CN1403269A - 原位产生的具有层状孔结构的微孔膜生产方法 - Google Patents

原位产生的具有层状孔结构的微孔膜生产方法 Download PDF

Info

Publication number
CN1403269A
CN1403269A CN01139677A CN01139677A CN1403269A CN 1403269 A CN1403269 A CN 1403269A CN 01139677 A CN01139677 A CN 01139677A CN 01139677 A CN01139677 A CN 01139677A CN 1403269 A CN1403269 A CN 1403269A
Authority
CN
China
Prior art keywords
strip
microporous barrier
ptfe
squeezed
fractional saturation
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
CN01139677A
Other languages
English (en)
Inventor
马克·E·狄龙
理查德·布兰迪马尔特
雷蒙德·E·特里格里奥
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BIOMED SCIENCES Inc
Original Assignee
BIOMED SCIENCES Inc
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by BIOMED SCIENCES Inc filed Critical BIOMED SCIENCES Inc
Publication of CN1403269A publication Critical patent/CN1403269A/zh
Pending legal-status Critical Current

Links

Images

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04Interconnection of layers
    • B32B7/10Interconnection of layers at least one layer having inter-reactive properties
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D67/00Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002Organic membrane manufacture
    • B01D67/0023Organic membrane manufacture by inducing porosity into non porous precursor membranes
    • B01D67/0025Organic membrane manufacture by inducing porosity into non porous precursor membranes by mechanical treatment, e.g. pore-stretching
    • B01D67/0027Organic membrane manufacture by inducing porosity into non porous precursor membranes by mechanical treatment, e.g. pore-stretching by stretching
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D69/00Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/02Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D69/00Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12Composite membranes; Ultra-thin membranes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D69/00Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12Composite membranes; Ultra-thin membranes
    • B01D69/1212Coextruded layers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D71/00Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06Organic material
    • B01D71/30Polyalkenyl halides
    • B01D71/32Polyalkenyl halides containing fluorine atoms
    • B01D71/36Polytetrafluoroethene
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D71/00Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06Organic material
    • B01D71/70Polymers having silicon in the main chain, with or without sulfur, nitrogen, oxygen or carbon only
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C44/00Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/20Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles for articles of indefinite length
    • B29C44/22Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles for articles of indefinite length consisting of at least two parts of chemically or physically different materials, e.g. having different densities
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/005Shaping by stretching, e.g. drawing through a die; Apparatus therefor characterised by the choice of materials
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B29C55/023Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets using multilayered plates or sheets
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/06Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/06Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/32Layered products comprising a layer of synthetic resin comprising polyolefins
    • B32B27/322Layered products comprising a layer of synthetic resin comprising polyolefins comprising halogenated polyolefins, e.g. PTFE
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00Ancillary operations in connection with laminating processes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00Ancillary operations in connection with laminating processes
    • B32B38/0032Ancillary operations in connection with laminating processes increasing porosity
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00Layered 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
    • B32B5/22Layered 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 the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/32Layered 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 the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed at least two layers being foamed and next to each other
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08L27/18Homopolymers or copolymers or tetrafluoroethene
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2325/00Details relating to properties of membranes
    • B01D2325/02Details relating to pores or porosity of the membranes
    • B01D2325/022Asymmetric membranes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2325/00Details relating to properties of membranes
    • B01D2325/02Details relating to pores or porosity of the membranes
    • B01D2325/022Asymmetric membranes
    • B01D2325/0233Asymmetric membranes with clearly distinguishable layers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29KINDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2027/00Use of polyvinylhalogenides or derivatives thereof as moulding material
    • B29K2027/12Use of polyvinylhalogenides or derivatives thereof as moulding material containing fluorine
    • B29K2027/18PTFE, i.e. polytetrafluorethene, e.g. ePTFE, i.e. expanded polytetrafluorethene
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2327/00Polyvinylhalogenides
    • B32B2327/12Polyvinylhalogenides containing fluorine
    • B32B2327/18PTFE, i.e. polytetrafluoroethylene
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2535/00Medical equipment, e.g. bandage, prostheses, catheter
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/24Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24942Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/24Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24942Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
    • Y10T428/24992Density or compression of components
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/249921Web or sheet containing structurally defined element or component
    • Y10T428/249953Composite having voids in a component [e.g., porous, cellular, etc.]
    • Y10T428/249962Void-containing component has a continuous matrix of fibers only [e.g., porous paper, etc.]
    • Y10T428/249964Fibers of defined composition
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/249921Web or sheet containing structurally defined element or component
    • Y10T428/249953Composite having voids in a component [e.g., porous, cellular, etc.]
    • Y10T428/249978Voids specified as micro
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/249921Web or sheet containing structurally defined element or component
    • Y10T428/249953Composite having voids in a component [e.g., porous, cellular, etc.]
    • Y10T428/249981Plural void-containing components
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/3154Of fluorinated addition polymer from unsaturated monomers
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/3154Of fluorinated addition polymer from unsaturated monomers
    • Y10T428/31544Addition polymer is perhalogenated
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/31652Of asbestos
    • Y10T428/31663As siloxane, silicone or silane

