CN101633244A - 发泡聚四氟乙烯膜及其制造方法 - Google Patents

发泡聚四氟乙烯膜及其制造方法 Download PDF

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CN101633244A
CN101633244A CN200910140159A CN200910140159A CN101633244A CN 101633244 A CN101633244 A CN 101633244A CN 200910140159 A CN200910140159 A CN 200910140159A CN 200910140159 A CN200910140159 A CN 200910140159A CN 101633244 A CN101633244 A CN 101633244A
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G·索特普拉苏
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Parker Hannifin Corp
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Abstract

本发明涉及发泡聚四氟乙烯膜及其制造方法。提供了多孔发泡PTFE制品。多孔发泡PTFE制品包括发泡PTFE树脂，该PTFE树脂包括第一细微粉末PTFE树脂和第二细微粉末PTFE树脂，第一PTFE树脂具有比由第二PTFE树脂形成的原纤(24)更多和更长原纤的特性，第二PTFE树脂具有比由第一PTFE树脂形成的节点更厚节点(22)的特性，发泡PTFE制品包括许多节点和原纤并具有至少约100μm的厚度。

Description

发泡聚四氟乙烯膜及其制造方法
技术领域
[0001]本发明领域一般性涉及多孔膜，更具体地涉及发泡聚四氟乙烯(ePTFE)膜。
背景技术
[0002]多孔ePTFE制品/膜可以用于形成许多有用的制品，例如过滤器、织物、衬垫和电绝缘。可以通过使聚四氟乙烯(PTFE)树脂与润滑剂共混，将共混的树脂压制成锭料，将锭料挤出成为挤出物，压延该挤出物(如果需要)，在至少一个方向拉伸或膨胀该挤出物，和任选烧结膨胀的挤出物形成最终制品来制造这些ePTFE制品。ePTFE制品可以制造成任何挤出的形状，包括片材、管、棒或长丝。
[0003]已知的ePTFE制品的多孔结构特征在于由许多原纤连接在一起的许多节点。节点基本上是PTFE材料的未加工分散体颗粒。结构内的节点和原纤的形状、大小和方向可以通过改变膨胀速率、膨胀率、膨胀轴数和其它工艺参数产生许多不同的结构来加以控制。
[0004]已知的ePTFE膜的厚度通常为约25微米(μm)或更少。在一些应用中，为了增加过滤效率，理想的是使用更厚的膜。通常，通过热的粘合剂层压将多个ePTFE薄膜叠层来获得增加的厚度。理想的将是不使用将若干层ePTFE薄膜层压在一起的附加步骤来制造增加厚度的ePTFE膜。
发明内容
[0005]在一个方面，提供一种制造多孔膜的方法。该方法包括将第一PTFE树脂和第二PTFE树脂混合在一起形成PTFE树脂混合物。第一PTFE树脂具有形成比由第二PTFE树脂形成的原纤更多和更长的原纤的特性。第二PTFE树脂具有形成比由第一PTFE树脂形成的节点更厚的节点的特性。该方法还包括由PTFE树脂混合物形成预成形体，将预成形体挤出成为带，使带经过许多相对的压延辊形成厚度为约380μm至约1200μm的压延带，和在横向拉伸该压延带形成具有许多节点和原纤并且厚度为至少约100μm的多孔膜。
[0006]在另一方面，提供一种多孔发泡PTFE制品。多孔发泡PTFE制品包括发泡PTFE树脂。PTFE树脂包括第一PTFE树脂和第二PTFE树脂。第一PTFE树脂具有形成比由第二PTFE树脂形成的原纤更多和更长的原纤的特性。第二PTFE树脂具有形成比由第一PTFE树脂形成的节点更厚的节点的特性，并且发泡PTFE制品包括许多节点和原纤和具有至少约100μm的厚度。
[0007]在另一方面，提供一种微过滤膜。微过滤膜以发泡PTFE膜形式形成。PTFE膜包括第一PTFE树脂和第二PTFE树脂。第一PTFE树脂具有形成比由第二PTFE树脂形成的原纤更多和更长的原纤的特性。第二PTFE树脂具有形成比由第一PTFE树脂形成的节点更厚的节点的特性。发泡PTFE膜具有许多节点和原纤并且具有至少约100μm的厚度。
附图说明
[0008]图1为根据本发明一个实施方案的一部分膜的一部分显微照片。
[0009]图2为图1所示的一部分膜的放大示意图。
[0010]图3为挤出和压延PTFE带的示例性设备的示意图。
[0011]图4为拉伸压延的PTFE带的示例性设备的示意图。
具体实施方式
[0012]以下详细地描述厚度为至少约100μm的单层发泡聚四氟乙烯(ePTFE)膜和制造该ePTFE膜的方法。在一个实施方案中，ePTFE膜具有约100μm至约380μm的厚度。较厚的ePTFE膜可以用于微过滤、液体过滤和微通风应用。同样，该膜可以用于重载服装，例如工作外衣和夹克。ePTFE膜增加的厚度提供相比已知膜增加的膜耐久性和过滤耐久性，以及改善的俘获效率。与厚度为25μm的已知ePTFE膜相比，较厚的ePTFE膜具有增加的剥离强度和无负载的流体静力学Mullen强度，同时保持与厚度为25μm的已知ePTFE膜相同的透气性。
[0013]图1为多孔ePTFE膜12的示例性实施方案的显微照片，图2为多孔ePTFE膜12的示意图。在一个方面，ePTFE膜12是多孔的，在另一方面，ePTFE膜12是微孔性的，许多节点22的三维矩阵或点阵类型结构由许多原纤24互连。在一个实施方案中，ePTFE膜12至少部分烧结。通常，已经至少部分烧结的原纤24的尺寸在垂直于原纤24经向范围的方向中的直径为约0.05μm至约0.5μm。“发泡”用来表示充分拉伸超过材料的弹性极限，向原纤24引入永久形变或伸长。在一个示例性实施方案中，膜12被加热或“烧结”，使ePTFE材料中的残余应力减少和减到最小。但是，在替代实施方案中，作为适合于膜12的预期用途的膜，膜12是未烧结的或部分烧结的。
[0014]节点22和原纤24的表面限定许多连通孔26，所述连通孔以曲径的形式在膜12的相对主要侧面之间完全贯穿膜12。在一个实施方案中，基础膜16中孔26的平均尺寸S足以被认为是微孔性的，但是可以使用任何孔径。在一个示例性实施方案中，基础膜16中孔26的适当的平均尺寸S为约0.01μm至约10μm，在另一个实施方案中为约0.1μm至约5.0μm。
