CN109733011A - 用于运输的具有改善的阻燃特性的柔软触感层压材料 - Google Patents

用于运输的具有改善的阻燃特性的柔软触感层压材料 Download PDF

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Publication number
CN109733011A
CN109733011A CN201910112263.4A CN201910112263A CN109733011A CN 109733011 A CN109733011 A CN 109733011A CN 201910112263 A CN201910112263 A CN 201910112263A CN 109733011 A CN109733011 A CN 109733011A
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Prior art keywords
laminated material
layer
pvc
polyurethane
fluoropolymer
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CN201910112263.4A
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M.A.哈思科克
R.G.皮尔森
M.D.滕南特
D.A.梅尔策尔
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Schneller LLC
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Schneller LLC
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Abstract

本申请涉及用于运输的具有改善的阻燃特性的柔软触感层压材料。公开了满足FAA要求的具有发泡或未发泡的PVC中间层和多嵌段共聚物或聚氨酯或硅酮顶层的柔软触感阻燃层压材料。本发明涉及用于表面覆盖应用的具有改善的阻燃特性的多层层压材料。这些材料具有皮革的外观和手感以及比当下可得的柔软触感层压材料更大的抗燃性。

Description

用于运输的具有改善的阻燃特性的柔软触感层压材料
相关申请
本申请是申请日为2014年3月14日、申请号为201480014694.2、名称为″用于运输的具有改善的阻燃特性的柔软触感层压材料″的发明专利申请的分案申请。本申请涉及2013年3月14日提出的美国临时申请号61/782907。
技术领域
本申请涉及具有改善的阻燃特性的用于表面覆盖应用的多层层压材料。这些材料具有皮革的外观和手感，比当下可得的柔软触感的层压材料具有更大的抗燃性。
背景技术
虽然“柔软触感”/“柔软手感”皮革类材料在本领域是已知的，当用在商业运输中(用于装饰或覆盖表面)时，传统产品具有不合意的燃烧特性；即它们易燃和/或释放有毒烟气/烟雾。用于一般用途(汽车、消费产品等)的现有“柔软触感”产品易于燃烧或熔化并产生有毒烟雾。在商业航空中，由于专为发生火灾时保护乘客安全而设计的严格法规要求，选择甚至更少。合成皮革构成所用产品的大部分。这些通常具有边际(marginal)燃烧特性，这限制了可以在何处以及如何使用它们。另外，许多耐久性较差并且容易污染。
本技术已尝试通过利用阻燃硅酮解决此问题。已经开发出可用于柔软手感的硅酮产品，并且它们中的一些可以满足航空要求。然而，这些硅酮感觉“黏”或“发粘”且同时柔软，通常不被误认为是皮革。另外，由于所述黏性，硅酮可吸入并保持污垢和污染物。
进一步，其它柔软手感产品不具有大的抗破坏性/耐久性，使它们不适合用于高磨损领域如飞机或其它内部部件，或者具有柔软手感但缺乏压缩品质，或者不能通过燃烧要求。
发明内容
本发明为具有例如类似皮革或合成皮革的柔软手感的设计的高性能装饰层压材料。它会满足或超越所有联邦航空管理局(“FAA”)法规。考虑了用于商用飞机的各个领域的关于火灾、烟雾和有毒气体的规范。它还具有卓越的耐污染性和耐久性。通过用阻燃多嵌段共聚物涂覆聚(卤乙烯)或聚(偏二卤乙烯)薄膜并优化该层的手感和燃烧，克服了这些限制。
附图说明
图1给出了层压材料的一个实施方案。
图2给出了实施例中所用结构。
图3给出了层压材料的另外一个实施方案。
图4给出了层压材料的又一个实施方案。
具体实施方式
本申请可以包括以下实施方案：
1.层压材料，其包含：
a)由在聚(卤乙烯)或聚(偏二卤乙烯)上的多嵌段共聚物层构成的双层薄膜
b)底漆层
c)PVC中间层(发泡或未发泡的)
d)浸渍的玻璃织物
e)聚(氟乙烯)或poly(fluoridene halide)
