CN104364078A - 电绝缘材料 - Google Patents

电绝缘材料 Download PDF

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Publication number
CN104364078A
CN104364078A CN201380030895.7A CN201380030895A CN104364078A CN 104364078 A CN104364078 A CN 104364078A CN 201380030895 A CN201380030895 A CN 201380030895A CN 104364078 A CN104364078 A CN 104364078A
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CN
China
Prior art keywords
woven
paper
goods according
fabric layer
woven fabric
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201380030895.7A
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English (en)
Inventor
罗伯特·H·特平
大卫·S·斯坦克斯
马丁·H·福克斯
米切尔·T·黄
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3M Innovative Properties Co
Original Assignee
3M Innovative Properties Co
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Filing date
Publication date
Application filed by 3M Innovative Properties Co filed Critical 3M Innovative Properties Co
Publication of CN104364078A publication Critical patent/CN104364078A/zh
Pending legal-status Critical Current

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    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/022—Non-woven fabric
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    • H01B3/485—Other fibrous materials fabric
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Abstract

本发明提供一种包含在两个非纤维素的非织造纸层之间的非纤维素的非织造织物层的制品，其中非织造纸和非织造织物之一或二者电绝缘。至少一些实施例是阻燃剂。

Description

电绝缘材料
技术领域
本发明涉及适用于电绝缘应用的材料。
背景技术
电气设备诸如电动机、发电机和变压器通常需要某些形式的电介质绝缘，以将处于一个电压的导体与处于不同电压的导体分开和/或为电子部件提供机械保护。电绝缘材料的层合物通常在工业中用于此目的。此类材料的示例在WO 2012/082180；JP 2000/008299；CA 2003221；和JP 9158092中被描述。
发明内容
在某些电绝缘应用中，需要达到高阻燃性等级(例如，UL 94V-0)同时在热老化后仍提供优异的机械强度和保留的柔韧性的材料。
