CN100503230C - 云母片和带 - Google Patents

云母片和带 Download PDF

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CN100503230C
CN100503230C CNB2003801058989A CN200380105898A CN100503230C CN 100503230 C CN100503230 C CN 100503230C CN B2003801058989 A CNB2003801058989 A CN B2003801058989A CN 200380105898 A CN200380105898 A CN 200380105898A CN 100503230 C CN100503230 C CN 100503230C
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M·R·勒维特
L·N·巴斯科姆
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EIDP Inc
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Abstract

本发明涉及一种用于电绝缘或阻燃的片结构，包含具有富云母表面和贫云母表面的阻隔层以及含有与阻隔层的贫云母表面连接的可饱和支撑层的增强层。

Description

云母片和带
发明背景
1.发明领域
本发明涉及一种用于电绝缘或阻燃的片结构，包含具有富云母表面和贫云母表面的阻隔层和含有与阻隔层的贫云母表面连接的可饱和支撑层(backing layer)的增强层。
2.相关技术的描述
基于云母的片和带用作电绝缘和阻燃材料是本领域公知的。这些片和带典型地由粘接在增强材料衬底上的云母纸组成。
美国专利4,286,010、4,769,276、6,103,382、6,153,301和欧洲专利申请0 373 137 A2公开了云母片和带的制备和在电绝缘和阻燃应用中的用途。但是，通过将云母纸粘接到支撑增强材料上所生产的云母带受到限制，因为粘合剂必须与通常在后续步骤中施用到带上的饱和树脂相容。粘合剂还必须在长时间内是热稳定的.例如，广泛使用的衬底玻璃布和作为粘合剂的环氧树脂的组合限制了绝缘带的最终使用温度是180℃，并限制了可以在浸渍步骤中使用的树脂(通常必须使用相同的环氧树脂)。而且，许多树脂的粘合方法通常涉及连续的溶剂基过程，以及于与发性有机物质处理(通风，溶剂的再恢复等)相关的所有技术和安全复杂性。
芳族聚酰胺-云母共混纸是由间-芳族聚酰胺纤维、间-芳族聚酰胺沉析纤维和云母的均匀共混物生产，由DuPont以纸型418销售。这些纸描述在例如美国专利6,312,561中。因为相对于云母纸的优异机械性能，从
Figure C200380105898D00042
418纸生产的带可以在不需要任何衬底增强的情况下使用。但是，在这种阻隔材料中的30-60重量％的有机(芳族聚酰胺)组分限制了其可能的抗电晕性或电压耐受性。另一种限制是在用基于这种纸的带绝缘的物品进行真空压力浸渍的过程中，必须将该物品旋转直到树脂完全固化，因为该带不是可饱和的，也就是说该带不具有能保留未固化的树脂的组分。
也公开了两层纸，其中一层由云母组成，另一层可以由芳族聚酰胺、玻璃、聚酯或其它纤维组分组成(俄国专利2051434，1996).这些纸不具有必要的增强，在片状形式时是较弱的，不能生产可接受的窄宽度的带。
所需要的是一种含有高浓度云母的片结构，其可以被制成带和容易用树脂饱和，并且具有用于电绝缘和阻燃结构的充足机械性能.
发明概述
本发明涉及一种片结构，包含含有富云母表面和贫云母表面的阻隔层和与阻隔层的贫云母表面连接的增强层，其中增强层含有可饱和的支撑层。在阻隔层的富云母表面中的云母含量是基于富云母表面中组分总量计的至少60重量％；贫云母表面含有小于40重量％的云母，基于贫云母表面中的组分总量计；增强层的可饱和支撑层是射流喷网法的芳族聚酰胺材料。在本发明的优选实施方案中，阻隔层的富云母表面具有基于富云母表面中组分总量计的大于85重量％的云母，贫云母表面含有基于贫云母表面中的组分总量计的小于10重量％的云母。除了云母之外，本发明的片结构还可以在阻隔层中包含芳族聚酰胺材料。在富云母表面和贫云母表面中的云母的量可以通过从该片结构仔细地用显微镜切薄片或用显微镜切割各种整合层并采用标准分析技术分析各层的组成而在片结构中检测.