Abstract

描述了含有至少两层的微孔膜生产方法,其中每层的特征是由微丝相互连接的节点,利用低于每种膜材料的熔点温度的塑性物流连接膜层,并且通过膨胀作用在原位形成孔结构。制造了每层的孔结构可以小心控制的层化微孔膜。所得物品可用于需要孔尺寸梯度的过滤应用及医疗应用。

Description

原位产生的具有层状孔结构的微孔膜生产方法
本发明背景
本申请为本申请人在中国第96196775.7号专利申请的分案申请。
发明领域
本发明涉及新型的微孔膜,并且部分涉及膨胀的聚四氟乙烯(PTFE),或者PTFE和硅氧烷的膨胀互穿高分子网络(IPN)。
现有技术描述
在美国专利3,315,020中,公开了制备PTFE的板状制品的方法,所述制品在未烧结的状态下,在板的主平面的所有方向都具有较高的延伸性和强度。在该方法中,将较大机筒的致密分散等级的PTFE颗粒经过按序排列的两个孔的模中。第一个孔是圆的,正方形的或长方形的孔,而第二个孔是长条形的孔。为了有助于颗粒PTFE的压出,先将其与有机液体润滑剂例如,煤油,VM&P石脑油或同量异位素进行混合。所述润滑剂有助于PTFE颗粒的塑性流动,使其在压力下聚集成粘性的浆料。该挤压方法因此生产出连续和被挥发性的有机液体部分饱和的PTFE料带。
在仍被部分饱和的情况下,通常在室温下对PTFE挤出料带进行压延。压延包括将料带在预定距离排列开的夹辊之间进行压制。该距离基本上比进入的挤出料带的厚度要小。由于进入的挤出料带含有润滑剂,并且冷流体易于加工,塑性流体使制品在机器方向的延伸与进入和流出压延机的厚度差成比例。通常,再将流出的挤出料带用热轧辊加热至某一温度,在该温度下有机润滑剂在合理的时间内挥发以生产出干燥的挤出料带。
在制造PTFE管—线密封胶材料中,对干燥的挤出料带的进一步定向是用差速轧辊机进行纵向拉伸来完成的。伸展量由第二轧辊对第一轧辊的速度比决定,例如,1.75∶1的比例代表75%的延伸。
在生产微孔PTFE膜时,通过使用某设备例如拉幅机架等将沿纵向定向的挤出料带在横向进行拉伸。拉幅机架是这样一种装置,它由可抓住料带两边的夹紧输送器组成。当输送器移动进入管型炉中时,它们彼此进一步分开。在炉的终端夹子放开。这样在较高温度下挤出料带在横向以连续的方式进行拉伸,并且可以容易地卷成卷。
当除去有机润滑剂并且将PTFE挤出料带进行拉伸时,该材料并不像普通塑料那样变薄。而是,PTFE具有不寻常的性能,它能进行一种被称作原纤化作用的内部断裂过程。PTFE最初是粘性的整体。在开始施加拉伸应力时,该整体断裂或被称作节的团块物。这些节互相用微丝相连接,所述微丝基本上是从节上拉出的定向的PTFE分子束。因此该物质就变成了多孔性的,其孔的构造由节和微丝决定的空间所确定。
在这种方式下,拉伸量以及纵向和横向拉伸的比例控制了孔的结构。当拉伸程度加深时,节断裂为更小的结构并且产生了更大量的微丝。这样就产生了多孔性,但是总体尺寸可能并没有显著的变化。在膜生产中,板材可能被拉伸了几十倍,但仅减小了一半厚度,这就导致了总体积的净增长。因此,将PTFE拉伸到原纤化结构的过程被称作膨胀。这种效果证明一些形式的膨胀PTFE板在与板的主平面垂直的方向上具有负的泊松(Poisson)比(Cherfas,1990)。
原纤化作用的一个并列的效果是拉伸的增加并不一定产生较大的孔,实际上却可能减少终产品的平均孔尺寸。相对少量的较大的孔被较大量的小孔所取代。对于由拉幅机架生产出的双轴向膨胀的PTFE,大量的纵向拉伸一般产生相对较小孔尺寸的终产品。但是,如果在各方向的拉伸都达到最大量,当PTFE节的量被用尽时,这种膜的孔尺寸最终增大。在这一点上,整体物质表现出较大的塑性,并且进一步的拉伸仅拉长了微丝并且增加了节之间的距离,直至微孔产生。