本发明的材料适用于在变压器、电动机、发电机和需要电子部件绝缘的其他装置中为电子部件提供绝缘，具体地讲，其适用于具有难燃性需求的那些。本发明的至少一些实施例提供具有优异的机械强度、柔韧性和阻燃性的独特柔性电绝缘制品。本发明的至少一些实施例能够达到高阻燃性等级，即使它们包含一些易燃材料。本发明的至少一些实施例提供具有所需的特性平衡的电绝缘材料，所述特性包括难燃性、电介质强度、拉伸强度和抗撕强度。本发明的至少一些实施例还提供所需的热导率特性。
本发明的至少一个实施例提供一种包括非纤维素的非织造织物层的制品，该非纤维素的非织造织物层具有相背的第一主表面和第二主表面，并且具有附接到非织造织物层的每个主表面的非纤维素的非织造纸层，其中非织造纸和非织造织物之一或二者电绝缘。
如本说明书中所用：
“非纤维素的”是指包含小于10重量％的纤维素材料，优选地包含小于5重量％的纤维素材料，更优选地仅包含微量的纤维素材料，以及最优选地不包含纤维素材料。
“直接融合”是指无居间层，诸如粘合剂层；
“非织造纸”是指主要由短纤维构成的片材料；
“非织造织物”是指主要由长纤维构成的片材料；
“短纤维”是指长度短于一英寸的纤维；
“长纤维”是指长度大于或等于一英寸的纤维；
“MD”或“纵向”是指与材料的连续片材的卷绕方向平行的方向；以及
“CD”或“横向”是指与材料的连续片材的卷绕方向垂直的方向。
本发明的至少一个实施例的优点是，即使其包含易燃纤维材料，其根据UL 94阻燃性测试仍达到V-0等级，同时也是柔性的并且具有良好的机械强度。
本发明的上述发明内容并不旨在描述本发明的每个公开的实施例或每种实施方式。下面的详细说明更具体地示出了本发明的实施例。
具体实施方式
在以下说明中，应当理解，其他实施例是可以预期的并且可以在不脱离本发明的范围或实质的情况下完成。因此，以下的具体实施方式不具有限制性意义。
除非另外指明，否则在所有情况下，本说明书和权利要求书中用来表述特征尺寸、数量和物理性能的所有数字均应理解为由术语“约”来修饰。因此，除非有相反的说明，否则本说明书和所附权利要求书中提出的数值参数均为近似值，并且根据本领域的技术人员利用本文所公开的教导内容获得的所需特性，这些近似值可以是变化的。使用由端值表述的数值范围包括该范围内的所有数字和任何值(例如，1至5包括1、1.5、2、2.75、3、3.80、4和5)。
本发明的至少一个实施例提供在两个非织造纸层之间的非织造织物层。其他实施例提供非织造纸和非织造织物的交替的层。一些实施例提供彼此相邻并且在非织造纸层之间的多个非织造织物的层。一些实施例还包括在两个相邻层之间的粘合剂。
提供阻燃性的制品的至少一些实施例包括易燃材料。例如，一些实施例包括易燃的聚对苯二甲酸乙二酯(PET)非织造织物。在至少一些实施例中，据发现，将易燃的非织造织物层放置在至少两个外非织造纸层之间为制品提供了优异的阻燃性。
本发明的至少一些实施例的非织造纸层包括由短纤维即长度短于一英寸(2.54cm)的纤维制成的片材料。在本发明的至少一个实施例中，非织造纸中的大部分纤维为有机的。然而，许多实施例可包括具有无机纤维或填料的非织造纸。
适用于本发明的市售非织造纸的示例包括以商品名CeQUIN得自美国3M公司(3M Company，USA)的那些，包括但不限于CeQUIN I(约90％的无机元素)、CeQUIN II(CeQUIN I的两层复合材料)、CeQUIN X(用于B阶段应用的增强湿强度)以及CeQUIN 3000(约74％的无机元素加有机纤维增强材料)；火焰屏障物(FLAME BARRIER)FRB包括但不限于火焰屏障物-FRB-NT压延的绝缘纸和火焰屏障物FRB-NC未经压延的绝缘纸；可以商品名NOMEX得自杜邦(DuPont)(www2.dupont.com)的那些，包括但不限于NOMEX纸410型、411型(低密度版本)、414型、418型(包含云母)、419型(418型的低密度版本)和E56型；以商品名X-FIPER得自中国圣欧集团的那些；以及以商品名METASTAR得自中国烟台美士达特种纸业股份有限公司的那些。
