CN104768757B - 多层聚合物结构 - Google Patents
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Abstract
本发明涉及具有至少三层的多层聚合物结构。这些层包括一个非丙烯酸的帽原料层、一个烯属基底层,以及一个结系层。结系层是选自烯属丙烯酸酯共聚物、乙烯基芳香族单体与脂肪族共轭二烯的嵌段共聚物或其衍生物、烯烃与部分或全部处于盐的形式的(甲基)丙烯酸的共聚物、高抗冲聚苯乙烯、和/或含乙烯基氰的化合物。每个层可以包含多个子层。该多层结构显示出优异的结构完整性、优异的表面外观、高冲击强度、高刮擦耐受性、以及优异的UV线耐受性。
Description
发明领域
本发明涉及具有至少三层的多层聚合物结构。这些层包括一个非丙烯酸帽原料(capstock)层、一个烯属基底层以及一个结系层。结系层是选自烯属丙烯酸酯共聚物、乙烯基芳香族单体与脂肪族共轭二烯的嵌段共聚物、烯烃与部分或全部处于盐的形式的(甲基)丙烯酸的共聚物、高抗冲聚苯乙烯、和/或含乙烯基氰的化合物。每个层可以包含多个子层。该多层结构显示出优异的结构完整性、优异的表面外观、高冲击强度、高刮擦耐受性、以及优异的UV线耐受性。
发明背景
多层聚合物结构可用于利用不同聚合物的特性。发现这些多层结构(或片材)部分地在许多行业中使用,包括汽车工业;通信诸如电话、收音机、TV、录音带等;电动工具;家电;商用机器;玩具;家具;医疗器械,建筑与结构等。当制备多层结构时,这些结构的层必须彼此牢固地粘附。如果该结构的各个层不彼此粘附,可以使用一种特种粘合剂或一个结系层来使多层结构的这些层连接在一起。
本发明的多层结构可以通过本领域中可供使用的任何方法,诸如通过共挤出技术、层压技术、热成形、注射模制、吹塑模制,或它们的任意组合来制造。共挤出是一种其中两种或更多种熔融的聚合物组合物通过一个进料模口或可替代地通过一个多歧管模口同时挤出以形成每一层具有不同的功能特性的层状结构的方法。进料模口可用于在一个单一的过程中向多歧管模口进料,以提供在多层结构的制造中的优异的柔性。层压是通过使用粘合剂、或通过热和压力的组合使预制的片材或薄膜层,或预制的并挤出的片材或薄膜层粘结在一起的过程。可替代地,热熔体层压或热层压使两个或更多个熔融的聚合物层在挤出模口外会聚在一起,通常在压辊中或在辊堆叠体的顶部辊处。
由不同的聚合物组合物的共混物形成的多层结构在现有技术中是已知的。
具有苯乙烯帽层和烯烃内芯层的多层结构的实例包括在美国专利号5,264,280、5,374,680和5,385,781中披露的那些。
US 6,455,171、US 6,420,050、以及US 2008/0220274披露了提供烯烃内芯层的物理特性以及丙烯酸帽层的刮擦耐受性和化学耐受性特性的多层结构。所披露的结系层或者是一种烯属丙烯酸酯共聚物,或者是一种乙烯基芳香族单体与脂肪族共轭二烯、部分氢化的二烯、或烯烃单体的嵌段共聚物。US 7,740,951披露了一个类似的基于烯烃的基底,使用苯乙烯嵌段共聚物与含乙烯基氰的化合物的共混物的丙烯酸帽层、以及结系层。
不幸的是,上述结系层本身均不会导致烯烃基底与帽层这二者的足够的粘附性,同时还提供高品质的片材表面。努力优化此类组合物可以改善与一个层的粘附性,但同时降低与其他层的粘附性。特定的环氧官能化的聚烯烃-丙烯酸酯共聚物已经表现出与这两个层的令人满意的粘附性;然而凝胶在这种类型的材料中的存在导致具有不可接受的表面外观的结构。
US 5,082,742披露了一种具有附接到热塑性树脂上的烯烃基底层的结构,该结构使用或者具有官能热塑性塑料和官能聚烯烃的双层粘结,或者是官能热塑性塑料和官能聚烯烃的共混物的单层粘结。这些官能团具体地选择为在用于制造该结系层的过程条件下是共反应性的。
出人意料地,现已发现不包含共反应性官能团的结系层可以被用来提供一个非丙烯酸的极性帽层与烯烃基底层的优异的粘附性。有用的结系层是选自烯烃丙烯酸酯共聚物、乙烯基芳香族单体与脂肪族共轭二烯的嵌段共聚物(其可以是部分或完全氢化的二烯,并且其中该二烯可以是官能化的)、烯烃与部分或全部处于盐的形式的(甲基)丙烯酸酸的共聚物、高抗冲聚苯乙烯、含乙烯基氰的化合物,以及它们的共混物。使用聚烯烃与极性帽层之间的新颖的结系层的结果是一种多层结构,该多层结构显示增强的结构完整性,以及优异的表面外观。
发明概述
本发明涉及一种多层热成形的结构,该结构具有:
a)至少一个基于聚烯烃的层,
b)至少一个极性的、非丙烯酸的层,以及
c)至少一个结系层,该结系层具有一种或多种选自下组的聚合物,该组由以下各项组成:烯属丙烯酸酯共聚物、乙烯基芳香族单体与脂肪族共轭二烯的嵌段共聚物、烯烃与部分或全部处于盐的形式的(甲基)丙烯酸酸的共聚物、高抗冲聚苯乙烯、以及含乙烯基氰的化合物,其中该结系层是直接邻近、并且在该基于聚烯烃的层与该极性非丙烯酸层之间。
