CN102405172A - 用于绝热和隔音毯的复合层压板 - Google Patents

用于绝热和隔音毯的复合层压板 Download PDF

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Publication number
CN102405172A
CN102405172A CN2010800176032A CN201080017603A CN102405172A CN 102405172 A CN102405172 A CN 102405172A CN 2010800176032 A CN2010800176032 A CN 2010800176032A CN 201080017603 A CN201080017603 A CN 201080017603A CN 102405172 A CN102405172 A CN 102405172A
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China
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poly
mer
composite laminate
thermoplastic film
blanket
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CN2010800176032A
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CN102405172B (zh
Inventor
L·B·理查森三世
W·F·克诺夫
J·王
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DuPont Safety and Construction Inc
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EI Du Pont de Nemours and Co
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Abstract

本发明涉及复合层压板，所述复合层压板按顺序包含(a)阻燃剂聚合物防潮层，(b)无机片层，和(c)阻燃剂热塑性膜层。本发明还涉及绝热和隔音毯，所述绝热和隔音毯包含被上述复合层压板包围的纤维材料芯或泡沫，其中所述复合层压板的热塑性膜层接触并包封所述芯。

Description

用于绝热和隔音毯的复合层压板
发明背景
1.发明领域
本发明涉及具有阻燃特性的复合绝热层压板。本发明还涉及复合层压板在绝热和隔音毯中的用途，所述毯如可存在于飞机机身或涡轮引擎隔室中。
2.发明背景
授予Fay等人的美国专利6,322,022公开了用于交通工具，尤其是飞机的防烧透系统。
授予Tomkins和Vogel-Martin的美国专利6,670,291描述了用于防火应用的层压片材料。
仍存在对绝热和隔音毯的持续需要，所述绝热和隔音毯用于具有降低的重量和改善的防止火焰传播的飞机结构。
发明内容
本发明涉及复合层压板，所述层压板按顺序包括：(a)具有6.0至25.0微米厚度和V-0的UL 94火焰分级的聚合物防潮层，(b)具有7.0至76.0微米厚度和V-0的UL 94火焰分级的无机片层，其中所述片包含具有100至20,000纵横比的片层，和(c)具有不大于25微米的厚度、不大于150％的平均断裂伸长率和V-0的UL 94火焰分级的热塑性膜层。本发明还涉及包含被上文复合层压板包围的无机或有机芯的绝热和隔音毯，其中所述复合层压板的热塑性膜层接触并包封所述芯。
附图简述
图1为贯穿本发明防烧透复合层压板的横截面示意图。
图2为贯穿结合了防烧透复合层压板的本发明的绝热和隔音毯的横截面示意图。
图3为用于烧透测试的设备的示意图。
发明详述
图1显示了贯穿包含聚合物防潮层11、无机片层12和热塑性膜层13的防烧透复合层压板10的区段。