合适的非织造纸可包括无机纤维和有机纤维，诸如但不限于包括间位芳族聚酰胺和对位芳族聚酰胺的芳族聚酰胺、聚苯硫醚(PPS)、聚酯、聚酰胺、丙烯酸类树脂、三聚氰胺、玻璃、聚烯烃和聚酰亚胺。在本发明的至少一个实施例中，非织造纸还包含聚合物粘结剂。合适的聚合物粘结剂包括但不限于丙烯酸类、腈、苯乙烯-丙烯酸胶乳、瓜耳胶、淀粉和天然橡胶胶乳。
在本发明的至少一个实施例中，非织造纸还包含一种或多种无机填料。合适的无机填料包括但不限于高岭土、滑石、云母、碳酸钙、氧化铝三水合物、蒙脱石、绿土、膨润土、伊利石、绿泥石、海泡石、绿坡缕石、多水高岭土、蛭石、合成锂皂石、累托石、珍珠岩、氮化铝、碳化硅、氮化硼以及它们的组合。合适类型的高岭土包括但不限于水洗高岭土、分层高岭土、煅烧高岭土和经表面处理的高岭土。
包含无机纤维和无机粒子之一或二者的本发明的非织造纸可以被称为无机基纸。与例如完全有机基间位芳族聚酰胺纸相比，无机基纸在电晕/局部放电的存在下提供具有改善的长期的耐电压性，因为无机材料已知比有机材料更耐电晕。(参见例如高温电绝缘短期课程第21页，2001年10月15日至2001年10月18日在俄亥俄州辛辛那提市举办的2001年电绝缘会议(EIC)暨电气制造与线圈绕组(EMCW)展览会)。与例如完全有机基间位芳族聚酰胺纸相比，这些无机基纸还可以为改善的热耗散提供更大的尺寸稳定性以及更高的热导率。
本发明的至少一些实施例的非织造织物层包含由长纤维即长度大于或等于一英寸(2.54cm)的纤维制成的片材料。
非织造织物层通常主要由有机纤维制成但可以包含无机纤维。适于制备非织造织物的有机纤维的示例包括但不限于芳族聚酰胺纤维，包括间位芳族聚酰胺和对位芳族聚酰胺纤维。适用于本发明的非织造织物的至少一些实施例可包含间位芳族聚酰胺和对位芳族聚酰胺纤维之一或二者。在本发明的至少一个实施例中，芳族聚酰胺纤维是非织造织物层的优选组分。本发明的非织造织物的至少一些实施例可包含一种或多种类型的芳族聚酰胺纤维。芳族聚酰胺纤维的类型包括但不限于间位芳族聚酰胺、对位芳族聚酰胺、改性的间位或对位芳族聚酰胺、或者其他类型的芳族聚酰胺。非织造纤维可包含0(零)至100重量％的芳族聚酰胺纤维。在至少一个实施例中，非织造织物包含约20重量％至约70重量％的芳族聚酰胺纤维。
合适的非芳族聚酰胺有机纤维包括但不限于聚苯硫醚(PPS)、包括聚对苯二甲酸乙二醇酯(PET)和聚对苯二甲酸环己烷二甲醇酯(PCT)的聚酯、二醇改性的聚酯、聚苯砜、聚酰胺(尼龙)和聚丙烯纤维。非织造织物可包含约0(零)至100重量％的非芳族聚酰胺纤维。在至少一个实施例中，非织造织物包含约30重量％至约80重量％的非芳族聚酰胺纤维。适用于本发明的非织造织物可包含短(即，非粘结)纤维和粘结纤维。短纤维可包括(例如)间位芳族聚酰胺和对位芳族聚酰胺、聚苯硫醚(PPS)、包括聚对苯二甲酸乙二醇酯(PET)的聚酯、二醇改性的聚酯、聚苯砜、尼龙和聚丙烯纤维。粘结纤维可包括(例如)间位芳族聚酰胺、聚苯硫醚(PPS)、包括聚对苯二甲酸乙二醇酯(PET)和聚对苯二甲酸环己烷二甲醇酯(PCT)的聚酯、二醇改性的聚酯、聚苯砜和聚丙烯纤维。通常，粘结纤维将在施加热量和/或压力时软化和/或流动，从而允许它们与短纤维粘结。
粘结纤维可包括单个聚合物和/或具有不同化学和/或物理特性的两种聚合物的双组分配置。对于适用于本发明的用短纤维和粘结纤维制成的非织造织物，短纤维可通常包括织物的约30重量％至约80重量％，并且粘结纤维可通常包括织物的约20重量％至约70重量％。
在本发明的一些实施例中，没有使用粘结纤维或除了使用粘结纤维之外，非织造织物可包含粘结剂以促进非织造织物内材料的粘结。其他粘结或加强非织造织物的方法包括水刺、点粘结或压延。
通常将纤维共混在一起，以形成非织造织物。共混不同纤维的能力在与现有技术方法诸如将非织造纸层合到连续聚酯膜以增加纸强度相比允许更大的设计柔韧性以符合产品性能。