本发明还涉及由该多层结构形成的物品。
发明详细说明
在此所用的所有百分数都是重量百分数,除非另有说明,并且所有的分子量都是由凝胶渗透色谱法测定的重均分子量,除非另有说明。将列出的所有文献通过引用结合在此。
本发明涉及一种多层聚合物结构,该多层聚合物结构包括至少一个帽原料层、一个结系层、以及一个基底层。
帽原料
本发明的多层结构包括至少一个非丙烯酸的极性帽原料层。极性帽原料层聚合物包括,但不限于,基于苯乙烯的聚合物、聚酯、聚碳酸酯、聚偏二氟乙烯、以及热塑性聚氨酯(TPU)。优选的帽原料层聚合物是基于苯乙烯的。
基于苯乙烯的聚合物包括但不限于,聚苯乙烯、高抗冲聚苯乙烯(HIPS)、丙烯腈-丁二烯-苯乙烯(ABS)共聚物、丙烯腈-苯乙烯-丙烯酸酯(ASA)共聚物、苯乙烯丙烯腈(SAN)共聚物、甲基丙烯酸酯-丙烯腈-丁二烯-苯乙烯(MABS)共聚物、苯乙烯-丁二烯共聚物(SB)、苯乙烯-丁二烯-苯乙烯嵌段(SBS)共聚物和它们的部分或完全氢化的衍生物、苯乙烯-异戊二烯共聚物、苯乙烯-异戊二烯-苯乙烯(SIS)嵌段共聚物和它们的部分或完全氢化的衍生物、以及苯乙烯-(甲基)丙烯酸酯共聚物诸如苯乙烯-甲基丙烯酸甲酯共聚物(S/MMA)。一种优选的苯乙烯聚合物是ASA。本发明的苯乙烯聚合物可通过本领域中已知的方法来制造,这些方法包括乳液聚合、溶液聚合、以及悬浮聚合。本发明的苯乙烯共聚物具有至少百分之10、优选至少百分之25的苯乙烯含量。
在一个实施例中,该帽原料层聚合物具有通过凝胶渗透色谱法(GPC)测量的在50,000与500,000g/mol之间、并且优选从75,000到150,000g/mol的重均分子量。该丙烯酸聚合物的分子量分布可以是单峰的、或多峰的,具有高于1.5的多分散性指数。
在一个实施例中,本发明的多层结构包含两个或更多个极性帽原料层,以及两个或更多个结系层,如极性帽原料/结系层/基于聚烯烃的聚合物/结系层/极性帽原料层的五层结构。该结构在每一侧可以具有不同的极性帽层。在其中在彼此不相邻的层使用多个极性帽原料层和/或多个结系层的结构中,这些极性帽原料层和结系层可以具有相同的或不同的组成,尽管在一个优选的实施例中,多个极性帽原料层和结系层是相同的。在另一个实施例中,这些极性帽原料层可以包括彼此直接接触的两个或更多个极性层。在另一个实施例中,这些结系层可以包括彼此直接接触的两个或更多个结系层。
本发明的帽原料层具有从0.025至3mm、并且优选从0.075至0.5mm的厚度。
基底
基于聚烯烃的层(在此也称为基底层)比合并的一个或多个帽原料层和一个或多个结系层厚。基于聚烯烃的层提供了一个具有刚性和冲击耐受性的良好平衡、优异的可加工性、以及相对较低成本的层。它可以包含一个或多个不同的聚烯烃层,并且聚烯烃层可以是两种或更多种不同的聚烯烃的共混物。在半结晶或结晶烯烃聚合物中所用的聚烯烃可以是包含一个或多个烯烃单体单元的均聚物、共聚物、三聚物、或它们的混合物。在一个基于聚烯烃的层中,这些聚烯烃通常存在的量是按重量计从30%至100%,优选至少55%,并且更优选按重量计至少60%。本发明的聚烯烃排除了环烯烃共聚物(COC)。常见的是这些聚烯烃层的一个或多个含有已经被加工成物品(如薄膜或片材)的再加工材料(rework)。该再加工聚烯烃然后造粒并在再挤出之前与未用过的聚烯烃共混。再加工材料可以含有非聚烯烃组分。
在本发明中优选α-烯烃或1-烯烃的聚合物,并且这些α-烯烃可以含有从2至约20个碳原子。优选含有2至约6个碳原子的α-烯烃。因此,这些烯烃聚合物可以衍生自以下烯烃,如乙烯、丙烯、1-丁烯、1-戊烯、4-甲基-1-戊烯、1-辛烯、1-癸烯、4-乙基-1-己烯等。聚烯烃的实例包括聚丙烯、聚乙烯、以及乙烯-丙烯共聚物。
在一个实施例中,这些聚烯烃包括聚丙烯和乙烯-丙烯聚合物。丙烯聚合物在结构上可以是半结晶的或结晶的。丙烯聚合物的数均分子量优选地为高于约10,000并且更优选地为高于约50,000。此外,优选的是在一个实施例中表观结晶熔点是高于约75℃,并且优选在约75℃与约250℃之间。在本发明中有用的丙烯聚合物是本领域技术人员众所周知的并且许多是可商购的。聚丙烯是优选的丙烯聚合物。
热塑性聚烯烃(TPO)是一种尤其优选的基底层。热塑性聚烯烃(TPO)组合物被定义为一种两相熔体共混物,该共混物含有至少一种半结晶聚丙烯组分的连续相和包含至少一种基本上无定形的弹性体组分的分散相。该弹性体组分典型地包括至少一种乙烯/α-烯烃共聚物、至少一种苯乙烯嵌段共聚物、或它们的混合物。优选的热塑性聚烯烃材料提供了刚度(例如,弯曲模量典型地范围为从270-2900MPa)、以及冲击耐受性(例如,在室温下可延展的,优选在-30℃下可延展的)的有益的平衡,但用最常规的热塑性加工设备是可熔融加工的。优选地,该基于聚烯烃的基底层组分的特征还在于典型地从0.813g/cm3至1.305g/cm3的密度。
