CN101065424B - Ptfe薄膜 - Google Patents
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- 229920001343 polytetrafluoroethylene Polymers 0.000 title claims abstract description 93
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Abstract
本发明涉及一种通过对PTFE薄膜施加高压来提高PTFE薄膜的尺寸稳定性的方法。所述方法减小和/或消除了使用现有方法制造PTFE薄膜通常伴随的松弛应力。
Description
该申请是2005年11月23日提交的PCT国际专利申请,除美国外所有指定国的申请人均为唐纳森公司(一家美国国营公司),对于美国指定国的申请人为Kirit Patel(美国公民),该申请要求2004年11月24日提交的美国临时专利申请系列号60/631,087的优先权,该美国临时申请全文纳入本文作为参考。
发明领域
本发明涉及透气性改进的薄膜,具体地涉及具有改进的热稳定性的聚四氟乙烯(PTFE)薄膜。
背景
PTFE薄膜,尤其是膨胀的PTFE薄膜,广泛用于制造透气性的防水织物。然而,很多PTFE薄膜由于与制造工艺相关的应力而造成尺寸不稳定,包括美国专利3,315,020(后面称为“’020专利”)中所描述的那些。’020专利描述了在拉力下单向或双轴向拉伸PTFE薄膜,尤其是在高温下,例如消防衣和很多工业过滤应用所经历的高温,得到尺寸很不稳定的薄膜。
当PTFE薄膜应用在包含不同材料的复合结构中时,现有的拉伸的PTFE薄膜的尺寸不稳定性会产生很大的问题。这些不同的材料各自显示出尺寸变化,尺寸变化的程度以比在相同条件下的大部分常规的PTFE薄膜小的多。在这些情况中,在较高的环境温度条件下,含有PTFE薄膜作为复合结构一部分的产品由于膨胀率和收缩率不同而产生不同层的层间剪切力。在上述条件下所得到的结果通常是差和/或不合格的产品。此外,不同层的分层会过早地导致产品破坏。
因此,需求尺寸稳定性改进的PTFE薄膜。
发明总结
本发明涉及改进PTFE薄膜的尺寸稳定性的方法,以及使用本发明的方法制造的尺寸稳定的PTFE薄膜。本文所述的方法减小和/或消除了使用现有方法制造PTFE薄膜所伴随的松弛应力。
部分地,本发明涉及改进PTFE薄膜的尺寸稳定性的方法。在某些实施方式中,本发明包括:使PTFE薄膜经受高温,达到一段给定的暴露时间,同时,使PTFE薄膜经受高压,达到一段给定的暴露时间。其中温度、压力和暴露时间的组合至少部分地对尺寸稳定性有影响。
具体地,本发明部分地涉及一种影响PTFE薄膜的尺寸稳定性,该方法使PTFE薄膜经受高温,持续一段给定的暴露时间;并同时使PTFE薄膜经受高压,持续一段给定的暴露时间。在该过程中,所述PTFE薄膜同时经受到高温和高压,并且温度、压力和暴露时间的组合至少部分地对尺寸稳定性有影响。
在本发明的一些实施方案中,所述薄膜升温到约325℃或更高,在其他实施方案中,薄膜的温度升高到340℃或更高。典型地,将温度升高到约325℃以上且低于约400℃,通常是约350℃以上到约360℃以下的温度,有时是360℃以上到约380℃以下的温度。
可使用诸如温度超过约335℃或超过350℃的辊子之类的装置,将薄膜加热到高温,当然也可以使用其他加热方法。典型地,辊子或其他装置的温度比处理过程中所需的PTFE薄膜的峰温度高至少10℃,更通常至少高约20℃。因此,在一些实施方案中,使用温度超过约360℃的辊子将薄膜加热到高温。
如上所述,所述PTFE薄膜应该在高压下被压缩的同时被加热。在本发明的大部分实施方案中,将所述薄膜加热到约325℃或更高的温度,同时在约1磅/平方英寸的压力下被压缩。在一些实施方案中,将所述薄膜加热到至少约325℃的高温,同时在至少5磅/平方英寸的压力下被压缩。在其他实施方案中,将所述薄膜加热到至少约325℃的高温,同时在至少20磅/平方英寸的压力下被压缩。