另外，本发明的片结构可以用于生产基于云母的带，和可以与基体树脂组合生产预浸件(prepregs)。
本发明还涉及一种生产片结构的方法，包括以下步骤：形成含有富云母表面和贫云母表面的阻隔层，并将含有可饱和支撑层的增强层连接到阻隔层的贫云母表面上。阻隔层可以在造纸机上形成，阻隔层的富云母表面和贫云母表面可以通过将分开的富云母和贫云母淤浆供应到造纸机来形成。另外，增强层可以通过层压或压延各层而与阻隔层连接。
详细描述
本发明提供了基于云母的片结构、带和预浸件，例如用于电绝缘。另外，本发明可以用作阻燃层，因为云母在组合物中的显著含量。
本发明的片结构或带包含基于总重量计的至少30重量％的云母，并由至少一层阻隔层和一层增强层构成。云母在阻隔层的一面或一侧浓缩，阻隔层的另一面或另一侧没有云母或具有低浓度的云母。“富云母”表示该表面具有至少60重量％的云母含量，基于在富云母表面中的组分的总重量计。“贫云母”表示该表面具有小于40重量％的云母含量，基于在富云母表面中的组分的总重量计。
虽然不限制生产方法，本发明的阻隔层可以在常规造纸机上生产，该造纸机配备了两个网前箱用于形成层合纸.具有云母和/或其它材料固体的所需比例的两种不同淤浆被供应到两个网前箱中，这两种淤浆然后作为层湿铺(wet-laid)到造纸线上，其中例如贫云母表面在造纸线上形成，富云母表面在贫云母表面之上形成。这形成了在富云母和贫云母表面的界面处具有纤维组分的混合的单片。
形成后，阻隔层可以然后与分开的增强层组合，增强层面对阻隔层的贫云母表面。这两层然后彼此连接，优选的方法是在不用粘合剂树脂或胶粘剂的情况下通过将这两层在造纸机的湿压机中或在热辊压延机的夹辊中层压而将这两层连接在一起.
本发明的片结构或带可以具有约30-300g/m2的基本重量和约0.02-1.0mm的厚度.
在本发明的基于云母的片或带中，阻隔层的富云母表面含有至少60重量％、优选至少85重量％的云母，基于在富云母表面中组分的总重量。富云母表面的其它组分可以包括间-芳族聚酰胺沉析纤维和其它粘合剂材料；和芳族聚酰胺、玻璃和其它纤维，它们可以用于减少来自云母带的起尘和调节富云母层的机械性能。
阻隔层的贫云母表面可以具有与富云母表面相同的组分，优选含有间-芳族聚酰胺沉析纤维作为粘合剂，以及芳族聚酰胺纤维或其它热稳定性絮凝物或纤维或者这些絮凝物或纤维的混合物。“热稳定性”表示给定的絮凝物或纤维可以经受长时间暴露于最终使用温度下，且没有显著的降解(通常，在暴露于必要的温度下100000小时后保留至少50％的初始性能)。其它热稳定性絮凝物或纤维可以包括、但不限于纤维例如聚酯和聚苯并咪唑，和基于含氟聚合物、玻璃和硅石的絮凝物和纤维。
本发明的片结构中的增强层含有可饱和的支撑层，其可以是织造的、编织的或非织造的织物，这些织物从任何热稳定性的有机或无机纤维或这些纤维的混合物生产。可能的纤维包括、但不限于芳族聚酰胺、聚酯和玻璃纤维。优选的是，增强层是射流喷网法非织造织物，因为这些织物在片结构的卷绕过程中显示良好的缓冲性能，以及这些非织造织物在树脂浸渍期间显示快速、均匀的树脂吸收。增强层可以包括其他层以赋予其它功能，只要可饱和的支撑层的饱和能力不受损害即可。
如上所述，在阻隔层的表面中的云母量可以根据特定的最终用途而不同，富云母表面具有基于该表面中组分总重量计至少60重量％的云母，贫云母表面具有基于该表面中组分总重量计的小于40重量％的云母.在用树脂浸渍之前，阻隔层可以是基于片结构总重量计的50-95重量％，增强层可以是基于片结构总重量计的5-50重量％。
各种类型的云母(白云母或金云母，热化学或热机械的)可以用于本发明中。对于任何具体片结构的最佳类型通常取决于最终用途。典型地，白云母优选用于电绝缘，金云母优选用于阻燃.