在一个实施例中,本发明的多层结构包括两个或更多个基底层。
结系层
在本发明中有用的结系层包括一种或多种选自下组的聚合物,该组由以下各项组成:烯属丙烯酸酯共聚物、烯烃与可以是部分或全部处于盐的形式的(甲基)丙烯酸酸的共聚物、高抗冲聚苯乙烯、含乙烯基氰的化合物、以及乙烯基芳香族单体与脂肪族共轭二烯的嵌段共聚物(其可以是部分或完全氢化的并且其中该二烯可以是官能化的)。
在一个实施例中,本发明的结系层包括乙烯基芳香族单体与脂肪族共轭二烯的两种或更多种嵌段共聚物的共混物(其可以是部分或完全氢化的并且其中该二烯可以是官能化的)。优选的结系层组合物包括具有小于约50重量%的结合的乙烯基芳香族单体的嵌段共聚物和具有大于约60重量%的结合的乙烯基芳香族单体的嵌段共聚物的共混物。
在另一个实施例中,该结系层具有如通过ASTM D638测定的大于50磅/平方英寸、优选大于100磅/平方英寸、更优选大于200磅/平方英寸、更优选大于300磅/平方英寸、更优选大于400磅/平方英寸、并且最优选大于500磅/平方英寸的高拉伸模量。
如果该结系层包括烯烃与部分或完全处于盐的形式的(甲基)丙烯酸的共聚物,该盐阳离子优选选自钠、钾、钙、锌、锂、镁、以及钡组成的组。
烯烃丙烯酸酯共聚物可以通过本领域中已知的任何方法来制备,包括但不限于高压高压釜和管式反应器,并且可以具有组成和分子量的均相或非均相分布。
在本发明的多层结构中,结系层和非丙烯酸层的厚度范围为从0.025至2.5mm,并且优选地厚度范围为从0.05至1mm。
一个或多个极性帽原料层、一个或多个基于聚烯烃的基底层和结系层可以含有一种或多种在聚合物领域中使用的类型的抗冲击改性剂、填充剂或纤维、或其他添加剂。抗冲击改性剂的实例包括但不限于,核-壳粒子以及嵌段或接枝共聚物。添加剂的实例包括,例如,UV光抑制剂或稳定剂、润滑剂、热稳定剂、阻燃剂、增效剂、颜料和其他着色剂。在根据本发明的一种典型的配混的聚合物共混物中采用的填充剂的实例包括滑石、碳酸钙、云母、消光剂、硅灰石、白云石、玻璃纤维、硼纤维、碳纤维、炭黑、颜料(如二氧化钛),或它们的混合物。消光剂的实例包括但不限于,不同几何结构的交联的聚合物颗粒,包括在每一层的聚合物组合物中的填充剂和添加剂的量可以从聚合物、添加剂和填充剂的组合重量的约0.01%至约70%变化。总体上,从约5%至约45%、优选从约10%至约40%的量都包括在内。
这些填充剂可以用偶联剂来处理以提高填充剂与树脂之间的粘合。例如,这些填充剂可以用诸如脂肪酸(例如硬脂酸)、硅烷、马来酸化的聚丙烯等材料来处理。所用的偶联剂的量是有效改善填充剂与树脂之间的粘合的量。
制造
本发明的多层结构可以包括三个或更多个层,其中调整这些层的数目和组成的选择以满足最终用途应用的需要。该结构可以通过本领域已知的任何方法来制备。这包括层的单独形成随后层压,所有层的共挤出(这是优选的),或共挤出和层压的组合。这还包括多射注塑模制、吹塑模制和嵌件模制。
本发明的多层聚合物结构可以或者直接加工成任何几何形状(诸如一种型材),或者可以首先加工成一个平面形状并且然后通过任何适合的方法进一步成形为一个三维部分。例如,热成形是将以薄膜或片材形式的塑料材料加热到其特定的加工温度并通过机械或气动装置针对模具的轮廓将该热并且柔性材料成形的方法。
该多层结构可以具有任何给定的几何形状,包括但不限于,平片、棒、或型材。该多层结构显示出优异的结构完整性、优异的表面外观、高冲击强度、高刮擦耐受性、以及优异的UV线耐受性。
实例
下面的片材结构是在一个实验室共挤出生产线上使用三歧管模具制备的:
1来自Styrolution公司的LURAN SE UV 797Natural。
2来自阿科玛公司(Arkema,Inc)的PRD-940B。
3来自麦泰斯聚合物公司(Mytex Polymers)的METAFORM 7200。
4来自阿科玛公司的SOLARKOTE A200。
共挤出后,复合片材被切成1英寸宽的长条并且帽原料与基底之间的粘附性是使用如在ASTM 6862-04中所描述的90°剥离试验测定的。
得到了以下结果:
实例1显示了各层之间的优异的粘附性。与此相反,实例2(不存在结系层)表现出非常小的粘附性。这表明使用烯烃-丙烯酸共聚物作为结系层用于在聚烯烃(如TPO)内共挤出苯乙烯(如ASA)的有用性。实例1和3表现出类似的粘附性,基于丙烯酸的聚合物或基于苯乙烯的聚合物作为帽原料层的选择取决于最终应用在成本和物理特性(硬度、光泽度、冲击)方面的要求。