防潮层防潮层是指聚合物层具有不能穿过液体的能力但具有穿过蒸汽的某种能力。通常，当用ASTM E96/E 96M-05的水方法测试时，所述阻挡材料的25微米厚的样品具有不超过60g/(m2·24h)的水蒸气渗透率。另外的要求是所述阻挡物应具有V-0的UL 94火焰分级。UL 94火焰分级为Underwriters Laboratory测试，The Standard for Flammability of PlasticMaterials for Parts in Devices and Appliances(用于设备和器具部件的塑性材料的可燃性标准)，所述测试测量一旦所述样品被点燃时火焰要么熄灭要么蔓延的趋势。V-0表示所述材料在竖直位置被测试，并且在点火源被移除后十秒之内自熄灭。防潮层的更多要求是其应具有在6.0至25微米范围内的厚度。更优选地，所述厚度范围应在6.0至20.0微米且最优选在6至10微米范围内。所述阻挡层进一步向所述层压板提供机械强度和硬度并且保护所述无机片层。优选的膜材料为含氟聚合物、聚酰亚胺、聚醚醚酮(PEEK)和聚醚酮酮(PEKK)，所有这些均为可商购获得的。适宜的含氟聚合物以商品名Tedlar得自E.I.du Pont de Nemours(Wilmington，DE)。与所述无机片层接触的阻挡层的表面可任选地进行处理以改善润湿能力和/或与所述无机片层的粘附性。适宜的表面处理方法包括但不限于电晕蚀刻和用偶联剂如铵、或锍盐进行洗涤。所述阻挡层的外表面，即不与无机片层接触的表面，可任选地被涂覆有聚四氟乙烯(PTFE)或可被金属化。
片层
单个片的厚度通常在约5埃至约5,000埃，更优选约10埃至约4,200埃的范围内。片的最大宽度的平均值通常在约10,000埃至约30,000埃的范围内。单个片的纵横比通常在100至20,000范围内。
在本发明的一个实施方案中，所述无机片层包含100％的片，即，没有诸如树脂、粘合剂、布料或纸材的载体材料。然而，会有一些残余的由片分散体干燥不完全而产生的分散剂。
在本发明的另一个实施方案中，轻型多孔编织稀松织物被嵌入到无机片层内或放置到无机片层上以向所述层提供附加的机械强度。所述稀松布可由天然的、有机或无机纤维制成，玻璃、棉、尼龙或聚酯是典型的实例。玻璃纤维稀松布尤其优选用于被嵌入到所述片层中。所述稀松布可为织造或针织结构并具有不超过40克/平方米的典型单位面积重量。所述稀松布要么在片材料已被涂覆到所述防潮层上之后，要么当片材料正被涂覆到所述防潮层之时被定位到片层中。
要求不含稀松布的片层的厚度为7.0至76微米，并更优选7.0至50微米。另一个要求是所述片层具有V-0的UL 94火焰分级。所述片层(其中相邻的片重叠)提供火焰和热气不可渗透的阻隔功能。所述无机片可为粘土，如蒙脱石、蛭石、云母、滑石以及它们的组合。优选地，所述无机氧化物片在约600℃，更优选在约800℃，并且最优选在约1000℃下是稳定的(即，不会燃烧、熔融或分解)。蛭石是就本发明而言优选的片材料。蛭石为水合的硅铝酸镁云母状的矿物质，以多层结晶天然存在。蛭石通常包含按(干重)重量计，基于理论氧化物，约38-46％的SiO2，约16-24％的MgO，约11-16％的Al2O3，约8-13％的Fe2O3并且残留物一般为钾、钙、钛、锰、铬、钠和钡的氧化物。“剥落的”蛭石指的是已被化学或热处理的蛭石，以膨胀并分离结晶层，产生高的纵横比蛭石片。适宜的蛭石材料以商品名MicroLite 963和MicroLite HTS-XE得自W.R.Grace(Cambridge，MA)。
膜层
要求热塑性膜层具有不大于25微米的厚度。在一个优选的实施方案中，所述热塑性膜层具有不大于15微米的厚度。更优选地，所述厚度不大于10微米。附加的要求是热塑性膜层还具有V-0的UL 94火焰分级。该薄膜层的另一个要求是所述膜的平均断裂伸长率不大于150％，并且更优选不大于125％。所谓平均伸长率是指如在纵向和横向上测量的伸长率的平均值，其中所述横向为正交于所述纵向的方向。优选地，所述膜层还必须能够软化。所谓软化是指所述膜层可足够柔软以粘结到另一热塑性膜层上而无需完全熔融。优选的热塑性材料为聚酮、聚酰亚胺、聚砜、聚芳硫醚、含氟聚合物、液晶聚合物和聚碳酸酯。聚酮的实例为聚醚醚酮(PEEK)和聚醚酮酮(PEKK)。聚醚砜和聚苯砜为聚砜的实例。聚对亚苯基硫醚是可用于本发明的适宜的聚芳硫醚。聚氟乙烯(PVF)和聚偏氟乙烯(PVDF)为适宜的含氟聚合物的实例。聚芳酯为适宜的液晶聚合物的实例。这些膜中的一些还可涂覆有第二种聚合物材料。例如，聚酰亚胺膜Kapton