非织造织物通常包括形成柔性片材料的纤维网，其无需机织或针织既可生产，并通过以下任一方法结合在一起：(i)机械联锁至少一些纤维，(ii)融合一些纤维的至少一些部分，或(iii)通过使用粘结材料粘结至少一些纤维。在粘结或融合某些纤维前，非织造织物可以像棉絮，即柔软蓬松的一大堆纤维。
非织造织物可以为任何合适的形式，例如但不限于梳理非织造织网、纺粘网、熔喷网、稀松布、布、单向网、毡、射流喷网、水解网等。
在至少一个实施例中，梳理非织造织网可以包含约20重量％至约70重量％的芳族聚酰胺纤维共混物以及约30重量％至约80重量％的其他非芳族聚酰胺纤维。
本发明的非织造织物可通过本领域已知的任何合适的方法制备。典型的方法包括用于通常等于或长于一英寸的纤维的干法成型(干法成网)工艺。用于干法成型工艺的较长纤维通常导致具有机械强度良好的开口、多孔结构的非织造织物。干法成型工艺的示例包括梳理法和纺粘法。在典型的干法成型梳理工艺中，将短纤维的团块机械分离成单独的纤维并形成粘接网。梳理机使用间距密集的针的相对运动床牵拉和分离团块。为了由针抓住，用于梳理法的输入纤维通常为卷曲的，即制成波纹状的。
适用于本发明的市售非织造织物包括以商品名THERMAL SHIELD(非织造PPS材料)得自3M公司(3M Company)以及以商品名NOMEXLT得自杜邦(DuPont)(www2.dupont.com)的那些(包括但不限于180型)。
非织造纸和非织造织物层可包含一个或多个片材，即层片或亚层，它们相结合形成相应的层。层片或亚层可以是相同或不同的材料。片材可通过任何合适的方法相结合，诸如使用化学粘合剂或通过诸如热压延的工艺。
在至少一个其他实施例中，将非织造织物层放置在两个非织造纸层之间并直接融合到两个非织造纸层。在至少一个实施例中，非织造织物层和至少一个非织造纸层通过热压延机叠堆的热和压力借助机械和热粘结而融合到一起。
在制备本发明的一些实施例的制品时，不施加粘合剂(即，不使用可用于形成非织造纸或织物层的材料)将各种层或亚层接合在一起。相反，非织造织物层和一个或多个非织造纸层通过仅利用热和压力来压延而粘结。
在制备本发明的一些其他实施例的制品时，使用层的一些类型的粘合。该粘合可以通过例如构造中的热塑性层的存在、各层之间的粘合剂的添加、或粘合增强表面处理诸如等离子处理而实现。可以使用任何合适的粘合剂。例如，粘合剂可以是水基或溶剂型的。粘合剂可以具有任何合适的组合物。合适的组合物的示例包括丙烯酸类树脂、苯乙烯和聚酯。任选地以及优选地，阻燃剂可以被添加到粘合剂中。阻燃剂可以是任何合适的材料。合适的阻燃剂的示例包括金属氢氧化物，例如，三水合氧化铝(ATH)和氢氧化镁(MgOH)以及有机磷酸酯类。阻燃剂可以包括最多至粘合剂的约50重量％，优选地最多至30重量％。添加太多的阻燃剂将降低粘合剂的粘合性能。
粘合剂在具有相对厚的非织造纸层的实施例中可以是最合适的。在这些类型的较厚产品构造中，需要加热较长时间(较慢的线速度)以转换为层。因此，在一些情况下，有利的是施加粘合剂以将某些层粘结在一起，使得可以利用较快的线速度。
非织造织物的配方也可设计为粘结到非织造纸或有利于与非织造纸的整合，使得不需要施加粘合剂。例如，在非织造织物层中存在粘结纤维、粘结剂或纺粘(热塑性)纤维可使在施加热和/或压力时将非织造纸和织物层粘结到一起。
一个或多个非织造纸层和非织造织物层可在连续工艺中(在线整合)或在分离步骤中(离线整合)形成和组合或整合。
如前所述，本发明的制品适于在变压器、电动机、发电机以及需要电子部件绝缘的其他装置中为电子部件提供绝缘。本发明的至少一些实施例适用于在具有阻燃性需求的变压器中使用，诸如在采矿、装运和铁轨行业中使用的变压器。不同产品应用的需求可通过本发明非织造纸和非织造织物的不同组合加以解决。例如，可以调整非织造纸和非织造织物的重量比。对于本发明的至少一些制品，非织造织物层包括约3重量％至约50重量％，并且非织造织纸层包括约50重量％至约97重量％。优选的结构将根据层的厚度和其他因素而改变。