PTFE分散级树脂是大约95%的结晶体,并且具有非常高的熔化粘性。当加热至高于327℃的温度时,PTFE微晶变形为无定形的聚合物。当冷却至低于327℃时,部分液体结构保留下来,这样与原来的PTFE相比增加了熔化的PTFE的无定形含量。这样对聚合物先加热随后冷却的过程称作烧结作用。对成型的微孔PTFE结构的烧结作用对聚合物产生了热固效果,这样就使形状得以保留并保证了热稳定性。一般通过在拉幅机设备的最终阶段产生一高温区来烧结微孔PTFE膜。
在现有技术中生产PTFE挤出物的过程中,在生产具有满意的分子定向的均一的压出物以利于充分的横向拉伸方面存在困难。挤出料带的分子定向很大程度上受聚合物组成的流变性能,施加于系统的压力,以及模的设计的影响。由于其不同的物理和分子特性,不同等级的PTFE树脂提供了特定的流变条件,因此即使在相同的挤出条件下,不同等级的树脂则产生出不同程度的分子定向。PTFE挤压系统很复杂并且难于控制。这些困难的实例可见于美国专利4,187,390。
在美国专利4,945,125中,公开了生产PTFE的原纤化IPNs及聚有机硅氧烷的方法。IPNs可用顺序法或同时法生成。同时法包括将聚硅氧烷组份与用于挤压作用的有机润滑剂预混和,然后将硅氧烷/润滑剂的混合物分散到颗粒状PTFE树脂中,再在与现有技术中相同的条件下将所述树脂进行挤压。人们发现硅氧烷的存在能有利于此类IPN产品的挤压作用及分散作用,硅氧烷在分子定向中显然充当了内部润滑剂的作用,并且在有机润滑剂挥发后在节/微丝的形成中也起了作用。
如果生产得当,IPN产品比常规的PTFE产品具有较高的强度和均一性。
在生产微孔PTFE膜或微孔IPN膜的现有技术中,在板材的厚度方向上孔的结构是同一的。这是由于(a)在挤出板材的厚度方向上聚合物的组成,以及流变挤压条件是同一的,(b)压延过程引起的定向均一施加于整个挤出料带上,(c)挤出物在任一方向上的膨胀均匀地施加于板材的厚度方向上,以及(d)烧结影响着膨胀膜的全部微观结构。
本领域技术人员也许熟悉几种将具有不同厚度和孔结构的膜进行叠层的方法,例如粘性叠层或热连接。对于粘性连接,两层或多层微孔膜粘在一起,得到所需要的孔尺寸梯度。这类粘合作用所具有的阻断气流或气流的有害作用与粘合剂所覆盖的面积成比例。在需要的条件下这类粘合系统易于脱层。热连接是依赖于热和压力以实现叠层的方法。这种方法对于具有很高的熔点及/或粘性的类PTFE聚合物特别不适用。但是,在足够的压力和温度下,微孔PTFE或PTFE/硅氧烷IPN膜能够叠在一起。但是,这类条件所引起的变形对膜的微观结构会有不利影响。热连接的膜也易于脱层,这是由于两层的连接只是表面上的,因为连接的程度取决于每层膜的节点之间的接触点的数量以及熔化的物流所达到的程度。PTFE的高的熔化粘性限制了该项技术的使用。
本发明概述
我们已经发现通过在压延过程中长久地将两层或多层挤出料带连接在一起,可以将PTFE或PTFE/硅氧烷IPN膜的孔结构小心控制在层化状态。通过使用不同的挤出物组成,由挤压和压延引起的分子定向的程度对于每层可以不同。因为在叠层时至少有一层挤出料带仍然被有机润滑剂部分饱和,冷物流很容易达到并且容易达到长久的连接。层化的挤出料带的任何随后的膨胀将在每层产生完全不同的或不同的构造的孔结构。结果,终产品实际上是具有层化孔结构的单层膜而不是不同膜的叠层。如果在压延—连接前对一层或多层挤出料带进行不同量的纵向和/或横向拉伸,那么这种效果将会更加明显。每层的厚度取决于叠层前被压延的程度,并且对产品的每层可以有所不同。