Claims (10)
1.一种共挤出的刚性多层热成形结构,其中所有的层都是一起共挤出的,该结构包括:
a)至少一个热塑性聚烯烃基底层,
b)至少一个基于苯乙烯的聚合物帽原料层,其具有0.075至2.5mm的厚度,其中该基于苯乙烯的聚合物选自下组,该组由以下各项组成:聚苯乙烯,高抗冲聚苯乙烯(HIPS),丙烯腈-丁二烯-苯乙烯(ABS)共聚物,丙烯腈-苯乙烯-丙烯酸酯(ASA)共聚物,苯乙烯丙烯腈(SAN)共聚物,甲基丙烯酸酯-丙烯腈-丁二烯-苯乙烯(MABS)共聚物,苯乙烯-丁二烯共聚物(SB),苯乙烯-丁二烯-苯乙烯嵌段(SBS)共聚物和所述SBS共聚物的部分或完全氢化的衍生物,苯乙烯-异戊二烯共聚物,苯乙烯-异戊二烯-苯乙烯(SIS)嵌段共聚物和所述SIS嵌段共聚物的部分或完全氢化的衍生物,以及苯乙烯-甲基丙烯酸甲酯共聚物(S/MMA),以及
c)至少一个结系层,其具有0.05至1mm的厚度,该结系层包含一种或多种选自由以下各项组成的组的均相或非均相聚合物:烯属丙烯酸酯共聚物,烯烃与(甲基)丙烯酸的共聚物,烯烃与部分或全部处于盐的形式的(甲基)丙烯酸的共聚物,
其中所述结系层是直接邻近并且在该热塑性聚烯烃基底层与该基于苯乙烯的聚合物帽原料层之间,其中所述结系层具有通过ASTM D638测定的大于300磅/平方英寸的拉伸模量。
2.如权利要求1所述的多层热成形结构,其中所述基于苯乙烯的聚合物具有通过凝胶渗透色谱法测量的在50,000与500,000g/mol之间的重均分子量。
3.如权利要求1所述的多层热成形结构,其中所述基于苯乙烯的聚合物包含丙烯腈-苯乙烯-丙烯酸酯(ASA)共聚物。
4.如权利要求1所述的多层热成形结构,其中所述基于苯乙烯的聚合物帽原料层另外包含一种或多种抗冲击改性剂和/或填充剂。
5.如权利要求1所述的多层热成形结构,其中所述基于苯乙烯的聚合物帽原料层另外包含一种或多种纤维。
6.如权利要求1所述的多层热成形结构,其中所述热塑性聚烯烃基底层按重量计包含至少30%的一种或多种聚烯烃材料。
7.如权利要求1所述的多层热成形结构,其中所述结系层具有通过ASTM D638测定的大于400磅/平方英寸的拉伸模量。
8.如权利要求1所述的多层热成形结构,其中所述结系层具有通过ASTM D638测定的大于500磅/平方英寸的拉伸模量。
9.一种由权利要求1所述的热成形结构形成的物品。
10.如权利要求9所述的物品,该物品是处于平片、棒或型材的形式。
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US11077597B2 (en) | 2016-02-23 | 2021-08-03 | Moistureshield, Inc. | Compositions and methods for reducing the surface temperature of composite articles |
WO2019067654A1 (en) * | 2017-09-27 | 2019-04-04 | Arkema France | MULTILAYER POLYMER STRUCTURES |
US20190344550A1 (en) | 2018-05-08 | 2019-11-14 | Crypton, Inc. | Treated fabrics and methods of forming same |
US20190344539A1 (en) | 2018-05-08 | 2019-11-14 | Crypton, Inc. | Treated fabrics and methods of forming same |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5306548A (en) * | 1992-05-20 | 1994-04-26 | The Dow Chemical Company | Coextruded weatherable film structures and laminates |
Family Cites Families (24)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3177269A (en) * | 1960-10-10 | 1965-04-06 | Dow Chemical Co | Graft copolymers of polyolefins and acrylic and methacrylic acid and method of making the same |