绝缘制品的每层均可有助于最终构造的独特性质。例如，在一些实施例中，非织造纸可提供阻燃性、长期耐热性和所需的电特性。非织造织物可提供优异的耐撕裂性，同时还增强热老化后的拉伸强度和总体柔韧性。这两种类型的层的组合提供具有阻燃性、物理强度和所需电特性的制品，同时在约464°F(240℃)下高温热老化后保持优异的柔韧性
在本发明的至少一些实施例中，绝缘制品在根据ASTM D149-09测量时具有大于100伏特/密耳(3.9千伏/毫米)、优选地大于或等于150伏特/密耳(5.9千伏/毫米)的电介质击穿强度。
在本发明的至少一些实施例中，绝缘制品在根据ASTM E1530-11测量时具有0.18W/m·K或更大的热导率。
示例
以下示例和比较例有助于理解本发明，且这些示例和比较例不应被理解为对本发明范围的限制。除非另外指明，否则所有的份数和百分比均按重量计。使用下述测试方法和方案来评价以下示例性示例和比较例。
材料列表
测试方法
比较例CE1和CE2
比较例CE1和CE2只使用非织造纸层制成，即，不使用非织造织物层。CE1和CE2使用市售非织造纸，其来源见以上“材料列表”。在表1中提供了结构、工艺条件和测试结果。CE2的“5-5-5”的复合结构指出三层火焰屏障物FRB-NC未经压延的非织造纸，其中每层在压延后为5密耳厚，被叠堆在一起并且在所指出的条件下压延以形成CE2。
表1：
非织造织物层：
六种不同非织造织物共混物用于制备示例1-27和比较例CE3-CE7。非织造织物共混物NW1-NW6由表2中提供的量的对位芳族聚酰胺纤维、聚酯(PET)短纤维、未拉伸的PET纤维、双组分聚酯粘结纤维、聚苯硫醚(PPS)粘结纤维、和/或双组分PET/PPS纤维组成。纤维混合物通过梳理机，以产生基重在22-24gsy(克每平方码)之间的非织造絮。非织造絮然后通过钢棉辊隙被压延，其中钢辊加热至温度在230-240°F(110-116℃)之间，并且辊隙压力在590磅/英寸(106kg/cm)-800磅/英寸(143kg/cm)之间。
表2：
用于厚复合纸的层合的粘合剂：
为制备如稍后所描述的示例27中使用的粘合剂，将CR-9-101催化剂添加到ROBOND L-330粘合剂分散体中并且在室温下混合15分钟。将TI-Rite#HA水分散体添加到混合物中并且混合直到很好地分散。下面提供粘合剂制剂的最终组合物。
产品名称 制剂的固体重量％
ROBOND L-330 63.9％
CR-9-101 5.7％
TI-Rite#HA 30.4％
复合绝缘纸
为创建比较例CE3-CE7和示例1-27的复合绝缘纸，非织造织物层和非织造纸层通过热压延机叠堆的热和压力借助机械和热粘结而被布置并融合到一起。表3-7中提供比较例CE3-CE7和示例1-27的非织造织物共混物、非织造纸厚度和复合构造。所有示例使用火焰屏障物FRB-NC未经压延的非织造纸。表2-7中列出的非织造纸厚度的值是指火焰屏障物FRB-NC的每层在压延后均可具有的厚度。下面的表提供非织造纸在压延前和压延后的等同厚度。
在表3-7中以标题“复合结构”的“NW”是指非织造织物层，并且数字是指非织造纸的厚度。例如，“7-NW-7”的复合结构指出一个非织造织物层被放置在两个非织造纸层之间，其中每一个在压延后均为7密耳厚。对于示例1-26，未对任何层的表面施加粘合剂。在375-385°F(191-196℃)之间的温度和1000磅/英寸(179kg/cm)的辊隙压力下，在钢辊之间进行最终复合压延。示例CE3-CE4、1-6和23-27两次通过钢-钢辊隙。
示例1、4、5和6由交替的层中的三个非织造纸层和两个非织造织物层构成，并具有非织造纸-非织造织物-非织造纸-非织造织物-非织造纸的结构。示例2、7、8和12-26由放置在两个非织造纸层之间的两个非织造织物层构成。示例3、9、10和11由放置在两个非织造纸层之间的一个非织造织物层构成。通过将两个非织造织物层放置在两个非织造纸层之间、压延以创建复合纸、将先前描述的阻燃剂粘合剂施加在该复合纸的两层之间、以及压延整个叠堆以创建厚复合纸来制备示例27。通过使用放置在两个非织造织物层之间的1个、2个或3个非织造纸层来形成比较例CE3-CE7。