在这里使用的术语“絮凝物”表示被切割成短长度和通常在湿铺片的制备中使用的纤维。典型地，絮凝物具有约3-20mm的长度.优选的长度是约3-7mm。芳族聚酰胺絮凝物是在阻隔层的富云母表面和贫云母表面中优选使用的絮凝物.絮凝物通常通过用本领域熟知的方法将连续纤维切割成所需的长度来生产。
在这里使用的术语“芳族聚酰胺”表示芳族聚酰胺，其中至少85％的酰胺(-CONH-)键直接与两个芳环连接。任选地，添加剂可以与芳族聚酰胺一起使用，可以分散在聚合物结构内。已经发现多达约10重量％的其它聚合物材料可以与芳族聚酰胺共混。也已经发现可以使用共聚物，其中多达约10重量％的其它二胺代替芳族聚酰胺的二胺，或多达约10重量％的其它二酰氯代替芳族聚酰胺的二酰氯。
在这里使用的术语“沉析纤维”表示非常小的、非颗粒的纤维状或膜状粒子，其中其三维的至少之一是相对于最大尺寸的小尺寸。这些粒子是通过用非溶剂在高剪切下沉淀聚合物材料的溶液来制备。在这里使用的术语“芳族聚酰胺沉析纤维”表示芳族聚酰胺的非颗粒的膜状粒子，具有高于320℃的熔点或分解温度。沉析纤维通常具有约0.2-1mm的最大长度，长度与宽度的纵横比是约5:1至约10:1。厚度是微米级，例如约0.1-1.0微米。虽然不是必须的，优选在沉析纤维仍然处于不干燥的状态下将芳族聚酰胺沉析纤维引入阻隔层中。除了芳族聚酰胺之外，芳族聚酰胺沉析纤维可以任选地含有染料、颜料和其它添加剂例如抗静电剂、表面活性剂，或填料例如碳黑、硅石和二氧化钛。
本发明的片结构和/或带的任一层可以含有用于进一步改进电压耐受性的特殊添加剂。这些添加剂可以包括、但不限于基于二氧化硅、氧化铝、二氧化钛、二氧化锆或其组合物的粒子。
在生产时，本发明的片结构和/或带优选原样不含在各层之间的任何粘合树脂，这使得可以在片或带的浸渍期间使用宽范围的树脂以生产最终的绝缘材料。
几种方法可以用于制备基于本发明片结构和/或带的最终树脂浸渍的绝缘材料.第一种常用方法包括在已经引入要绝缘的物品或缠绕在要绝缘的物品之后用树脂浸渍片或带，然后固化该树脂。第二种常用方法包括在引入要绝缘的物品或缠绕在要绝缘的物品之前用树脂浸渍片或带，然后固化该树脂。
令人惊奇和出乎预料的是，在本发明的优选方式中，阻隔层的贫云母表面能提供阻隔层和增强层之间的良好粘合，且不需要使用任何额外的粘合树脂。在本领域公知的是一层芳族聚酰胺纸或板可以在热压延夹辊中或在热压机中与另一层芳族聚酰胺纸或板层压，如果这两层都含有沉析纤维、可模塑的纤维或一些其它粘合剂的话，描述在例如美国专利4,481,060和4,752,355中。但是，出乎预料的是，足够的粘合和片强度可以通过用含有可饱和支撑材料的增强层在不含任何沉析纤维、可模塑的纤维或粘合剂的情况下层压阻隔层来实现；或可饱和的表面将具有足够的孔隙率用于在这种层压之后进一步进行树脂浸渍。
在这里使用的术语“预浸件”包括通过树脂浸渍的基于云母的片或带，并具有足够的压制和/或成型成最终复合材料的可成型性。当片或带用热固性树脂浸渍时，该树脂通常是处于预浸件中的固化阶段B(部分可溶解的)，可以另外随后被固化到阶段C(已交联的，不能溶解的)。
基于本发明云母片或带的预浸件可以通过任何公知的技术使用基体树脂溶液、分散体或能流入本发明结构中的熔体生产。基体树脂的粘度对于本发明不是特别关键的。如果基体树脂具有非常高的粘度，则它应该溶解在溶剂中溶解以形成溶液，然后该溶液可以用于浸渍片材.如果使用低粘度的基体树脂，则溶液或分散体不是必要的。例如，开发用于真空压力浸渍(VPI)的低粘度环氧树脂组合物现在在工业中使用，可以与本发明的材料一起使用，且不需要添加任何溶剂。
实验方法
以下实验方法用于下面的实施例中。本发明的云母基片或带的拉伸性能是在Instron型实验机上用2.54cm宽和18cm标准长度的实验样品按照ASTM D 828-93进行检测。
