CN1033428C - 聚四氟乙烯多孔薄膜及其制备和使用 - Google Patents
聚四氟乙烯多孔薄膜及其制备和使用 Download PDFInfo
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Abstract
一种聚四氯乙烯多孔薄膜,是通过延展半烧结聚四氟乙烯材料并以高于聚四氟乙烯熔点的温度加热延展材料来制备的,具有99∶1到75∶25的纤丝对结点的面积比,0.05到0.2μm的平均纤丝直径,不大于2μm2的最大结点面积和0.2到0.5μm的平均孔径,并达到低的压力损耗。
Description
本发明涉及聚四氟乙烯(下文称为“PTFE”)多孔薄膜、制备该薄膜的过程以及由该薄膜组成的过滤器。更具体地说,本发明涉及可用作空气过滤器的新颖PTFE多孔薄膜,所述空气过滤器适合于吸收半导体工业所用的净化室中空气或其它气体中的混悬微粒并且引起空气或其它气体小的压力损耗。
作为用于净化室的空气过滤器的材料,可用玻璃纤维混合体制成薄片来进行制备,并且通常要使用粘合剂。然而,这种滤材有若干缺陷,例如,滤材中存在粘着的微小纤维;在加工或折叠滤材时出现自起灰尘;或使抑制自生灰尘所加粘合剂用量的增加引起的压力损耗增加(参见日本专利公开公报16019/1988号或相应美国专利4877433号。此外,当这种滤材和诸如氢氟酸的某种化学品相接触时,由于玻璃和粘合剂变质而造成灰尘。
要解决此类问题,日本专利公开号53365/1979提出一种合成纤纤制成的驻极体滤材,但它有驻极体变质的不足。
为克服上述缺陷,建议使用延展的PTFE多孔薄膜作为滤材辅助件(参考日本专利公开号16019/1988和284614/1990)。
然而,该建议使用孔径为1μm或更大的多孔PTFE薄膜以避免压力损耗的增加。
其颗粒尺寸小于上述孔经尺寸的混悬颗粒被收集的理论依据如下:
存在以下三种用过滤器将液体中粒颗除去的机制(参见DomnickHunter Filters limited的小册子)。
1.直接拦截
较大颗粒可用滤材的微纤维拦截并除去如同它们被过筛。
2.惯性碰撞
当颗粒通过微纤维中的通风空间时,它们不能象气体那样快地改变其移动方向使得它们与微纤维相碰撞并粘附于其上。
3.扩散/布朗运动
非常小颗粒的运动由分子间的力及静电控制并在气体中螺旋形运动,便得其外观直径增大并如同在惯性碰撞情形一样粘附到微纤维上。
此外,混悬颗粒可由电荷收集机制通过驻极体加以收集(见日本专利公开号53365/1979)。然而,如从日本专利公开号284614/1990和相应的欧洲专利EP-A-395331中可知,颗粒尺寸小于等于1μm的颗粒不能完全由该机构除去。
在日本专利公开17216/1981和相应美国专利号4187390中公开了被用作滤材的一种典型的PTFE多孔薄膜。
用这种PTFE多孔薄膜,拉伸比应做得大以增加孔隙率,从而形成压力损耗小的滤材。结果,增大了孔经。为减小孔径,拉伸比不能做得大,而生产出的多孔薄膜有大的压力损耗。
本发明的一个目的是提供一种孔径小、压力损耗也小的PTFE多孔薄膜。
本发明的另一目的是提供一种具有改进的收集极细微颗粒能力的滤材。
按照本发明的第一方面,提供一种PTFE多孔薄膜,该薄膜是通过延展半烧结PTFE材料,并以高于烧结PTFE熔点的渴度加热该经延展的材料来制备的,该PTFE多孔薄膜具有99∶1到75∶25的微丝对结点的面积比;微丝的平均直径为0.05到0.2μm,最大结点面积不大于2μm2,它们是通过扫描电子显微照片确定的,平均孔经为0.2到0.5μm。
按照本发明的第二方面,提供一种其厚度不大于半烧结PTFE材料的1/20的PTFE多孔薄膜(例如,当半烧结材料的厚度为100μm,则多孔薄膜厚度为5μm,当空气以5.3cm/秒流速通过该薄膜时压力损耗为10到100mmH2O。
图1示意性地示出实例中所用延展设备;
图2示出未烧结PTFE材料和烧结PTFE材料的结晶熔化曲线;
图3示出半烧结PTFE材料的结晶熔化曲线;
图4和图5分别为实例1和2制备的PTFE多孔薄膜的SEM照片;
图6和图7分别是通过处理图4和图5所得到的图象;
图8和图9分别是与图6和图7分开的微丝的图象;
图10和11分别是与图6和图7分开的结点的图象;