将薄膜升至高温的时间期间因实施方案而异,但通常小于1秒,例如为0.1到1.0秒。在一些实施方案中,高温的时间期间为0.05到0.5秒。将薄膜经受高压的时间期间因实施方案而异,但通常小于1秒,例如为0.1到1.0秒。在一些实施方案中,高温的时间期间为0.05到0.5秒。高温的时间期间不需要与高压的时间期间一样。
按照本发明制造的PTFE薄膜与单向或双轴向膨胀的未处理的PTFE层压物相比,尺寸稳定性得以提高。在一些实施方案中,纵向的收缩率小于10%,纵向的收缩率通常小于5%。得到的PTFE薄膜通常具有良好的透气性、空隙度和与制造透气性织物相关的其他特性。例如,在某些实施方案中,所述PTFE薄膜在0.7巴时的透气性至少为4升/分钟/平方厘米。
本发明的上述概述并不是描述本发明讨论的各个实施方案。下面的附图和详细描述用来描述本发明讨论的各个实施方案。
附图简述
结合下面的本发明的各种实施方案的详细描述和附图,可更完整地了解本发明。
图1示出了用于形成本发明的稳定的PTFE薄膜的设备的示意图。
图2是出了按照本发明制造的PTFE薄膜的电子显微照片。
详细描述
本发明涉及改进PTFE薄膜的尺寸稳定性的方法,以及使用本发明的方法制造的尺寸稳定的PTFE薄膜。本文所述的方法减小和/或消除了与使用以前已有的方法制造的PTFE薄膜相关的松弛应力。
具体地,本发明部分地涉及通过使PTFE薄膜经受高温高压来影响PTFE薄膜的尺寸稳定性的方法。可以按照例如美国专利3,953,566;4,187390和4,194,041(纳入本文作为参考)的揭示,来制造按照本发明的方法进行热处理的薄膜。在本发明的方法中,所述PTFE薄膜同时受到高温和高压,并且温度、压力和暴露时间的组合至少部分地对尺寸稳定性有影响。
在PTFE聚合时,它以伸长链晶体的形式排列,通常的结晶度约95%,熔点为约344℃。熔融以后,以有序度降低的形式重结晶,再不能恢复到原来的高结晶度。熔点下降到约332℃,熔融热减小约2/3。正是在第一次熔融后这一不可逆转变的再生性,使得热稳定化的薄膜具有尺寸稳定性。
如上所述,已经发现通过使PTFE单向和/或双轴向原纤化薄膜处于高于晶体熔点的温度,通常在大气压下为约327℃(624°F),内部形成的应力(built-in stress)明显减小,PTFE薄膜的尺寸稳定性改善。在一些实施方案中,取决于条件,高于325℃的高温是适合的,在其它实施方案中,使用高于327℃的温度,在其它实施方案中,温度升高到340℃以上。典型地,将温度升高到至少约320℃且低于约450℃,通常升高到至少约330℃,有时升温至至少约360℃。所述PTFE薄膜在加热的同时应该被压缩。在本发明的大部分实施方案中,将所述薄膜加热到大于约327℃的高温,同时在至少约1磅/平方英寸的压力下压缩。在某些实施方案中,将所述薄膜加热到大于约327℃的高温,同时在至少约5磅/平方英寸的压力下压缩。在某些实施方案中,将所述薄膜加热到大于约327℃的高温,同时在至少约20磅/平方英寸的压力下压缩。
将薄膜升至高温的时间期间因实施方案而异,但通常小于约1秒,例如为0.1到1.0秒。在一些实施方案中,高温的时间期间为0.05到0.5秒。在某些实施方案中,所述时间期间小于0.5秒,小于0.1秒,或甚至小于0.01秒。
可使用温度超过340℃的辊子将薄膜加热到高温,当然也可以使用其他加热方法。典型地,辊子的温度比加工过程中所需的PTFE薄膜的峰温度至少高10℃,更通常至少高约20℃。
暴露于热和压力后,得到的PTFE薄膜通常具有良好的透气性、孔隙度和与制造透气性织物(例如透气性的多层织物)相关的其他特性。例如,在某些实施方案中,所述被处理的PTFE薄膜在0.7巴时的透气性至少为4升/分钟/平方厘米。此外,在一些实施方案中,所述PTFE薄膜的库尔特气孔度(Coulter Porometer)至少为0.10MFP,更有利的是至少0.20MFP,最有利的是至少为0.25MFP.