本发明的云母基片或带的厚度和基本重量是通过分别按照ASTMD645/D 645-M-96和ASTM D646-96检测实验非织造片样品的厚度和面积重量来测定。
云母基片的内部抗撕裂性是按照ASTM D689-96a使用Elmendorf-Type Tearing Tester用单片检测。
树脂吸收性是基于检测在浸渍前和在浸渍和树脂完全固化之后的云母基片的重量测定。在每次称重之前，该材料在烘箱中于110℃干燥24小时。按重量百分比计的树脂吸收性是基于下式计算：
{(Wt.后-Wt.前)/(Wt.后)x100％
其中Wt.前和Wt.后分别是浸渍之前和之后的材料重量。
实施例
含有间-芳族聚酰胺絮凝物和间-芳族聚酰胺沉析纤维的混合物的水分散液被制成具有以下非含水组分的相对含量(重量％)：
间-芳族聚酰胺絮凝物：约60重量％
间-芳族聚酰胺沉析纤维：约40重量％
另一种含有云母和间-芳族聚酰胺沉析纤维的混合物的水分散液被制成具有以下非含水组分的相对含量(重量％)：
云母：约95重量％
间-芳族聚酰胺沉析纤维：约5重量％
这些分散液被泵送通过Fourdrinier型造纸机的第一和第二网前箱，形成了层合湿铺层板，其中在顶部是富云母层，在底部是含有主要芳族聚酰胺组分的贫云母层。顶层的基本重量是约84.8g/m2，底层的基本重量是约50.9g/m2。
使用的云母是白云母型，Electrical Samica Flake(US SAMICAIncorporated，Rutland，Vermont，USA生产)
间-芳族聚酰胺沉析纤维是从聚间苯二甲酰间苯二胺按照美国专利3,756,908中一般描述的方式生产.
间-芳族聚酰胺絮凝物是聚间苯二甲酰间苯二胺絮凝物，线型密度是0.22特，长度是0.64cm(由E.I.du Pont de Nemours and Company以商品名
Figure C200380105898D00101
销售)。
层合的湿铺层板形成阻隔层，并在压延机的热夹辊中在约3000N/cm的夹辊压力下用非织造的间-芳族聚酰胺材料的增强层层压。底辊的温度(面对射流喷网法材料)是约350℃，顶辊的温度(面对富云母层)是约180℃。用作增强层的非织造的间-芳族聚酰胺材料是聚间苯二甲酰间苯二胺射流喷网法织物，具有68g/m2的基本重量(由E.I.du Pont de Nemours and Company以商品名
Figure C200380105898D00102
射流喷网法织物型E88，320型销售)。
所得的基于云母的片结构具有约205g/m2的基本重量和约0.208mm的厚度。该片总重量的约66.1重量％包含在阻隔层中，其中在富云母表面中含有基于富云母表面组分的95重量％的云母，在贫云母表面中基本不含云母。该片总重量的约33.9重量％包含在增强层中.基于总重量的总云母含量是约39.2重量％.最终云母基片的其它性能显示在表1中。一部分制备的云母基片然后被分成约12.7mm宽度的云母基带。另一部分制备的云母基片被切成20cm x 20cm的样片，用不含溶剂的低粘度环氧组合物类型E-833(由P.D.George Co.，St.Louis，MO，USA销售)浸渍。为了模拟真空压力浸渍过程，将一片该片材在烘箱中于110℃干燥24小时，然后用该树脂在真空烘箱中于室温下在约5kPa残余压力下浸渍，最后在平板压机中按照多步法在约650kPa的恒定压力和约135℃的温度下热处理60分钟，在156℃下热处理120分钟，在177℃下热处理60分钟，和在93℃下热处理1分钟。
对比实施例
以上实施例的阻隔层在没有增强材料的情况下在与该实施例中相同的条件下压延。压延的纸具有约0.105mm的厚度。一些其它性能列在表1中。