图12和13分别是现成商品PTFE薄膜A和B的SEM照片;
图14和15分别是与通过处理图12和13所得到的图象分开的微丝的图象;
图16和17分别是与通过处理图12和13所得到的图象分开的结点的图象;
图18到24示出PTFE多孔薄膜微丝-结点结构的模型;
图25示意性示出实例3和4中所用延展和层压设备。
本发明的PTFE多孔薄膜可这样使用或通过层压低压力损耗的独立加强材料予以加强。层压的PTFE多孔薄膜具有改进的可操作性。该层压的PTFE多孔薄膜可以褶的形式折叠并用作收集特细小颗粒的过滤器。
作为加强材料,可使用非纺织纤维、纺织纤维、网或其它多孔材料。加强材料可用诸如聚烯烃(例如聚乙烯、聚丙烯等)、聚酰胺、聚酯、芳族聚酰胺的各种原材料或它们的组合物制成,这些组合物例如其纤维具有内核/外层结构的非纺织纤维、低熔点材料和高熔点材料的双层非结织纤维、氟树脂(例如四氟乙烯/全氟烷基乙烯基醚共聚体)(PFA)、四氟乙烯/六氟丙烯共聚体(FEP)、PTFE等)等等。其中,其纤维具有内核/外层结构的非纺纤维及低溶点材料与高熔点材料的双层非纺织纤维由于在层压时不收缩而被优选。带有这类加强材料的层压薄膜很容易以HEPA(高效微粒空气)过滤器的形式加以处理,并可在将其作为过滤单元处理时增大折叠间距数。
层压的结构不受限。例如,加强材料的一个或两个表面上可层压本发明的PTFE多孔薄膜,或将PTFE多孔材料夹在一对加强材料之间。
PTFE多孔薄膜和加强材料可用任何常规方法层压,例如,溶化部分加强材料或将聚乙烯、聚酯或PFA、或热熔树脂粉未作为粘合剂的热压粘合。
从如上所述颗粒去除机构来看,有必要防止附着于过滤器上纤维的颗粒的解吸附作用或屏蔽颗粒通路以便无误地收集颗粒。因此,应使用其孔经小于肯定被收集的颗粒的粒径的滤材,因此,具有小的平均孔径的PTFE多孔材料是最优的。
薄膜厚度越小则越好,因为当孔径和滤材孔隙率相同时压力损耗与薄膜厚度成正比。即使滤材的压力损耗、孔内径、孔隙率和薄膜厚度相同,收集细小颗粒的能力也因材料而变。理论上来说,最好使用直径0.5μm或更小的纤维,并减少粘合剂用量,即减少纤维以外材料的用量(参考化学工程协会的Emi Jun的52年未定稿版)。
本发明的PTFE多孔薄膜满足这些条件。
结合其生产过程更详细地说明本发明的PTFE多孔薄膜。
在本发明中用作原材料的未延展PTFE薄膜材料是在日本专利公开152825/1984(相应美国专利申请4596837)号中公开的半烧结的PTFE材料。
半烧结PTFE材料以至少50的面积拉伸比双轴向延展,最好是至少100,而250拉伸比更好,然后进行烧结,该经烧结的PTFE多孔薄膜具有非常一致的薄膜结构,并包含基本无结点的纤维。
这样产生的PTFE多孔薄膜具有很小的平均孔经例如从0.2到0.5μm,而其厚度减小为未延展的半烧结PTFE材料厚度的1/20到1/100。
这些参数适合于空气过滤材料,用以在半导体上形成的微模式中保持极为清洁的空间。
具有上述结构的PTFE多孔薄膜尚不能用常规过程制造。例如,日本专利公报17216/1981在11列23行说明“图1示出了单轴方向的延长效果”。借助双轴向延展或所有方向延展,以这些方向加工微纤维从而开成蜘蛛网结构或交叉链接结构,并带来强度增加。由于聚酯的结点与微纤维间空间数和大小的增加,孔隙率也增大。这意味着拉伸比增加只引起孔径的增加。
由于孔径增加或薄膜厚度减小,压力损耗减小。要生产小孔径并且压力损耗低的空气过滤器,应使用薄的PTFE薄膜。在日本专利公报17216/1981号中常规过程中,伸拉比的增加并未导致宽度和厚度减小。当拉伸比极大地增大时,孔径被扩大。因此,在延展前应薄膜厚度做薄,并应以小的拉伸比延展该薄膜。
然而,在延展前技术上可用薄膜的厚度至多为30到50μm。考虑所产薄膜的质量和产量,延展前薄膜厚度为100μm左右。
本发明的一个特征是最终PTFE多孔薄膜可用其厚度约100μm的未延展薄膜制成。
本发明参数的一般范围和最佳范围如下:
一般范围 最佳范围
烧结度 0.30-0.80 0.35-0.70
拉伸比 MD 4-30 5-25
TD 10-100 15-70
总 50-1000 75-850
当总拉伸比为250或更大,烧结度最好为0.35到0.48。