US4440824A (en) * | 1981-10-23 | 1984-04-03 | Composite Container Corporation | Thermoformable coextruded multilayered structure |
US4939009A (en) * | 1988-03-17 | 1990-07-03 | Eastman Kodak Company | Multilayered sheets having excellent adhesion |
US5017436A (en) | 1988-12-01 | 1991-05-21 | Dick Schwarz | Clear thermoplastic polymer composite material |
US5310584B1 (en) * | 1992-04-14 | 1999-02-16 | Amoco Corp | Thermoformable polypropylene-based sheet |
US5264280A (en) | 1992-09-21 | 1993-11-23 | Ferro Corporation | Multilayer thermoformable structure |
US6455171B2 (en) * | 2000-02-03 | 2002-09-24 | Ferro Corporation | Multilayer structure with acrylic cap layer, polyolefin core layer, and intermediate tie layer |
US6420050B2 (en) | 2000-02-03 | 2002-07-16 | Ferro Corporation | Multilayer composite structure with formulated acrylic cap |
US6852405B2 (en) * | 2000-07-17 | 2005-02-08 | Atofina | Acrylic polymer capstock with improved adhesion to structural plastics |
AU2001290978A1 (en) * | 2000-09-14 | 2002-03-26 | Rohm And Haas Company | Adhesive compositions containing low molecular weight polymeric additives |
DE60219948T2 (de) * | 2001-11-06 | 2007-09-06 | Dow Global Technologies, Inc., Midland | Fasern aus isotaktischem propylencopolymerisat, deren herstellung und verwendung |
US6696117B2 (en) * | 2001-11-27 | 2004-02-24 | Guardian Industries, Inc. | Composite laminate structures especially useful for automotive trim components, and methods and tie layers employed to make the same |
US7135234B2 (en) * | 2003-06-12 | 2006-11-14 | Nova Chemicals (International) S.A. | Multilayer coextrusions |
US20050031822A1 (en) * | 2003-08-07 | 2005-02-10 | Mitsui Chemicals, Inc. | Adhesive sheet |
DE602005006573D1 (de) * | 2004-07-15 | 2008-06-19 | Du Pont | Zusammensetzung, enthaltend ethylencopolymere und polyolefine |
PL1926590T3 (pl) * | 2005-09-23 | 2015-02-27 | Arkema France | Kompozyt akryl/termoplastyczna olefina |