[0015]通过使第一PTFE细微粉末树脂、第二PTFE细微粉末树脂和烃润滑剂混合在一起形成PTFE细微粉末树脂的混合物，制造膜12。混合时间可以为约30分钟至约一小时。在另一个实施方案中，混合时间可以大于一小时。加工过程中第一PTFE树脂具有比第二PTFE树脂更高的原纤化程度。更高的原纤化程度表示相比由具有低原纤化程度的第二PTFE树脂形成的原纤，第一PTFE树脂具有形成更多和更长原纤的特性。更长原纤促进膜12的高透气性。更多原纤倾向于提高在原纤延伸的总体方向获得的膜强度。同样，第二PTFE树脂具有形成比由第一PTFE树脂形成的节点更厚的节点的特性。更厚的节点影响膜12的厚度。使第一PTFE树脂和第二PTFE树脂混合在一起包括使约60wt％至约68wt％的第一PTFE树脂，约15wt％至约17wt％的第二PTFE树脂和约15wt％至约25wt％的烃润滑助剂混合在一起，wt％基于PTFE树脂混合物的总重量。在另一个实施方案中，将第一PTFE树脂和第二PTFE树脂混合在一起包括将约66wt％至约68wt％的第一PTFE树脂，约16wt％至约17wt％的第二PTFE树脂，和约15wt％至约17wt％的烃润滑助剂混合在一起，wt％基于PTFE树脂混合物的总重量。PTFE树脂混合物包括第一PTFE树脂和第二PTFE，比率为约4份第一PTFE树脂对约1份第二PTFE树脂。
[0016]购自Daikin America，Inc.，Orangeburg，New York，商标为DAIKIN-POLYFLON，和购自E.I.du Pont de Nemours and company，Wilmington，Delaware，商标为TEFLON PTFE树脂的PTFE树脂适合用作第一和第二PTFE树脂。用作第一PTFE树脂的DAIKIN-POLYFLON树脂的合适实例包括但不限于F-107和F-131 DAIKIN-POLYFLON树脂，用作第二PTFE树脂的DAIKIN-POLYFLON树脂的合适例如包括但不限于F-201和F-205 DAIKIN-POLYFLON树脂。用作第一PTFE树脂的TEFLON PTFE树脂的合适实例包括但不限于601A TEFLON PTFE树脂，用作第二PTFE树脂的TEFLON PTFE树脂的合适实例包括但不限于603A TEFLON PTFE树脂。润滑剂可以为任何合适的烃溶剂，例如矿油精，购自Exxon Mobil Chemical，商标为ISOPAR。ISOPAR烃溶剂的合适实例包括但不限于ISOPAR M和ISOPAR K烃溶剂。
[0017]同样参考图3，PTFE树脂混合物在压力下成形为预成形体。预成形体可以为任何合适的形状，例如圆柱形。预成形体然后用挤出机40糊状挤出成为带42并形成大部分原纤结构。带42以约10至约25英尺/分的速率穿过一系列相对的热压延辊44，形成厚度为约380μm至约1200μm的压延带46。压延辊44的温度维持在约400°F至约550°F，以驱除混合物步骤中使用的润滑助剂。
[0018]同样参考图4，在横向(XD)拉幅或拉伸或膨胀工艺拉伸压延带46，以形成具有许多节点22和原纤24并且厚度为至少约100μm的多孔膜12。在示例性实施方案中，不在纵向(MD)，仅在横向拉伸压延带。在示例性实施方案中，压延带在横向拉伸3至15倍。在其它实施方案中，压延带在纵向拉伸0至12倍。在一个实施方案中，膜12被成形为具有约100μm至约380μm的厚度。拉伸工艺包括使压延带46以约10至约60英尺/分的线速率通过许多加热的拉伸辊50以拉伸压延带46，然后卷绕在卷取辊52上。压延带46通过拉伸工艺在横向将压延带46拉伸3至15倍，在纵向将压延带56拉伸0至12倍，以获得所需的膜12的厚度和渗透度。拉伸辊50的最高温度为约500°F至约680°F。
[0019]所得ePTFE膜具有约100μm至约380μm的厚度，同时保持与厚度为约25μm的已知ePTFE膜相同的透气和透水性。在另一个实施方案中，ePTFE膜具有约100μm至约255μm的厚度。以下表格比较多孔膜12(试样A)的示例性实施方案与厚度为约25μm(试样B)的已知膜的性能。
  性能   试样A   试样B
  单位重量(oz/yd2)   1.58   0.54
  厚度(μm)   127   ～25
  泡点(psi)   15-18   15-22
  空气流量(cfm)   0.26   0.20
  27英寸Hg真空下的水流量-mL/min/cm2   17   18
  Mullen(未负载)(psi)   35   18
  Mullen(负载)(psi)   80   60
  剥离强度(lbf/in)MDXD 1.040.52 0.340.2
  拉伸伸长率(％)MDXD 32941 350104
MD＝纵向
XD＝垂直于纵向
[0020]试样A为试样B厚度的约5倍，并具有与试样B大致相同的气流和水流性能。另外，在纵向和横向，试样A是试样B流体静力学Mullen强度的约两倍和剥离强度的至少两倍。
[0021]Mullen流体静力学测试用来测量膜试样的物理强度、防水性(流体静力学抗性)和疏水性。圆形试样的下表面暴露于预定的流体静压，并在视觉上检查上表面的水渗透性。以上报告了以磅/平方英寸(psi)计的试样A和B的最高流体静压，在其下没有渗透性。
[0022]剥离强度测试用来测试层压至织物材料的膜试样的粘结强度。拉伸测试设备用来从织物剥离膜试样。从织物剥离膜试样所需的以每英寸磅力(lbf/in)计的测量力为剥离强度。
[0023]所记载的说明书使用实施例来公开本发明，包括最佳方式，并且还能够使本领域任何技术人员实施本发明，包括制造和使用任何设备或系统并进行任何合并方法。本发明的可专利性范围由权利要求确定，并且可以包括本领域技术人员想到的其它实施例。如果它们具有不同于权利要求的字面措辞的结构单元，或如果它们包括与权利要求的字面措辞没有实质性差别的等效结构单元，那么这种其它实施例预期是在权利要求的范围内。
部件列表
  12   膜
  16   基础膜
  22   许多节点
  24   原纤
  26   孔
  40   挤出机
  42   带
  44   热压延辊
  46   压延带
  50   拉伸辊
  52   卷取辊
  56   压延带