一般范围 最佳范围平均孔径 0.2-0.5μm 0.2-0.4μm薄膜厚度 0.5-15μm 0.5-10μm原纤维对结点的面积比率 99/1~75/25 99/1~85/15平均原纤维直径 0.05-0.2μm 0.05-0.2μm最大结点面积 <2μm2 0.05-1μm2压力损耗 10-100mmH2O 10-70mmH2O
在实例中定义了烧结度。
本发明的PTFE多孔薄膜可用作空气过滤器。此外,当液体通过作为分隔薄膜的本发明的PTFE多孔薄膜时可获得不含液体中不纯颗粒的洁净空气。这种应用的一个实例是去湿设备中的分离薄膜。
按照本发明,可大量生产非常薄的PTFE多孔薄膜,本发明的PTFE多孔薄膜可用于需要水渗透性或空气排斥性的应用场合。
通过以下实例,详细地对本发明作进一步说明。实例1
将用PTFE细粉(由Daikin实业公司制造的Polyflon(商标)细粉F-104)制备的厚度为100μm的未烧结、未延展的PTFE薄膜在炉中加热并在339℃下保持50秒以获得0.50烧结度的连续的半烧结薄膜。
将半烧结薄膜切为大约9cm2的样本,用能双向同时或接续地延展薄膜的设备(由Iwamoto制造公司制造)的夹子夹持其四个边,然后在320℃环境温度加热15分钟再以100%/秒的速率,以拉伸比5在薄膜的纵向(称为“MD”方向)上延展。
然后,以拉伸比15在薄膜的宽度方向(称为“TD”方向)上连续延展该样本同时固定MD方向的长度以获得以总拉伸经(面积拉伸比)75的延展的多孔薄膜。
该延展薄膜置于框架上以防收缩,置于炉中热,保持350℃3分钟。实例2
用在实例1的烧结度0.5的同样的半烧结薄膜以实例1中同样方式,在MD方向以拉伸比8、在TD方向以拉伸比25(总拉伸比200)进行延展以获得延展的PTFE多孔薄膜。
以实例1同样方式将该多孔薄膜在350℃加热3分钟。实例3
用实例1所用的同样的PTFE细粉通过常规的糊挤压、辊子压延和润滑干燥来制备厚度100μm的未延展、未烧结的PTFE薄膜,并在炉中以338℃加热45秒以获得0.40烧结度的连续的半烧结薄膜。在此加热步骤之前,薄膜有215mm宽度和1.55g/cm3的比重,在此加热步骤之后,薄膜宽度为200mm,比重为2.25g/cm3。然而加热前后的厚度基本相同。
用图1所示设备以拉伸比20在纵方向上延展该半烧结薄膜。
纵方向的延展条件如下:
辊子3和4: 馈给速度: 0.5m/分
温度:室温
薄膜宽度: 200mm
辊子6: 周边速度: 4m/分
温度: 300℃
辊子7: 周边速度 10m/分
温度: 300℃
辊子10: 周边速度: 10m/分
温度: 25℃
卷绕辊子2:卷绕速度: 10m/分
温度:室温
薄膜宽度: 145mm
辊子6和7周边间距离: 5mm
纵向面积拉伸比计算应为14.5。
然后以大约拉伸比34延展该纵向延展的薄膜并用能连续以夹子夹持薄膜的两边的图25的设备加热凝结。
图25中,标号代表以下部件:
13: 薄膜供给辊子
14: 供给控制机构
15: 预加热炉
16: 用于宽度方向延展的炉
17: 热凝结炉
18、19: 层压辊子(19:加热辊子)
20: 卷绕控制机构
21: 卷绕辊子
22、23: 用于层压非织纤维的滚筒
在以上步骤中,延展和加热凝结条件加下:
薄膜馈给速度:3m/分
预加热炉温度:305
宽度方向延展炉温度:320℃
加热凝结炉温度:350℃
总面积拉伸比计算为大约490。实例4在以宽度方向延度薄膜的两个表面上,用图25的设备层压非织纤维。
层压条件如下:
上层非织纤维:ELEVES T 1003 WPO
(UNITIKA制造)
下层非织纤维:Melfit BT 030 E
(UNI SEL制造)
加热辊子19温度:150℃
该层压PTFE多孔薄膜平均压力损耗为25mmH2O。压力损耗测量如下:
以相等距离切割延展薄膜的各边以获得宽度为800mm的薄膜,在等间距的同一宽度线上的四个点测量压力损耗。最大压力损耗为27mmH2O,最小压力损耗为23mmH2O。对比实例
用图1设备对实例1所用相同半烧结PTFE薄膜进行延展。也就是,由馈给辊子1,将半烧结PTFE薄膜通过辊子3、4、5馈给辊子6、7,从而以拉伸比6在MD方向对薄膜延展。