人们进一步设想在叠层作用前对层化料带的每层用表面活性剂等进行单独修饰,以生产出在每面具有不同的表面性能的微孔板材。并且,通过按序重复该方法可以生产出多层的物品。另外,可将具有相同聚合物组成的多个薄层叠在一起,以使挤出料带的膨胀厚度大于用给定的挤压模所达到的厚度。
本方法的产品可以有多种用途。例如,层化的孔结构在过滤过程中有明显的作用。具有小孔尺寸的很薄的膜可与具较大孔尺寸的较厚的膜相连接。其作用是具有薄的,小孔尺寸膜的大部分过滤效率的同时,又具有较厚膜的总的物质完整性。由于在该方法中不使用粘合剂,流率和过滤系统的效率不会因为开孔的阻塞而降低。由于膨胀过程在原位产生了孔尺寸梯度,这就避免了热连接两层微孔膜时的破碎作用。
本发明特别涉及在其厚度方向上具有层化孔结构的微孔层膜。膜的一层平均孔尺寸基本上小于或大于其它层的平均孔尺寸。通过下面的方法在原位产生该层化孔结构:1)将聚四氟乙烯(PTFE)树脂或PTFE/硅氧烷互穿聚合物网络(IPN)挤压成第一料带;2)可选择地,压延所述第一料带使其厚度减小;3)可选择地,通过沿至少一个方向拉伸来定向所述第一料带;4)挤压具有相同或不同组成的第二PTFE或IPN料带;5)可选择地,压延所述第二料带使其厚度减小;6)在另外的压延过程中将第一片材叠加到第二挤出料带上;7)通过沿至少一个方向进行拉伸定向步骤(6)的料带,以生产出具有层化孔结构的微孔膜;以及8)可选择地,加热所得膜高于其晶体熔点以使其烧结。在高塑性的条件下完成了料带层之间的连接,而每层的多孔性则由膨胀过程决定。
本发明对现有技术的改进在于(a)膜的各层不能分离;(b)不需要额外的粘合系统;以及(c)膜的孔结构不经过在压力下发生热连接分离微孔片材的变形作用。成品适用于需要孔尺寸梯度的分离应用及医疗应用。
附图简述
附图是本专利申请实施例4的放大600倍的扫描电子显微照片。图1显示了被拉伸了两次和第一料带层的表面微观结构。图2显示了只经过拉幅机架设备一次的第二料带层的表面。从这些照片可以清楚看出每层膜表面的形态互相不同。对于第一膜层平均节间距离(通过平均微丝长度测量)是6.4微米,而对于第二膜层则是1.6微米。对几个实施方案的详细描述
本发明的几个实施方案公开于下述说明性的实施例中,所述实施例并非用于限制本发明。对于本领域技术人员可对本发明作一些明显的修饰。实施例1: 不同的聚合物树脂
按照现有的混和技术制备下面组份的混和物:
                   表I
    1号混和物     数量
    Cd-123 FluonPTFE树脂(美国的ICI)     9.072kg
    Q7-2218 Silastic硅氧烷(Dow Corning)     0.082kg
    石蜡溶剂     1.940kg
    2号混和物     数量
    Te-3641 TeflonPTFE树脂(E·I·杜邦)     9.072kg
    QT-2218 Silastic硅氧烷(Dow Corning)     0.082kg
    石蜡溶剂     1.940kg