f)胶粘层。
2.如方案1的层压材料，其中所述多嵌段共聚物为可交联的热塑性或热固性共聚酰胺、共聚酯、苯乙烯类或聚氨酯。
3.如方案1的层压材料，其中所述PVC中间层进一步包含颜料。
4.如方案1的层压材料，其中所述PVC中间层进一步包含阻燃剂。
5.如方案1的层压材料，其中所述底漆层由丙烯酸类、聚酯、聚氨酯或酚醛树脂构成。
6.如方案1的层压材料，其中所述胶粘层由丙烯酸类、聚酯、聚氨酯或酚醛树脂构成。
7.如方案6的层压材料，其中所述胶粘层进一步包含阻燃剂。
8.层压材料，其包含：
a)包含硅酮泡沫的基层
b)含氟聚合物层
c)PVC中间层，其为发泡或未发泡的
d)多嵌段共聚物顶层
e)任选的胶粘层。
9.如方案8的层压材料，其进一步包含在所述基层和PVC中间层之间的含氟聚合物层。
10.如方案8的层压材料，其中所述PVC中间层进一步包含颜料。
11.如方案8的层压材料，其中所述PVC中间层进一步包含阻燃剂。
12.如方案8的层压材料，其中所述基层进一步包含增强织物。
13.如方案12的层压材料，其中所述增强织物由玻璃纤维构成。
14.如方案1的层压材料，其中所述胶粘层由丙烯酸类、聚酯、聚氨酯或酚醛树脂构成。
15.如方案6的层压材料，其中所述胶粘层进一步包含阻燃剂。
16.层压材料，其包含：
a)包含含氟聚合物的基层
b)至少一个PVC中间层，其为发泡或未发泡的
c)聚氨酯/硅酮顶层
d)任选的胶粘层。
17.如方案16的层压材料，其中所述PVC层的至少之一是发泡的。
18.如方案16的层压材料，其中所述PVC中间层进一步包含颜料。
19.如方案16的层压材料，其中所述PVC中间层进一步包含阻燃剂。
20.如方案16的层压材料，其中所述基层进一步包含增强织物。
21.如方案20的层压材料，其中所述增强织物由玻璃纤维构成。
22.如方案16的层压材料，其中所述PVC中间层进一步包含阻燃剂。
23.如方案16的层压材料，其中所述胶粘层由丙烯酸类、聚酯、聚氨酯或酚醛树脂构成。
24.如方案16的层压材料，其中所述胶粘层进一步包含阻燃剂。
此处所用的“多嵌段共聚物”包括聚氨酯(PU)、共聚酰胺(COPA)、共聚酯(COPE)以及苯乙烯类，如SIS、SBS、SIBS等。这些共聚物优选为可交联的热塑性或热固性塑料。
此处所用的“聚(氯乙烯)”或“PVC”包括氯乙烯的均聚物，以及氯乙烯与一种或多种共聚单体的聚合产物。例如，PVC树脂可以为氯乙烯和乙烯的共聚物，或氯乙烯与丙烯的共聚物。PVC树脂还可以为氯乙烯与具有式H2C＝C(R1)OC(＝O)R2或H2C＝C(R1)C(＝O)OR2的酯单体的聚合产物，其中R1和R2独立地为C1-12烷基。此类树脂的一个实例为氯乙烯单体与甲基丙烯酸甲酯单体的共聚物。此类树脂的另一实例为氯乙烯单体与乙酸乙烯酯单体的共聚物。也可使用这些PVC树脂的组合。
此处所用的“聚(偏二氟乙烯)”或“PVDF”包括偏二氟乙烯的均聚物，以及偏二氟乙烯与一种或多种共聚单体的聚合产物。例如，PVDF树脂可以为偏二氟乙烯与六氟丙烯的共聚物，或偏二氟乙烯与氯三氟乙烯的共聚物。PVDF树脂还可以为偏二氟乙烯与具有式H2C＝C(R1)OC(＝O)R2或H2C＝C(R1)C(＝O)OR2的酯单体的聚合产物，其中R1和R2独立地为C1-12烷基。此类树脂的一个实例为偏二氟乙烯单体与甲基丙烯酸甲酯单体的共聚物。此类树脂的另一实例为偏二氟乙烯单体与乙酸乙烯酯单体的共聚物。也可使用这些PVDF树脂的组合。也可使用PVDF与其它聚合物的共混物，例如，PVDF/丙烯酸类共混物。
“预浸料”为聚合物如PET、PPS和PEEK悬浮于任选地具有阻燃剂的有机液体中的涂料。
“硅酮泡沫”为包含开孔和/或闭孔的硅酮材料，并且可从多个生产商获得。泡沫可用在多种硬度计中，并且为了耐久性而具有玻璃衬背。为了满足本发明的目的，需要专门选择和设计的具有超越硅酮基材料的天然阻燃特性的改善的阻燃特性的体系。
“有机溶胶”为PVC悬浮于任选地具有阻燃剂的有机液体中的涂料。
合适的胶粘剂和底漆包括但不限于：酚醛树脂、聚酯、环氧树脂、聚氨酯和甲基丙烯酸类。由于胶粘剂需要与它们所接合的材料兼容并提供应用的必需强度，层压材料层的生产商通常会详细说明使用何种胶粘剂或底漆与它们的产品兼容。