所得到的PTFE薄膜具有很多适合的用途,包括在层压物中例如用于布料。外套和消防衣是利用了由尺寸稳定的PTFE制造的层压物的衣服的例子。所得到的PTFE还适合过滤,例如空气或气体过滤、液体过滤和化学滤饼过滤。
按照本发明的方法处理的PTFE薄膜与单向或双轴向膨胀的未处理的PTFE层压物相比,尺寸稳定性提高。在一些实施方案中,纵向的收缩率小于10%,纵向的收缩率通常小于5%。
与将PTFE薄膜加热到高温相关的一个问题是可能发生薄膜收缩,导致尺寸减小。以下所述的方法可以使尺寸不稳定性最小化,同时增加韧性。调节温度、压力和加热持续的时间,来得到所需的尺寸稳定化的PTFE薄膜。在本发明的某些实施方案中,所述方法包括使用传动热钢辊(driven heated steel roll)、橡胶展平辊(rubber nip roll)和与橡胶展平辊匹配的从动辊(idle roll)。
以下的加工范围确立了在该一般实施方案中处理加工中的每个变量的优选设定。首先,对于温度,推荐的加热温度通常大于约340℃,且通常小于400℃。然而,有用的范围延伸到该值之外。在大部分实施方案中,所述温度范围为约350℃到390℃,通常为约360℃到380℃。如上所述,需要将PTFE薄膜的温度升高至PTFE的晶体熔点或晶体熔点之上,所述PTFE的晶体熔点为约327℃,这可以通过使用327℃或更高温度的热辊来实现。PTFE薄膜与热辊的接触时,接触时间越长,所需要的热辊温度越低(一般而言)。
将所述薄膜保持在高温下的持续时间通常很短暂,典型地为十分之一秒、或甚至小于千分之一秒,取决于被加热的钢辊的温度。对于一些实施方案,010到1.0秒的持续时间是合适的,而对于大部分的实施方案,0.05-0.50秒的持续时间是合适的,尽管在一些情形下更长或更短的持续时间也是满足需要的。
PTFE薄膜所要经受的压力保持在通常至少为1磅/平方英寸(PSI),更典型地为大于5PSI,最典型地为大于20PSI。将所述薄膜保持在高压下的持续时间通常与保持在高温下的持续时间相同。
按照一般的方法,将制备好的卷状的PTFE薄膜的延伸的一段夹在两个表面之间,其中至少一个表面被加热到高温。通常,如通常所知的一样,所述PTFE薄膜被夹在两个圆筒或辊之间。可以加热一个辊或两个辊。
参看图1,示出了一段PTFE膜绕在芯15上。加工装置包括从动辊20、辊30与40之间形成的间隙、和第二从动辊50。图1还示出了一段尺寸稳定化的PTFE膜绕在芯65上。
在第一实施例中,将双轴向拉伸的PTFE薄膜(例如芯15上的PTFE10)的延伸的一段放置在展平辊(例如辊30)的一侧上,其余的放在从动辊(例如20)和展平辊(例如30)上。所述PTFE薄膜10绕着展平辊30逆行,至正好与薄膜卷10/15所放置的位置相反的位置。接收辊,例如芯65,位于那侧的展平辊30和从动辊(例如第二从动辊50)之间。一旦薄膜10绕着展平辊30已经成形,就降低展平辊30,直至它与第二辊(例如辊40)接触,所述第二辊可以是旋转的热钢辊。一旦接触,展平辊30带着薄膜10在被加热的钢辊40上,使薄膜10受到加热,并限制其移动,同时受挤压。当在展平辊30和钢辊40之间被挤压时,薄膜10经历高于结晶温度的温度,形成定型的或稳定化的PTFE。
以下的实施例示出了标准膨胀的PTFE薄膜(购自唐纳森公司,名称为Tetratex TX2203)、与按照本发明被加热处理后的同样的薄膜的测试结果比较。
使用图1所示的设备结构,将标准的膨胀的PTFE薄膜加热到327℃以上,同时在至少20磅/平方英寸的压力下受压。
表1
薄膜 | 标准 | 热处理 | |
透气性 | Textest(cfm) | 0.7 | 0.4 |
库尔特(升/分钟/平方厘米@0.7巴) | 7.0 | 4.0 | |
孔分布 | 最小 | 0.32 | 0.26 |
最大 | 0.44 | 0.33 | |
库尔特气孔度 | MFP | 0.37 | 0.29 |
收缩率% | 纵向 | 30.0 | 3.0 |
横向 | 22.7 | 3.5 |
如上面的表1所示,按照本发明处理后的经受热和压力处理过的薄膜,具有非常小的纵向和横向收缩率。此外,尽管透气性有一些减小,但是热和压力处理过的薄膜在透气性和孔分布性方面仍然具有较高的值。
图2示出了按照本发明制造的PTFE薄膜的两张扫描电子显微照片,两张显微照片在不同的照明条件下拍摄。
下面的表2示出了用与上面相同的方式处理的经受热和压力处理过的薄膜的其它实施例。
应理解本发明不限于上述的具体实施例,而是应当明白:权利要求书所述的范围覆盖了本发明的所有方面。本发明所涉及领域的技术人员在阅读本发明的说明书后,可以对本发明进行各种修改、使用等价的方法以及本发明可以应用的很多结构。
Claims (15)
1.一种提高PTFE薄膜的尺寸稳定性的方法,所述方法包括:
a)使PTFE薄膜经受大于327℃且小于450℃的高温,达到一段不到1秒的暴露时间,并
b)使PTFE薄膜经受至少5磅/平方英寸的高压不到1秒,
其中所述PTFE薄膜同时经受高温和高压,温度、压力和暴露时间的组合至少部分地对尺寸稳定性有影响,其中在经受高温和高压后,所述PTFE薄膜在0.7巴时的透气性至少为4升/分钟/平方厘米。
2.如权利要求1所述的影响PTFE薄膜的尺寸稳定性的方法,其特征在于,将所述薄膜升温至大于340℃且小于450℃的温度。
3.如权利要求1所述的影响PTFE薄膜的尺寸稳定性的方法,其特征在于,将所述薄膜升温至大于327℃且小于400℃的温度。
4.如权利要求1所述的影响PTFE薄膜的尺寸稳定性的方法,其特征在于,将所述薄膜升温至大于350℃且小于360℃的温度。
5.如权利要求1所述的影响PTFE薄膜的尺寸稳定性的方法,其特征在于,将所述薄膜升温至大于360℃且小于380℃的温度。
6.如权利要求1所述的影响PTFE薄膜的尺寸稳定性的方法,其特征在于,使用温度超过340℃的辊子将所述薄膜加热至高温。