从表1可见，实施例1的增强层显著提高了云母基阻隔片的拉伸和撕裂性能，以及提高了树脂吸收性。这证实了通过阻隔层的贫云母层进行的粘合是充足的，增强层的可饱和表面在层压过程之后仍然能被树脂可饱和。
表1
 
材料 在纵向上的拉伸强度，N/cm 在纵向上的初始抗撕裂性，N 在横向上的初始抗撕裂性，N 浸渍过程中的树脂吸收，重量％
实施例 41.3 13.2 14.8 47
对比实施例 27.1 2.0 3.0 36

Claims (13)

1.一种片结构，包含：
(a)含有富云母表面和贫云母表面的阻隔层；和
(b)含有树脂可饱和支撑层的增强层，其中所述增强层与阻隔层的贫云母表面连接；
其中阻隔层的富云母表面具有基于富云母表面中组分总量计的至少60重量％的云母，贫云母表面含有基于贫云母表面中组分总量计的小于40重量％的云母。
2.权利要求1的片结构，其中云母含量是片结构总组成的至少30重量％。
3.权利要求2的片结构，其中增强层的树脂可饱和支撑层是射流喷网的芳族聚酰胺材料。
4.权利要求1的片结构，其中除了云母之外，阻隔层还包含芳族聚酰胺材料。
5.权利要求1的片结构，其中阻隔层的富云母表面具有基于富云母表面中组分总量计的至少85重量％的云母，贫云母表面含有基于贫云母表面中组分总量计的小于10重量％的云母。
6.基于云母的带，含有权利要求2的片结构。
7.预浸件，含有权利要求2的片结构和基体树脂。
8.一种生产片结构的方法，包括以下步骤：
a)形成含有富云母表面和贫云母表面的阻隔层，和
b)将增强层连接到阻隔层的贫云母表面上，其中所述增强层含有树脂可饱和的支撑层；
其中阻隔层的富云母表面具有基于富云母表面中组分总量计的至少60重量％的云母，贫云母表面含有基于贫云母表面中组分总量计的小于40重量％的云母。
9.权利要求8的方法，其中阻隔层是在造纸机上形成。
10.权利要求9的方法，其中阻隔层的富云母表面和贫云母表面是通过将分开的富云母和贫云母淤浆供应到造纸机来形成。
11.权利要求8的方法，其中增强层的树脂可饱和支撑层是射流喷网的材料。
12.权利要求8的方法，其中增强层是通过层压或压延各层而与阻隔层连接。
13.一种导电体或半导体，在表面上具有包含以下物质的结构：
(a)含有富云母表面和贫云母表面的阻隔层；和
(b)含有树脂可饱和支撑层的增强层，其中所述增强层与阻隔层的贫云母表面连接；
其中阻隔层的富云母表面具有基于富云母表面中组分总量计的至少60重量％的云母，贫云母表面含有基于贫云母表面中组分总量计的小于40重量％的云母。
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US20040115422A1 (en) 2004-06-17
US6991845B2 (en) 2006-01-31
CN1726134A (zh) 2006-01-25
BR0316598A (pt) 2005-10-04
BR0316598B1 (pt) 2015-01-27
CA2507925A1 (en) 2004-07-01
MXPA05006249A (es) 2005-08-19
KR101069028B1 (ko) 2011-09-29
EP1581387A2 (en) 2005-10-05
US20060019081A1 (en) 2006-01-26
AU2003301046A8 (en) 2004-07-09
CA2507925C (en) 2011-05-24
KR20050084239A (ko) 2005-08-26
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AU2003301046A1 (en) 2004-07-09
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