示例1-26和比较例CE3-CE7的标准特性和UL 94垂直燃烧测试结果在表3-7中示出。示例1-6和23-26以及比较例CE3和CE4具有约15密耳(0.38mm)的最终复合厚度。示例7、8、11、12和15-18为约7密耳(0.18mm)厚。示例9、10、13和14以及比较例CE5-CE7为约5密耳(0.13mm)厚。示例19-22具有约10密耳(0.25mm)的最终复合厚度。示例27为24.6密耳(0.62mm)厚。
虽然标准火焰屏障物FRB-NT非织造纸自身具有优异的难燃性特性，如表1中示例CE1和CE2中所见，但将其与非织造织物层结合改善了机械(拉伸和撕裂)强度和保留的热老化柔韧性。
表5：
＊不可分类的
表6：
＊不可分类的
表7：
＊不可分类的
虽然本文出于说明优选实施例的目的对具体实施例进行了举例说明和描述，但是本领域的普通技术人员应当理解，在不脱离本发明范围的前提下，各种可选的和/或等同形式的具体实施可以取代图示和描述的具体实施例。本专利申请旨在涵盖本文所讨论的优选实施例的任何修改形式或变型形式。因此，显而易见，本发明旨在只由本发明的权利要求书及其等同物限制。

Claims (20)

1.一种制品，包括：
非纤维素的非织造织物层，其具有相背的第一主表面和第二主表面并具有附接到所述非织造织物层的每个主表面的非纤维素的非织造纸层，其中所述非织造纸和非织造织物之一或二者电绝缘。
2.根据权利要求1所述的制品，其中所述非织造纸层中的至少一层直接融合到所述非织造织物层。
3.根据权利要求1所述的制品，其中所述非织造纸层中的至少一层通过粘合剂附接到所述非织造织物层。
4.根据权利要求3所述的制品，其中所述粘合剂包括阻燃剂。
5.根据权利要求4所述的制品，其中所述粘合剂包括最多至30重量％的阻燃剂。
6.根据权利要求4所述的制品，其中所述粘合剂包括最多至50重量％的阻燃剂。
7.根据权利要求1所述的制品，包括非织造纸与非织造织物的多个交替的层，其中两个外部层均为非织造纸。
8.根据权利要求7所述的制品，包括五个交替的层。
9.根据权利要求1或权利要求7所述的制品，其中所述非织造纸层中的至少一层包括多于一个非织造纸片材。
10.根据权利要求9所述的制品，其中所述包括片材的所述非织造纸层中的至少一层具有不同的特性。
11.根据权利要求10所述的制品，其中所述不同的特性选自厚度、组成、密度、柔韧性、抗撕强度、拉伸强度、电介质强度和阻燃性。
12.根据权利要求1所述的制品，其中所述非织造织物层包括多于一个的非织造织物片材。
13.根据权利要求7所述的制品，其中至少一个非织造织物层包括多于一个非织造织物片材。
14.根据权利要求12所述的制品，其中所述包括片材的所述非织造织物层中的至少一层具有不同的特性。
15.根据权利要求14所述的制品，其中所述不同的特性选自厚度、组成、密度、柔韧性、抗撕强度、拉伸强度、电介质强度和阻燃性。
16.根据权利要求1所述的制品，具有根据ASTM D149-09大于或等于150伏特/密耳的复合部分介电击穿强度。
17.根据权利要求1所述的制品，其中所述制品达到V-0的UL 94阻燃性测试等级。
18.根据权利要求12所述的制品，其中所述非织造织物层包括易燃材料。
19.根据权利要求1所述的制品，其中所述非织造织物包括芳族聚酰胺纤维。
20.根据权利要求1所述的制品，其中所述非织造织物层的重量％为约3至约50，并且所述一个或多个非织造纸层的重量％为约50至约97。
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US20130337246A1 (en) 2013-12-19
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