所述组合物包含一种或多种阻燃剂或阻燃剂的组合。阻燃剂可以为液体或固体。优选的阻燃剂包括但不限于三氢氧化铝，其可从各个供应商，包括Alcoa以产品名HydratedAluminas获得；氢氧化镁，其可从各个供应商，包括Albermarle以商品名MAGNIFIN(例如Magnifin H-10或Magnifin H-5)获得；阻燃增塑剂，如磷酸酯增塑剂，其可从各个供应商，包括Ferro以商品名SANTICIZER(例如Santicizer 2148)获得，四溴邻苯二甲酸酯，聚合增塑剂(例如Admix 412，其购自Teknor Apex)，溴代和氯代邻苯二甲酸酯的组合(例如，Unitex 44-55)，以及氯代烃(例如Cercelor S52)；八钼酸铵，其可从各个供应商，包括Polymer Additives Group以商品名Climax AOM获得；烷基膦酸铝和烷基次膦酸铝，如分别由ICL-IP和Clariant出售的AMMP和DEPAL，由Sachtleben出售的硫化锌，由US Borax Inc出售的硼酸锌以及由3N International作为ZS 286出售的羟基锡酸锌；由3N International出售的氧化铋。其它阻燃剂描述于Linsky等人的美国专利号5,886,072和Shtekler等人的WO 2012/088080中，二者在此整体通过引用并入本发明。该组合物每100份聚氯乙烯树脂优选包含至少总计约50份阻燃剂，并且更优选地每100份聚氯乙烯树脂约总计50份至约200份阻燃剂。例如，该组合物每100份聚氯乙烯树脂可包含约5份至约60份，约10份至约50份，或约20份至约40份阻燃增塑剂。
在本发明的一个实施方案中，如图2示意性所示，所述层压材料包含与透明聚(卤乙烯)或聚(偏二卤乙烯)薄膜接合的透明阻燃多嵌段共聚物薄膜的顶层，其任选包含阻燃剂。然后，该层压材料与包含颜料和阻燃剂的阻燃PVC层接合。可能有必要使用底漆以获得层压材料和PVC层之间的良好粘附。这些层与已浸渍有熔融有机溶胶材料的合适玻璃织物接合。任选地，含氟聚合物层可以接合在该浸渍的玻璃的另一面，在这种情况下可能需要任选的底漆层。用于该实施方案的合适材料的商业可得的实例阐释如下：
柔软触感薄膜为获自Akzo Nobel的Aerofine等级，优选为2.5-2.7密耳厚度并且由PVC基础上的聚氨酯构成的8901。玻璃纤维是售自BGF的7628 Greige玻璃。中间PVC层为Spectrum出售的S1670。预浸料为Spectrum出售的S1687。丙烯酸类底漆为68080，其为Dupont出售的柔性产品胶粘剂。
在本发明的另一个实施方案中，层压材料包含与含阻燃剂的透明PVDF/丙烯酸类薄膜接合的透明聚氨酯/聚碳酸酯薄膜的顶层，该PVDF/丙烯酸类薄膜然后与含颜料和阻燃剂的PVC层接合。用合适的胶粘剂将这些层与阻燃硅酮泡沫/玻璃织物接合。任选地，在PVC层和硅酮泡沫之间可存在含氟聚合物层。
参考图1，在此实施方案中，层压材料包含在聚(卤乙烯)或聚(偏二卤乙烯)层上的阻燃多嵌段共聚物的约0.5密耳至3密耳透明层的顶层。合适的薄膜为例如Akzo Nobel出售的Aerofine 8900。任选地，使用厚度最大0.5密耳的合适底漆与该顶层接合。然后，前述材料与可为发泡或未发泡的厚度为1-25密耳的PVC层接合。有机溶胶浸渍的玻璃织物任选地与该PVC层接合，其中玻璃织物重约1至约10盎司/码2，并且该有机溶胶为熔融的。含氟聚合物层(PVC或PVDF)，如Dupont提供的或Akzo Nobel提供的产品任选地直接与PVC层接合，间接地需要底漆层用于连合任选的含氟聚合物层。含氟聚合物层优选为约0.5-3.0密耳厚。然后，接合胶粘层作为最终层；该胶粘层优选为1-5盎司/码2。
参考图3，在此实施方案中，层压材料包含透明的1.0-3密耳的聚氨酯/聚碳酸酯薄膜的顶层。合适的薄膜由Akzo Nobel生产。利用合适的胶粘剂如Dupont 68080胶粘底漆将0.8-1.5密耳的透明PVDF/丙烯酸类薄膜与该顶层接合，该PVDF/丙烯酸类薄膜含有阻燃剂，如Schneller提供的Airfilm LHR(低的热释放)。然后，前述材料与含氟聚合物层(PVC或PVDF)，如Dupont提供的或Akzo Nobel提供的Soliant产品接合。该含氟聚合物层优选为约0.5-2.0密耳厚。利用合适的胶粘剂如来自Schneller的HA211将具有玻璃衬背的硅酮泡沫与该含氟聚合物层接合。在一个实施方案中，硅酮泡沫为63密耳厚。合适的硅酮泡沫可由Rogers Corporation以品牌出售。
参考图4，在此实施方案中，层压材料包含含氟聚合物衬背，如PVDF或PVF，在其上施加厚度为2-10密耳的PVC材料。该PVC可为压延、挤出或涂覆的；它可以包含用于着色的颜料和阻燃剂。在一些情况下，它可由一对不同的PVC层构成，并且其部分或全部可为发泡的。将0.1-0.5密耳的聚氨酯/硅酮顶层施加到该PVC上。
下表1列出了本发明层压材料的期望特性，包括适用之处的相关法规。
可通过任何合适的方法施加本发明的层压材料。在某些情况下，它们利用本领域中已知的方法来真空成形到位置中(into place)，或利用辊或其它外部压力的手段来施加。
本领域技术人员可以理解，与此处所述的方法和材料有实质程度上的偏差是可行的，并仍然在本发明的精神内。
表1