US20080248294A1 (en) | 2005-09-28 | 2008-10-09 | Arkema France | Low Moisture Absorbing Acrylic Sheet |
CN103692746B (zh) * | 2005-11-15 | 2017-04-12 | 陶氏环球技术有限责任公司 | 取向多层收缩标签 |
US20090241450A1 (en) * | 2005-11-30 | 2009-10-01 | Frank Lane Italiane | Composition of a weatherable roofing composite product |
US20070190333A1 (en) * | 2006-02-13 | 2007-08-16 | Mitsui Chemicals, Inc. | Polyolefin-based molded product coated with polar polymer, method for producing the same, and uses of the same |
US7713636B2 (en) * | 2006-12-15 | 2010-05-11 | Exxonmobil Chemical Patents Inc. | Multi-layer films comprising propylene-based polymers |
US7740951B2 (en) * | 2007-04-11 | 2010-06-22 | Lyondellbasell Advanced Polyolefins Usa Inc. | Multilayered polymeric structure and methods |
WO2013025739A1 (en) * | 2011-08-17 | 2013-02-21 | Arkema France | Multilayer polymer structures |
WO2013070502A1 (en) | 2011-11-07 | 2013-05-16 | Arkema France | Multilayer polymer structure |
-
2013
- 2013-04-03 EP EP13775125.1A patent/EP2836362B1/en active Active
- 2013-04-03 CN CN201380019836.XA patent/CN104768757B/zh active Active
- 2013-04-03 BR BR112014025310-2A patent/BR112014025310B1/pt not_active IP Right Cessation
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- 2013-04-03 WO PCT/US2013/035067 patent/WO2013154877A2/en active Application Filing
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Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5306548A (en) * | 1992-05-20 | 1994-04-26 | The Dow Chemical Company | Coextruded weatherable film structures and laminates |
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EP2836362B1 (en) | 2020-10-14 |
MX361050B (es) | 2018-11-26 |
EP2836362A4 (en) | 2016-04-27 |
US11607869B2 (en) | 2023-03-21 |
BR112014025310B1 (pt) | 2020-12-15 |
EP2836362A2 (en) | 2015-02-18 |
MX2014012357A (es) | 2014-11-25 |
WO2013154877A3 (en) | 2015-06-18 |
WO2013154877A2 (en) | 2013-10-17 |
CN104768757A (zh) | 2015-07-08 |
US20150111014A1 (en) | 2015-04-23 |
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