Figure BPA00001447640800041
可涂覆有氟化的乙烯丙烯、FEP并且用于本发明。
在一个优选的实施方案中，所述水分阻隔膜层为聚酰亚胺，并且所述热塑性膜层为PEKK。
隔音毯
如上所述的复合层压板可被用做绝热和隔音毯的组件。本发明的绝热和隔音毯包含：
(a)当根据BSS7230方法F1测试时，具有不大于10秒的自熄灭时间和不大于102mm的最大燃烧长度的无机或有机芯。
(b)包围所述芯材料的复合层压板，所述层压板进一步包含
(1)具有6.0至25.0微米的厚度和V-0的UL 94火焰分级的聚合物防潮层，
(2)具有7.0至76.0微米的厚度和V-0的UL 94火焰分级的无机片层，其中所述片包含具有100至20,000纵横比的片层，和
(3)具有不大于25微米的厚度、不大于150％的平均断裂伸长率和V-0的UL 94火焰分级的热塑性膜层，
其中所述复合层压板的热塑性膜层接触并包封所述芯。
图2显示贯穿适用于飞机机身的绝热和隔音毯20的区段，所述毯包含被防烧透复合层压板包封的芯材料14，所述复合层压板按顺序包含与所述芯接触的热塑性膜层13、无机片层12和形成所述层压板的外表面的防潮层11。所述毯抵靠飞机机身的内部表皮放置。
要求所述芯14满足下列易燃性要求。在一个竖式测试(60秒点燃)中，当根据联邦航空条例第25节附录F第1部分测量时，所述芯必须在不大于10秒内自熄灭并且必须具有不大于102mm的最大燃烧长度。在一个45度角测试中，当根据BSS7230测量时，所述自熄灭时间必须不大于5秒，并且所述残炽不大于10秒。
所述芯可为泡沫或有机或无机纤维材料。适宜的泡沫材料为聚酰亚胺，以商品名INSULMIDE购自Johns Manville Insulations Group(Denver，CO)或以SOLIMIDE购自Inspec Foams(Allen，TX)。适宜的非金属纤维包括但不限于玻璃纤维、芳族聚酰胺纤维、结晶的陶瓷氧化物(包括石英)纤维、氮化硅纤维、碳化硅纤维、氧化的聚丙烯腈纤维、碳纤维、以及它们的组合。
玻璃纤维为优选的材料，而E-玻璃(一种低碱硼硅酸盐玻璃)是尤其适宜的。陶瓷氧化物材料通常为已被热的作用巩固的金属氧化物。陶瓷氧化物纤维一般来讲是指通常包含一种或多种铝、硅、和硼的氧化物的纤维种类。在所述纤维内还可存在许多其它的添加剂(如钠、钙、镁、和磷的氧化物)，尽管所述纤维主要包括金属氧化物。通常，所述陶瓷氧化物纤维为结晶的陶瓷和/或结晶的陶瓷与玻璃的混合物(即，包含结晶的陶瓷和玻璃相两者的纤维)。优选的陶瓷氧化物纤维为硅铝酸盐、铝硼硅酸盐、和矾土纤维，并可为纱线的形式或为短纤维的形式。非金属纤维优选的形式为絮，其为柔软的大团纤维的组合件，通常为已经梳理过的。絮具有5.5至24.0kg./m3的典型密度范围。适宜的玻璃絮以商品名MICROLITE AA购自Johns Manville OEM Insulations Division(Denver，CO)。所述芯可包含一个以上的材料层。在所述芯的不同层中的材料不必相同。
所述芯被复合层压板包封。这通过将复合层压板围绕芯14包裹使得热塑性膜层13邻近所述芯来实现。使复合层压板经受充足的热量以部分地软化并将两个热塑性膜层熔合在一起，如图2的15所示。在所述芯的“上部”和“下部”表面上的热塑性膜层因此围绕芯的所有四个边缘来包封所述芯。所述部分软化可通过诸如热风枪或超声波结合的方法实现。可调节芯和层压板材料的相对的量以适合特定的绝热和隔音毯的规格，但一般目标是以尽可能低的毯重量来满足必需的火焰和噪音标准。所述毯组合件的防潮层外层使水分摄入最小化，因此在使用期间毯的重量增加也最小化。所述复合层压板向毯组合件提供阻挡火焰蔓延性能。
测试方法