Claims (18)

1.层压材料，其包含：
a)包含硅酮泡沫的基层；
b)含氟聚合物层；
c)PVC中间层，其为发泡或未发泡的；和
d)多嵌段共聚物顶层。
2.如权利要求1所述的层压材料，其进一步包含在所述基层和所述PVC中间层之间的含氟聚合物层。
3.如权利要求1所述的层压材料，其进一步包含胶粘层。
4.如权利要求1所述的层压材料，其中所述硅酮泡沫层为10-100密耳厚。
5.如权利要求1所述的层压材料，其中所述含氟聚合物层为0.5-3.0密耳厚。
6.如权利要求1所述的层压材料，其中所述PVC层为2-25密耳厚。
7.层压材料，其包含：
a)包含含氟聚合物的基层；
b)至少一个PVC中间层，其为发泡或未发泡的；和
c)聚氨酯/硅酮顶层。
8.如权利要求7所述的层压材料，其包含多个PVC中间层，其中所述PVC层的至少之一是发泡的。
9.如权利要求1或7所述的层压材料，其中所述PVC中间层进一步包含颜料。
10.如权利要求1或7所述的层压材料，其中所述PVC中间层进一步包含阻燃剂。
11.如权利要求1或7所述的层压材料，其中所述基层进一步包含由玻璃纤维构成的增强织物。
12.如权利要求1或7所述的层压材料，其进一步包含胶粘层，所述胶粘层由丙烯酸类、聚酯、聚氨酯或酚醛树脂构成。
13.如权利要求12所述的层压材料，其中所述胶粘层进一步包含阻燃剂。
14.如权利要求7所述的层压材料，其中所述含氟聚合物PVC层厚度为2-10密耳。
15.如权利要求7所述的层压材料，其中所述PVC层为压延的、挤出的或涂覆的。
16.如权利要求7所述的层压材料，其中所述聚氨酯/硅酮顶层的厚度为0.1-0.5密耳。
17.如权利要求1或7所述的层压材料，其中所述层压材料根据FAA规范是阻燃的。
18.如权利要求1或7所述的层压材料，其中所述层压材料符合FAR 25.853的60秒垂直燃烧要求、NBS烟雾密度和OSU。
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US10583636B2 (en) 2020-03-10
US10596788B2 (en) 2020-03-24
US20140315010A1 (en) 2014-10-23
US20170087805A1 (en) 2017-03-30
US10696026B2 (en) 2020-06-30
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US9492988B2 (en) 2016-11-15
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