经延展薄膜通过辊子8、9、加热凝结辊子10、冷却辊子11和辊子12,并卷绕在卷绕辊子2上。
延展条件如下:
辊子6: 辊子表面温度: 300℃
周边速度 1m/分
辊子7: 辊子表面温度: 300℃
周边速度: 6m/分
辊子6和7周边间距: 5mm
辊子10: 辊子表面温度: 300℃
周边速度:与辊子7同步
将该延展的薄膜切割为长1m、宽15cm,将经切割薄膜以TD方向加以延展而不需将宽度定在拉伸比4以及在350℃加热凝结3分钟。在该延展薄膜中,未发现按照本发明定义的结点。
将实例1、2和3及对比实例所生产的薄膜和两种孔经0.1μm(A:Millipore制造的用FLUOROGURAD TP支架组装的P TFE多孔薄膜;B:Advantec Toyo制造的T300A 293-D PTFE薄膜过滤器)市场上现成的PTFE薄膜作为比较实例,平均孔经、薄膜厚度、纤丝对结点的面积比,纤丝平均直径,最大结点面积和压力损耗测量如下述。结果示于表中。 表
实例号 | 薄膜厚度(μm) | 平均孔径(μm) | 纤丝对结点面积比 | 纤丝平均直径(μm) | 最大结点面积(μm2) | 压力损耗(mmH2O) |
1 | 4.5 | 0.26 | 90/10 | 0.15 | 1.2 | 65 |
2 | 1.0 | 0.28 | 95/5 | 0.14 | 0.38 | 45 |
3 | 0.8 | 0.30 | 96/4 | 0.14 | 0.36 | 15 |
54 | 0.27 | -- | 0.27 | -- | 1300 | |
Com.Ex.AB | 7070 | 0.282.90 | 65/35 | 0.15 | 7.5 | 129055 |
从表的结果可知,尽管本发明的PTFE多孔薄膜和商业上可得到的薄膜A和对比实例的薄膜具有基本相同的平均孔径,但其压力损耗比后者小得多,尽管实例1和2的PTFE多孔薄膜具有和商业上可得到的薄膜B具有基本相同的压力损耗,但它们的平均孔径比后者要大得多。此外,可以看到,当如实例3以大约500面积拉伸比延展该薄膜时,尽管平均孔经在同一水平但压力损耗可进一步减小。
实例中的PTFE多孔薄膜具有比商业上可得到薄膜A要大的纤丝对结点的面积比。实例的PTFE多孔薄膜具有比对比实例小的平均纤丝直径。本发明的PTFE多孔薄膜的最大结点面积比商业上可得到薄膜A的要小得多。
该表特征测量如下:
平均孔径
按照ASTMF-316-86测量的平均流孔经用作平均孔径。其中,用Coulter Porometer(Coulter Electronics UK制造)测量该平均流孔径。薄膜厚度
用1D-110MH型薄膜厚度仪(由Mitsutoyo公司制造)测量层列薄膜的总厚度并将测量值除5以得到一薄膜的薄膜厚度。
压力损耗
将PTFE多孔薄膜切为直径47mm圆形,置于具有12.6cm2有效传输面积的过滤器夹持器上。以0.4kg/cm2空气对入口侧加压,通过用流量计(Ueshima制造公司制造)调节来自出口侧的空气流速将通过多孔薄膜的传输速率控制为5.3cm/秒。在这种条件下,用压力计测量压力损耗。
烧结度
半烧结的PTFE材料的烧结度定义如下:
从未烧结的PTFE材料称取3.0±0.1mg的样本,用此样本测量结晶熔化曲线。从半烧结的PTFE材料,称取3.0±0.1mg样本,用此样本测量结晶熔化曲线。
用诸如Shimadzu生产的DSC-50的差异扫描量热器(下文称为“DSC”)记录该结晶熔化曲线。
将未烧结的PTFE材料的样本装入DSC的铝皿,用以下步骤测量未烧结PTFE材料的熔解热和烧结的PTFE材料的熔解热。
(1)以50℃/分加热速率加热样本到250℃,然后以10℃/分加热速率从250℃加热到380℃。在此加热步骤记录的结晶熔化曲线的一个实例示于图2中的曲线A。出现吸热峰值的温度定义为“未烧结PTFE材料的溶化点”或“PTFE细粉的熔化点”。
(2)当温度达到380℃后立即以10℃/分冷却速率冷却到250℃。
(3)然后,再次以10℃/分加热速率将样本加热到380℃。
加热步骤(3)记录的结晶熔化曲线的一个例子在图2中以曲线B示出。
出现吸热峰值的温度定义为“烧结的PTFE材料的熔点”。
其次,以步骤(1)同样方式记录半烧结的PTFE材料的结晶熔化曲线。在该步骤的结晶熔化曲线的一个例子在图3中示出。