烧穿时间，如在2007版的NFPA 2112的第8.2节：Standard on Flame-Resistant Garments for Protection of Industrial Personnel Against Flash Fire中所规定，在改进的热防护性能(TPP)仪器上测量。这进一步通过参考图3来解释。通常显示为30的TPP仪包括两个Meeker燃烧器35，与垂直提供的火焰呈45度角以冲击所述样品31。此外，有一排石英管37提供热辐射。所述样品通过支撑物33被保持在位。一根9.5mm铜气流管36使每分钟大约20升的气流通过火焰，因此在样品下方提供质量流量压力。这允许模拟在联邦航空条例(FAR)25.856(b)中规定的质量流量。给燃烧器的丙烷流被设置为每分钟5.0升以在样品处产生2.3cal/cm2-秒且温度超过1000℃的总体热流量。水冷的遮板34防止火焰和热量到达所述样品，直到测试准备开始，此时遮板被移开。使样品经受热量和质量流直到在样品中形成孔洞，此时记录时间为烧透时间，所述测试完成。
实施例
在以下实施例中，除非另外指明，所有份数和百分比均按重量计并且所有温度均按摄氏度计。根据本发明制备的实施例用数值来指示。对照实施例或比较实施例用字母来指示。与比较实施例和本发明的实施例相关的数据和测试结果示于表1中。
实施例A为127微米厚的Nomex
Figure BPA00001447640800061
型418TM纸材样品，其具有149g/m2的单位面积重量。Nomex
Figure BPA00001447640800062
型418TM为如下生产的纸材：共混约50％云母片与短纤维(絮状物)和合成的间芳族聚酰胺聚合物的膜状颗粒(纤条体)，随后通过在高温和压力下压延所述纸材。Nomex
Figure BPA00001447640800063
型418TM纸材得自E.I.DuPontde Nemours(Wilmington，DE)。使用Nomex型418TM作为防烧透纸材用于飞机绝热毯的用途进一步描述于美国专利6,627,561和6,670,291，以及PCT专利申请WO2006/028666中。提供该纸材的三个样品来用于烧透测试，并提供在1.05至2.28分钟范围内的燃烧时间，平均燃烧时间为1.61分钟。测试时间的结束与烧透时间相同。纸材等级测试遵从FAR 25.856(b)。
实施例1以下列方式制备。以商品名Kapton得自DuPont的聚酰亚胺膜的7.6微米层被用作防潮层。所述聚酰亚胺膜具有12.2g/m2的单位面积重量。MicroLite
Figure BPA00001447640800065
963等级的蛭石片含水分散体按原样使用，并使用得自PaulN.Gardner Company Inc.(Pompano Beach，FL)的可调节的微米膜施用装置涂覆到所述聚酰亚胺膜上。涂覆的蛭石膜在室温下干燥过夜以除去残余的分散剂。所述蛭石层具有37.9g/m2的单位面积重量。具有9.2g/m2的单位面积重量和120％的平均断裂伸长率的6.0微米厚的PEKK层被用作热塑性膜层，并且被置于所述蛭石层之上。然后将复合组合件在180℃的温度下置于压力机中40秒以将所述层合并在一起，形成重量为59.3g/m2的层压板。对所述合并的复合层压板进行烧透测试。5分钟后没有烧透，此时停止测试。所述复合层压板仅为Nomex
Figure BPA00001447640800071
型418TM对照物重量的40％但却具有极其优异的防烧穿性能。
实施例2以下列方式制备。具有9.2g/m2单位面积重量的6.0微米厚的PEKK层被用作防潮层。MicroLite963等级的片被涂覆到PEKK膜上，如在实施例1中那样。涂覆的膜在室温下干燥过夜以除去痕量的残余分散剂。所述蛭石层具有51.1g/m2的单位面积重量。具有9.2g/m2的单位面积重量和120％的平均断裂伸长率的6.0微米厚的PEKK层被用作热塑性膜层，并且被置于所述蛭石层之上。然后将复合组合件在180℃的温度下置于压力机中40秒以将所述层合并在一起，形成重量为69.5g/m2的层压板。对所述合并的复合层压板进行烧透测试。5分钟后没有烧透，此时停止测试。所述复合层压板仅为Nomex
Figure BPA00001447640800073
型418TM对照物重量的47％但却具有极其优异的防烧穿性能。
表1
Figure BPA00001447640800074
预期实施例1或2所述的复合层压板可与玻璃纤维絮的芯如具有6.7Kg/m3密度的25.4mm厚的Microlite
Figure BPA00001447640800081