7.如权利要求1所述的影响PTFE薄膜的尺寸稳定性的方法,其特征在于,使用温度超过360℃的辊子将所述薄膜加热至高温。
8.如权利要求1所述的影响PTFE薄膜的尺寸稳定性的方法,其特征在于,将所述薄膜加热至大于327℃且低于450℃的高温,同时在至少20磅/平方英寸的压力下被压缩。
9.如权利要求1所述的影响PTFE薄膜的尺寸稳定性的方法,其特征在于,所述给定的暴露时间为0.1到小于1秒。
10.如权利要求1所述的影响PTFE薄膜的尺寸稳定性的方法,其特征在于,所述给定的暴露时间为0.05-0.5秒。
11.使用权利要求1的方法制造的PTFE薄膜。
12.如权利要求11所述的PTFE薄膜,其特征在于,所述PTFE薄膜在0.7巴时的透气性至少为4升/分钟/平方厘米。
13.如权利要求11所述的PTFE薄膜,其特征在于,所述PTFE薄膜的库尔特气孔度至少为0.25MFP。
14.如权利要求11所述的PTFE薄膜,其特征在于,所述PTFE薄膜的纵向收缩率小于10%。
15.如权利要求11所述的PTFE薄膜,其特征在于,所述PTFE薄膜的纵向收缩率小于5%。
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Families Citing this family (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7922946B2 (en) | 2004-11-24 | 2011-04-12 | Donaldson Company, Inc. | PTFE membrane |
FR2903934B1 (fr) * | 2006-07-21 | 2012-06-15 | Axon Cable Sa | Unite et procede de thermoformage permettant l'obtention de formes complexes |
US8249686B2 (en) * | 2007-09-14 | 2012-08-21 | Corventis, Inc. | Adherent device for sleep disordered breathing |
US8460189B2 (en) | 2007-09-14 | 2013-06-11 | Corventis, Inc. | Adherent cardiac monitor with advanced sensing capabilities |
US8790257B2 (en) | 2007-09-14 | 2014-07-29 | Corventis, Inc. | Multi-sensor patient monitor to detect impending cardiac decompensation |
EP2257216B1 (en) | 2008-03-12 | 2021-04-28 | Medtronic Monitoring, Inc. | Heart failure decompensation prediction based on cardiac rhythm |
US8784710B2 (en) * | 2009-07-16 | 2014-07-22 | Phillips Scientific Inc. | Expandable polymer membrane and tubes, and a method of manufacturing thereof |
US9451897B2 (en) | 2009-12-14 | 2016-09-27 | Medtronic Monitoring, Inc. | Body adherent patch with electronics for physiologic monitoring |
JP5473824B2 (ja) * | 2010-08-05 | 2014-04-16 | ニチアス株式会社 | 高密度ポリテトラフルオロエチレンテープ及びその製造方法 |
US9132616B2 (en) | 2010-08-31 | 2015-09-15 | Bha Altair, Llc | Multi-layer composite membrane materials and methods therefor |
JP2015009221A (ja) * | 2013-07-01 | 2015-01-19 | 住友電工ファインポリマー株式会社 | 多孔質ポリテトラフルオロエチレン膜の製造方法 |
WO2015108564A1 (en) * | 2014-01-15 | 2015-07-23 | Cohesive Systems Llc | Fabrication process for garments and other fabric products |
CN105233707A (zh) * | 2015-09-17 | 2016-01-13 | 重庆润泽医药有限公司 | 一种聚四氟乙烯膜的制备方法 |
KR20190062168A (ko) | 2017-11-28 | 2019-06-05 | 주식회사 엘지화학 | 불소계 수지 다공성 막의 제조방법 |
CN112339388B (zh) | 2020-11-05 | 2021-08-03 | 中国长江三峡集团有限公司 | 一种基于ptfe纳米功能复合膜制备方法及应用 |
CN112500593B (zh) | 2020-11-05 | 2021-07-06 | 中国长江三峡集团有限公司 | 一种对基于ptfe膜进行纳米深度表面活化的方法 |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1475316A (en) * | 1973-03-19 | 1977-06-01 | Sumitomo Electric Industries | Preparation of porous polytetrafluoroethylene sheets |