未烧结PTFE材料(图1中的ΔH1)、烧结的PTFE材料(图1中ΔH2)和半烧结PTFE材料(图2中ΔH3)中各个熔解热与结晶熔化曲线和底线所围面积成正比,熔解热用Shimadzu的DSC-50自动计算。
然后,按以下等式计算烧结度:
烧结度=(ΔH1-ΔH3)/(ΔH1-ΔH2)其中,ΔH1是未烧结PTFE材料的熔解热,ΔH2是烧结PTFE材料的熔解热,而ΔH3是半烧结PTFE材料的熔解热。
在日本专利公开152825/1984(相应美国专利号4596837)中可以找到半烧结PTFE材料的详尽说明。
图象分析
纤丝对结点的面积比、平均纤丝直径和最大结点面积测量如下:
用扫描电子显微镜(Hitachi S-400,用Hitachi E-1030蒸发)(SEM照片,放大1000到5000倍)拍摄PTFE多孔薄膜表面照片。用图象处理设备扫描该照片(硬件:日本Avionics公司生产的电视图象处理器TVIP-4100II,控制软件:Latock系统工程公司提供的电视图象处理器图象命令4198)将纤丝与结点分开以获得纤丝的图象和结点的图象。通过处理结点图象,获得最大结点面积,通过处理纤丝图象获得平均纤丝直径(总面积与总周边长度1/2的比)。
纤丝对结点的面积比可计算为纤丝图象总面积与结点图象总面积之比。
图4和图5分别是实例1和实例2制备的PTFE多孔薄膜的SEM照片。
图6和图7分别是通过加上处理图4、5得到的图象。
图8和图9分别是从图6和图7分割出的纤丝图象。
图10和图11分别是从图6和图7分割出的结点图象。
图12和图13分别是商业上可得到的PTFE薄膜A和B的SEM照片。
图14和15分别是从处理图12、13得到的图象中分出的纤丝的图象。
图16和图17是从处理图12、13得到的图象中分出的结点的图象。结点的定义
此文中,结点满足以下特征之一:
(1)多个纤丝连接到的块(图18中带点的区域)
(2)大于连接到该块的纤丝的直径的块(图21和22中画划阴影线区域)
(3)原始颗粒或从中容易延展纤丝的聚结的原始颗粒(图12、22和23中划阴影线区域)
图24是不认为是结点的一种结构的实例。在图24中,分支出纤丝,但分支区域大小和纤丝直径相同。在本发明中,该分支出区域不认为是结点。
Claims (3)
1.一种聚四氟乙烯多孔薄膜,其特征在于,其平均孔径为0.2至0.5μm,薄膜的厚度由0.5至15μm,当空气以5.3cm/秒流速通过时,压力损耗由98至980帕(10至100mmH2O)。
2.根据权利要求1的聚四氟乙烯多孔薄膜,其特征在于:该薄膜至少有一个表面用或不用粘合剂以从由烯族多孔材料薄膜和氟树脂多孔薄膜构成的组中选出的加强材料薄膜层压而成。
3.一种包含如权利要求1或2所述的聚四氟乙烯多孔薄膜的空气过滤器。
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- 1992-07-21 CA CA002074349A patent/CA2074349C/en not_active Expired - Fee Related
- 1992-07-22 RU SU5052430A patent/RU2103283C1/ru not_active IP Right Cessation
- 1992-07-22 US US07/916,618 patent/US5234739A/en not_active Expired - Lifetime
- 1992-07-23 CN CN92108754A patent/CN1033428C/zh not_active Expired - Lifetime
- 1992-07-23 EP EP92112569A patent/EP0525630B1/en not_active Expired - Lifetime
- 1992-07-23 ES ES94107246T patent/ES2126672T3/es not_active Expired - Lifetime
- 1992-07-23 DE DE69208552T patent/DE69208552T2/de not_active Expired - Fee Related