AA片合并。在此类组合中，复合层压板的片被置于絮的两个外表面之上，使得层压板的热塑性膜层邻近所述絮的外表面并与所述絮的外表面接触。此外，所述复合层压板比所述絮具有更大的面积并在所述絮的四个边缘之上延伸。所述絮通过将延伸到所述絮之上的复合层压板的边缘卷曲到一起并通过在褶皱区域施加热量以软化并将两个层压板熔合到一起来包封，所述絮被包封。
还预期实施例1或2所述的复合层压板可与聚酰亚胺泡沫的芯如具有6.4Kg/m3密度的25.4mm厚的Solimide
Figure BPA00001447640800082
TA-301片合并。在此类组合中，复合层压板的片被置于泡沫的两个外表面之上，使得层压板的热塑性膜层邻近所述泡沫的外表面并与所述泡沫的外表面接触。此外，所述复合层压板比所述泡沫具有更大的面积，并在所述泡沫的四个边缘之上延伸。所述泡沫通过将延伸到所述泡沫之上的复合层压板的边缘卷曲到一起并通过在褶皱区域施加热量以软化并将两个层压板熔合到一起来包封，所述泡沫被包封。

Claims (14)

1.复合层压板，所述复合层压板按顺序包含：
(a)具有6.0至25.0微米的厚度和V-0的UL 94火焰分级的聚合物防潮层，
(b)具有7.0至76.0微米的厚度和V-0的UL 94火焰分级的无机片层，其中所述片包含具有100至20,000的纵横比的片层，和
(c)具有不大于25微米的厚度、不大于150％的平均断裂伸长率和V-0的UL 94火焰分级的热塑性膜层。
2.权利要求1的复合层压板，其中所述防潮层包含聚合物，其中所述聚合物选自含氟聚合物、聚酰亚胺、聚醚醚酮和聚醚酮酮。
3.权利要求1的复合层压板，其中所述防潮层的外表面被金属化。
4.权利要求1的复合层压板，其中所述无机片层包含片，所述片选自粘土、蛭石、云母、滑石以及它们的组合。
5.权利要求1的复合层压板，其中所述热塑性膜包含聚合物，所述聚合物选自聚酮、聚酰亚胺、聚砜、聚芳硫醚、含氟聚合物、液晶聚合物和聚碳酸酯。
6.权利要求5的复合层压板，其中所述热塑性膜包含聚合物，所述聚合物选自聚醚醚酮、聚醚酮酮、聚醚酰亚胺、聚醚砜、聚苯砜、聚(对亚苯基硫醚)、聚氟乙烯、聚偏氟乙烯和聚芳酯。
7.绝热和隔音毯，所述绝热和隔音毯包含
(a)当根据BSS7230方法F1测试时，具有不大于10秒的自熄灭时间和不大于102mm的最大燃烧长度的无机或有机芯；
(b)包围所述芯材料的复合层压板，所述层压板还包含
(1)具有6.0至25.0微米的厚度和V-0的UL 94火焰分级的聚合物防潮层，
(2)具有7.0至76.0微米的厚度和V-0的UL 94火焰分级的无机片层，其中所述片包含具有100至20,000的纵横比的片层，和
(3)具有不大于25微米的厚度、不大于150％的平均断裂伸长率和V-0的UL 94火焰分级的热塑性膜层，
其中所述复合层压板的热塑性膜层接触并包封所述芯。
8.权利要求7的毯，其中所述芯包含矿物纤维絮的层。
9.权利要求7的毯，其中所述芯包含聚合物泡沫。
10.权利要求7的毯，其中所述防潮层包含聚合物，其中所述聚合物选自含氟聚合物、聚酰亚胺、聚醚醚酮和聚醚酮酮。
11.权利要求7的毯，其中所述防潮层的外表面被金属化。
12.权利要求7的毯，其中所述无机片层包含片，所述片选自粘土、蛭石、云母、滑石以及它们的组合。
13.权利要求7的毯，其中所述热塑性膜包含聚合物，所述聚合物选自聚酮、聚酰亚胺、聚砜、聚芳硫醚、含氟聚合物、液晶聚合物和聚碳酸酯。
14.权利要求13的毯，其中所述热塑性膜包含聚合物，所述聚合物选自聚醚醚酮、聚醚酮酮、聚醚酰亚胺、聚醚砜、聚苯砜、聚(对亚苯基硫醚)、聚氟乙烯、聚偏氟乙烯和聚芳酯。
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DE202010018425U1 (de) 2016-06-28
CN102405172B (zh) 2014-08-06
USRE46658E1 (en) 2018-01-02
USRE46859E1 (en) 2018-05-22
DE202010018433U1 (de) 2016-08-10
EP2421750A1 (en) 2012-02-29
US20110094826A1 (en) 2011-04-28
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