Claims (10)

1.一种多孔发泡PTFE制品，包括：
发泡PTFE树脂，该PTFE树脂包括第一细微粉末PTFE树脂和第二细微粉末PTFE树脂，该第一PTFE树脂具有形成比由第二PTFE树脂形成的原纤更多和更长原纤(24)的特性，第二PTFE树脂具有形成比由第一PTFE树脂形成的节点更厚节点(22)的特性，所述发泡PTFE制品包括许多节点和原纤并具有至少约100μm的厚度。
2.根据权利要求1的多孔发泡PTFE制品，其中所述发泡PTFE制品包括约100μm至约380μm的厚度。
3.根据权利要求1的多孔发泡PTFE制品，其中所述发泡PTFE制品包括至少约1.0盎司每平方码的单位重量。
4.根据权利要求1的多孔发泡PTFE制品，其中所述发泡PTFE制品包括至少约1.0磅力每英寸的纵向剥离强度。
5.根据权利要求1的多孔发泡PTFE制品，其中所述发泡PTFE制品在横向被拉伸约3至约15倍和在纵向被拉伸0至约12倍。
6.一种微过滤膜，包括：
发泡PTFE膜(12)，该PTFE膜包括第一细微粉末PTFE树脂和第二细微粉末PTFE树脂，第一PTFE树脂具有形成比由第二PTFE树脂形成的原纤更多和更长原纤(24)的特性，第二PTFE树脂具有比由第一PTFE树脂形成的节点更厚节点(22)的特性，所述发泡PTFE膜包括许多节点和原纤并具有至少约100μm的厚度。
7.根据权利要求6的微过滤膜，其中所述发泡PTFE膜(12)包括约100μm至约380μm的厚度。
8.根据权利要求6的微过滤膜，其中所述发泡PTFE膜(12)包括至少约1.0盎司每平方码的单位重量。
9.根据权利要求6的微过滤膜，其中所述发泡PTFE膜(12)包括至少约1.0磅力每英寸的纵向剥离强度。
10.根据权利要求6的微过滤膜，其中所述发泡PTFE膜(12)在横向被拉伸约3至约15倍和在纵向被拉伸0至约12倍。
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