US4187390A (en) * | 1970-05-21 | 1980-02-05 | W. L. Gore & Associates, Inc. | Porous products and process therefor |
US4194041A (en) * | 1978-06-29 | 1980-03-18 | W. L. Gore & Associates, Inc. | Waterproof laminate |
US5476589A (en) * | 1995-03-10 | 1995-12-19 | W. L. Gore & Associates, Inc. | Porpous PTFE film and a manufacturing method therefor |
US5814405A (en) * | 1995-08-04 | 1998-09-29 | W. L. Gore & Associates, Inc. | Strong, air permeable membranes of polytetrafluoroethylene |
CN1387991A (zh) * | 2001-05-25 | 2003-01-01 | 周钦俊 | 一种铁氟龙第三轴向多向性延伸膜及制备方法 |
US20030194547A1 (en) * | 2002-04-15 | 2003-10-16 | Fuhrmann Louis P. | Membrane composite structure and method of production |
Family Cites Families (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3315020A (en) * | 1962-03-21 | 1967-04-18 | Gore & Ass | Process for preparing biaxially fibrillated sheets |
US3962153A (en) * | 1970-05-21 | 1976-06-08 | W. L. Gore & Associates, Inc. | Very highly stretched polytetrafluoroethylene and process therefor |
US6080472A (en) * | 1979-11-27 | 2000-06-27 | Yeu Ming Tai Chemical Ind. Co., Ltd. | Porous polytetrafluoroethylene molded article |
JP3580687B2 (ja) * | 1996-12-27 | 2004-10-27 | 宇明泰化工股▲ふん▼有限公司 | ポリテトラフルオロエチレン多孔質成形体 |
US4891407A (en) * | 1985-11-13 | 1990-01-02 | Tetratec Corporation | Interpenetrating polymeric networks comprising polytetrafluoroethylene and polysiloxane |
US5066683A (en) * | 1987-01-05 | 1991-11-19 | Tetratec Corporation | Microporous waterproof and moisture vapor permeable structures, processes of manufacture and useful articles thereof |
US5157058A (en) * | 1987-01-05 | 1992-10-20 | Tetratec Corporation | Microporous waterproof and moisture vapor permeable structures, processes of manufacture and useful articles thereof |
US4945125A (en) * | 1987-01-05 | 1990-07-31 | Tetratec Corporation | Process of producing a fibrillated semi-interpenetrating polymer network of polytetrafluoroethylene and silicone elastomer and shaped products thereof |
US5362553A (en) * | 1987-01-05 | 1994-11-08 | Tetratec Corporation | Microporous waterproof and moisture vapor permeable fabric |
JP2792354B2 (ja) * | 1991-07-23 | 1998-09-03 | ダイキン工業株式会社 | ポリテトラフルオロエチレン多孔膜 |
JP3221074B2 (ja) * | 1992-06-23 | 2001-10-22 | 住友電気工業株式会社 | 高結晶化度ポリテトラフルオロエチレン連続成形体の製造方法 |
US5552100A (en) * | 1995-05-02 | 1996-09-03 | Baxter International Inc. | Method for manufacturing porous fluoropolymer films |