将1号混和物通过1.5×228.6mm的长方形孔的模进行挤压,并压延成0.64mm的厚度。将部分饱和的挤出物累积在轧辊上以备后续处理之用。将2号混和物通过同样的模进行挤压,并在相同的条件下压延成0.89mm的厚度。将物料集中在轧辊上,然后将轧辊安装到挤压模附近的架子上。将1号挤出物放置到邻近2号挤出物轧辊的相同的架子上。将两种挤出物展开并通过缝隙设定值为0.19mm的压延机送回。所得到的物料经过一系列加热轧辊以除去有机润滑剂并且将它们重新卷成卷。
该双层挤出物与常规方法得到的物料难以区分,因为在料带中没有双层结构的标记。用拉幅机架设备对双层物料进行加工,在纵向将其拉伸64%,而在横向拉伸达76.2mm至2.0mm(2,525%)。升高在拉幅机架中最终加热区的温度以实现烧结。所得到的微孔膜外表均一,无肉眼可见的孔,并且其厚度约为17.8微米。
本实施例描述了一种双层微孔膜,其中每层,由不同级的树脂组成,但却经历相同的膨胀条件。实施例2: 相同的聚合物树脂;不同的挤出物组成;不同的膨胀条件
按照现有技术制备下列组份的混和物:
                         表II
    3号混和物     数量
    Cd-123 FluonPTFE树脂(美国的ICI)     27.22kg
    Q7-2218 Silastic硅氧烷(Dow Corning)     2.454kg
    石蜡溶剂     5.820kg
    4号混和物     数量
    Cd-123 FluonPTFE树脂(美国的ICI)     27.22kg
    QT-2218 Silastic硅氧烷(DoW Corning)     2.454kg
    石蜡溶剂     5.223kg
重复实施例1的方法。将第一挤出物压延为厚度0.20mm。将有机润滑剂挥发掉,并将挤出物在拉幅机架中进行处理。将物料在纵向拉伸5%,并且横向拉伸从127mm至1.96m(1,443%)。将微孔膜卷成卷并测量其厚度约为0.127mm。将微孔膜卷进行修整,然后将其切成小卷,每个约为23cm宽。
将4号混和物如前面物料一样进行挤压。在进入压延设备之前,将3号混和物的微孔板展开铺到4号混和物的部分饱和的料带上。将这两种物料一起压延至厚度0.10mm。然后处理挤出物以除去有机润滑剂,并将其重新卷成卷。如实施例1,该双层挤出物与常规方法得到的材料难以区分,因为没有双层结构的标记。
然后将双层挤出物用拉幅机架进行处理,使其纵向拉伸为75%,横向拉伸从114mm至1.96m(1,619%)。升高最终加热区的温度以实现烧结。所得到的微孔板材外表均一,测得厚度约为0.025mm,并且无肉眼可见的孔。
该实施例描述了一种双层膜,其中两层膜有相同的聚合物组成。但是,其中一层(第一层)膨胀的程度比另一层大。下表描述了每层的膨胀百分比:
                         表III
     最初膨胀         总膨胀
    纵向   横向   纵向   横向
    第一层     5%   1,443%   84%   26,453%
    第二层     -   -   75%   1.619%
膨胀百分率=100×[(最终长度一起始长度)/起始长度]例如:100×[(1,960-127)/127]=1,443总膨胀百分率=100×[(1+膨胀率1)×(1+膨胀率2)]例如:100×[(1+14.40)×(1+16.19)]=26,473实施例3: 相同的聚合物树脂;不同的挤出物组成;不同的膨胀条件
