia of Polymer Science and Engineering,第12卷,Wiley&Sons,NewYork(1988),ISBN 0 471-80944,第75-117页，以及其中所引用的参考文献中。
热塑性聚氨酯(TPU)可以通过二异氰酸酯、短链二醇或二胺和长链二醇或二胺之间的反应来形成。通常用作二异氰酸酯的是4,4'-二苯基甲烷二异氰酸酯(MDI)。短链二醇可被用作扩链剂。这种短链二醇的实例包括乙二醇、1,4-丁二醇和1,6-己二醇。优选使用聚醚二醇或聚醚二胺作为长链二醇。优选使用如上所述用于共聚醚酯的相同的聚醚二醇或二胺作为长链二醇。可以使用相应的二胺代替二醇。
优选地，根据本发明的屋顶隔膜的阻隔膜的聚合物组合物包含优选地10–70重量份(pbw)TPU和90–30pbw TPEE，TPU和TPEE的量总计100pbw。更优选地，聚合物组合物包含20-60pbw TPU和80–40pbw TPEE，TPU和TPEE的量总计100pbw。甚至更优选地，聚合物组合物包含30-50pbw TPU和70–50pbw TPEE，TPU和TPEE的量总计100pbw。
优选地，聚合物组合物由TPU、TPEE和非聚合物添加剂组成，非聚合物添加剂例如着色剂、稳定剂和加工助剂。
根据本发明的屋顶隔膜可以包含阻隔膜和在该膜的一个或两个表面处的绒头织物。作为绒头织物，通常使用无纺或针刺的绒头织物。
在另一个实施方案中，屋顶隔膜由聚合物组合物的膜组成。这种膜也称为单片膜。单片膜的优点是膜易于生产，并且在低温下仍然非常柔韧，使得膜能够抵抗在低温下由风引起的机械应力。
可以在第一步骤中挤出平坦膜，或者通过吹塑成型挤出膜。在第二步骤中，根据本发明的屋顶隔膜可以通过使用胶将膜附着到绒头织物上来形成。
优选地，使用平坦膜挤出方法，其中阻隔膜被挤出，并且其中在此后阻隔膜仍然处于与绒头织物接触的熔融状态中，使得在该膜冷却之后，膜附着到绒头织物上。
阻隔膜的厚度可以高达200μ，优选地，厚度为25至150μ，更优选地50至100μ。
在附图中进一步说明本发明，但本发明并不限于此。
图1示出了由阻隔膜和绒头织物组成的根据本发明的隔膜。
图2示出了由绒头织物和两个阻隔膜组成的根据本发明的隔膜，其中在绒头织物的每侧均有一个阻隔膜。
图3示出了由阻隔膜和两个绒头织物组成的根据本发明的隔膜，其中在阻隔膜的每侧均有一个绒头织物。
图4示出了进行本发明的优选方法的共挤出线。
图1示出了由阻隔膜(2)和绒头织物(3)组成的根据本发明的隔膜(1)，所述阻隔膜(2)由包含TPU和TPEE的聚合物组合物组成。
图2示出了由绒头织物(3)和两个阻隔膜(2)组成的根据本发明的隔膜(11)，其中在绒头织物的每侧均有一个阻隔膜。
图3示出了由阻隔膜(2)和两个绒头织物(3.1)和(3.2)组成的根据本发明的隔膜(21)，其中在阻隔膜的每侧均有一个绒头织物。
图4示出了用于生产根据本发明的隔膜的平坦膜挤出线。挤出线包含挤出机(20)，其用于将包含TPU和TPEE的熔融聚合物组合物传送至模头(30)。在离开模头后，聚合物组合物的阻隔膜(2)与绒头织物(3)接触，使得冷却后，膜附着到绒头织物上。
参照如下的实施例和对比例来进一步说明本发明，但本发明不限于此。
使用的材料
EM400：EM400，由DSM Engineering Plastics提供的共聚醚酯。
E2-UV：母料E2-UV，包含UV稳定剂的共聚醚酯的母料，由DSMEngineering Plastics提供。
MVT 75AT3：Estane MVT 75AT3，由Lubrizol Advanced Materials提供的热塑性聚氨酯弹性体(TPU)。
6-BK-20：母料BLK MB 6-BK-20，包含UV稳定剂的TPU的母料，可从LubrizolAdvanced获得。
绒头织物：聚丙烯无纺布，可从在Gronau的RKW获得。
屋顶隔膜的制备
在SML(奥地利)公司的挤压涂布机上生产屋顶隔膜。挤出机配有屏障型螺杆(barrier screw)、熔体筛和齿轮泵。在使用前，将TPEE和TPU树脂干燥。在挤出前，将TPEE、TPU和母料干混，其量如表1所示。用前述干混物填充挤出机。将挤出机中获得的熔体挤出在绒头织物材料的顶部上。此后，使膜冷却，将膜粘合到绒头织物上。该结构在图1中进一步说明。
实施例1&2和对比例A&B的样品组合物列于表1中。实施例1&2涉及根据本发明的片材，其包括如上所述的TPEE和TPU的阻隔膜。对比例A&B涉及包含TPEE和母料或者TPU和母料的阻隔膜。对于实例来说，屋顶隔膜的制备是相同的。
表1.根据本发明的实施例和对比例的组合物
表1中列出的样品组合物以不同的挤出速度进行加工。挤出机设置使得两个挤出机的输出相等。涂层厚度由重量确定。所有挤出条件的目标层厚度为40克/平方米。不同的挤出条件列于表2中。
表2.挤出速度与涂层厚度
实施例 对比例 挤出速度 层厚度 挤出速度 层厚度 挤出速度 层厚度
M/Min Gram/M2 M/Min Gram/M2 M/Min Gram/M2
1 20 42 60 41 80 42
2 20 38 60 43 80 41
A 20 40 60 NP* 80 NP*
B 20 41 60 40 80 42
*不可加工
对比例A&B示出了共聚醚酯组合物与TPU组合物相比的加工性能的差异。共聚醚酯组合物可以以每分钟80米的线速度以薄层形式生产，而没有任何问题，以提供40克/平方米的膜。另一方面，如果要求40克/平方米的涂层厚度，则TPU组合物不能以每分钟60米的速度加工。实施例1和2表明当使用包含共聚醚酯和TPU的组合物来挤出膜时，可以将机器的线速度提高到每分钟80米。

Claims (5)

1.包含阻隔膜的屋顶隔膜，所述阻隔膜由包含热塑性聚氨酯(TPU)和热塑性聚醚酯(TPEE)的聚合物组合物组成。
2.根据权利要求1所述的屋顶隔膜，其中所述聚合物组合物包含：
10–70pbw TPU和
90–30pbw TPEE，
TPU和TPEE的量总计100pbw。
3.根据权利要求1所述的屋顶隔膜，其中所述聚合物组合物包含：
20-60pbw TPU和
80–40pbw TPEE，
TPU和TPEE的量总计100pbw。
4.根据权利要求1所述的屋顶隔膜，其中所述聚合物组合物包含
30-50pbw TPU和
70–50pbw TPEE，
TPU和TPEE的量总计100pbw。
5.根据前述权利要求中任意一项所述的屋顶隔膜，其中所述聚合物组合物由所述TPU、所述TPEE和非聚合物添加剂组成。
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