DE19544912A1 (de) * | 1995-12-01 | 1997-06-05 | Gore W L & Ass Gmbh | PTFE-Körper aus mikroporösem Polytetrafluorethylen mit Füllstoff und Verfahren zu dessen Herstellung |
US6235377B1 (en) * | 1995-09-05 | 2001-05-22 | Bio Med Sciences, Inc. | Microporous membrane with a stratified pore structure created in situ and process |
US6162514A (en) * | 1995-09-22 | 2000-12-19 | Japan Gore-Tex, Inc. | Molded article of liquid crystal polymer |
JP3273735B2 (ja) * | 1996-05-17 | 2002-04-15 | 日東電工株式会社 | ポリテトラフルオロエチレン多孔質膜およびその製造方法、シート状ポリテトラフルオロエチレン成形体、並びに、エアーフィルター用濾材 |
JPH10165787A (ja) * | 1996-12-11 | 1998-06-23 | Nitto Denko Corp | ポリテトラフルオロエチレン多孔質膜およびその製造方法 |
JPH10328539A (ja) * | 1997-06-02 | 1998-12-15 | Nitto Denko Corp | ポリテトラフルオロエチレン多孔質膜及びその製造方法 |
US6770086B1 (en) * | 2000-11-02 | 2004-08-03 | Scimed Life Systems, Inc. | Stent covering formed of porous polytetraflouroethylene |
JP4659241B2 (ja) | 2001-03-19 | 2011-03-30 | ジャパンゴアテックス株式会社 | ポリテトラフルオロエチレン膜及びその製造方法 |
US7922946B2 (en) | 2004-11-24 | 2011-04-12 | Donaldson Company, Inc. | PTFE membrane |
-
2005
- 2005-11-23 US US11/287,164 patent/US7922946B2/en active Active
- 2005-11-23 WO PCT/US2005/042777 patent/WO2006058233A1/en active Application Filing
- 2005-11-23 JP JP2007543535A patent/JP5592056B2/ja active Active
- 2005-11-23 CN CN2005800402189A patent/CN101065424B/zh active Active
- 2005-11-23 EP EP05850014.1A patent/EP1819757B1/en active Active
-
2010
- 2010-10-18 US US12/906,356 patent/US9409132B2/en active Active
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4187390A (en) * | 1970-05-21 | 1980-02-05 | W. L. Gore & Associates, Inc. | Porous products and process therefor |
GB1475316A (en) * | 1973-03-19 | 1977-06-01 | Sumitomo Electric Industries | Preparation of porous polytetrafluoroethylene sheets |
US4194041A (en) * | 1978-06-29 | 1980-03-18 | W. L. Gore & Associates, Inc. | Waterproof laminate |
US5476589A (en) * | 1995-03-10 | 1995-12-19 | W. L. Gore & Associates, Inc. | Porpous PTFE film and a manufacturing method therefor |
US5814405A (en) * | 1995-08-04 | 1998-09-29 | W. L. Gore & Associates, Inc. | Strong, air permeable membranes of polytetrafluoroethylene |
CN1387991A (zh) * | 2001-05-25 | 2003-01-01 | 周钦俊 | 一种铁氟龙第三轴向多向性延伸膜及制备方法 |
US20030194547A1 (en) * | 2002-04-15 | 2003-10-16 | Fuhrmann Louis P. | Membrane composite structure and method of production |
Non-Patent Citations (1)
Title |
---|
CN 1387991 A,全文. * |
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