- 1992-07-23 KR KR1019920013185A patent/KR100258485B1/ko not_active IP Right Cessation
- 1992-07-23 EP EP94107246A patent/EP0611790B1/en not_active Expired - Lifetime
- 1992-07-23 DE DE69228002T patent/DE69228002T2/de not_active Expired - Fee Related
- 1992-07-23 ES ES92112569T patent/ES2086591T3/es not_active Expired - Lifetime
Cited By (6)
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CN105794031A (zh) * | 2013-11-29 | 2016-07-20 | 旭化成株式会社 | 高分子电解质膜 |
CN105794031B (zh) * | 2013-11-29 | 2019-01-29 | 旭化成株式会社 | 高分子电解质膜 |
US10644339B2 (en) | 2013-11-29 | 2020-05-05 | Asahi Kasei Kabushiki Kaisha | Polymer electrolyte membrane |
US10688448B2 (en) | 2013-11-29 | 2020-06-23 | Daikin Industries, Ltd. | Porous body, polymer electrolyte membrane, filter material for filter, and filter unit |
US10944121B2 (en) | 2013-11-29 | 2021-03-09 | Asahi Kasei Kabushiki Kaisha | Polymer electrolyte film |
US11084895B2 (en) | 2013-11-29 | 2021-08-10 | Daikin Industries, Ltd. | Modified polytetrafluoroethylene fine powder and uniaxially stretched porous body |
Also Published As
Publication number | Publication date |
---|---|
CA2074349A1 (en) | 1993-01-24 |
EP0525630A2 (en) | 1993-02-03 |
RU2103283C1 (ru) | 1998-01-27 |
ES2086591T3 (es) | 1996-07-01 |
DE69208552D1 (de) | 1996-04-04 |
EP0525630B1 (en) | 1996-02-28 |
DE69228002T2 (de) | 1999-06-10 |
EP0611790A3 (en) | 1994-09-28 |
KR100258485B1 (ko) | 2000-06-15 |
DE69228002D1 (de) | 1999-02-04 |
CA2074349C (en) | 2004-04-20 |
EP0611790B1 (en) | 1998-12-23 |
EP0525630A3 (en) | 1993-03-17 |
KR930002425A (ko) | 1993-02-23 |
US5234739A (en) | 1993-08-10 |
DE69208552T2 (de) | 1996-09-05 |
ES2126672T3 (es) | 1999-04-01 |
EP0611790A2 (en) | 1994-08-24 |
CN1072351A (zh) | 1993-05-26 |
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