将部分3号混和物的挤出物用拉幅机架进行处理,得到线性拉伸为400%,横向拉伸从102mm至1.96m(1,822%)。所得到的微孔膜非常薄(0.10mm),但却没有孔。然后切割该物料并且用设定值为0.10mm的压延机将其叠加至4号混和物的部分饱和的挤出物上。除去有机润滑剂,然后将双层挤出物在压延机中处理,得到纵向伸为9%,横向拉伸从51mm至2.4m(4,606%)。如前面的实施例,将最终加热区的温度升高以实现烧结。所得到的微孔膜外表面均一,测量厚度约为0.08mm,并且无孔。
每层的膨胀百分率如下:
                   表IV
   最初膨胀     总膨胀
纵向 横向 纵向 横向
第一层 400% 1,882% 545% 90,449%
第二层 - -   9% 4,606%
实施例4: 相同的聚合物树脂;不同的挤出物组成;不同的膨胀条件
重复实施例3,但是第一挤出物拉伸800%而非400%。将0.10厚的物料叠加至4号混和物的挤出生成物上,纵向伸9%,横向拉伸4,606%,并进行烧结。所得到的微孔膜外表均一,无孔。表V给出了每层膜的膨胀量。
                           表V
     最初膨胀         总膨胀
  纵向     横向     纵向     横向
  第一层   800%     5%     981%     90,442%
  第二层   -     -     9%     4,606%
实施例5: 三层结构;相同聚合物树脂;不同的挤出物组成
按照现有的技术制备下列组份的混和物:
                         表VI
    5号混和物     数量
    Cd-123 FluonPTFE树脂(美国的ICI)     27.2kg
    石蜡溶剂     5.45kg
    6号混和物     数量
    Cd-123 FluonPTFE树脂(美国的ICI)     27.2kg
    石蜡溶剂     5.223kg
    7号混和物     数量
    Cd-123 FluonPTFE树脂(美国的ICI)     27.2kg
    石蜡溶剂     7.35kg
将每种混和物分别进行挤压,并且压延至0.51mm。将每种部分饱和的挤出物料带累积到辊子上以备后续加工之用。将三种料带叠在一起安装到架子上,6号混和物的料带于中间。将每层展开并通过设定值为0.18mm的平行的压延机设备送回。将所得到的物料通过一系列加热轧辊以除去有机润滑剂,并将它们重新卷成卷。
用拉幅机架设备处理三层挤出料带,纵向拉伸是100%,横向拉伸从114.3mm至1.52m(1,233%)。升高最终加热区的温度以实现烧结。所得到的微孔膜测定厚度约为17.8微米。

Claims (3)

1.生产微孔膜的方法,所述方法包含的步骤有:
将被润滑剂部分饱和的第一高分子组合物挤压成料带,
将被润滑剂部分饱和的相同或不同组成的第二高分子组合物挤压成料带,
在低于任一料带材料的熔点温度之下将所述第一料带压延粘接到所述第二料带上,
将所述润滑剂从料带中挥发出来,
拉伸所述层状料带以产生微孔膜,以及
加热上述的微孔膜至其晶体熔点以上。
2.生产微孔膜的方法,所述方法包含的步骤有:
将被润滑剂部分饱和的第一高分子组合物挤压成料带,
将所述料带沿着至少一个方向进行定向,
将被润滑剂部分饱和的相同的或不同组成的第二高分子组合物挤压成料带,
在低于任一料带材料的熔点温度之下将所述第一料带压延粘接到所述第二料带上,
将所述润滑剂从料带中挥发出来,以及
拉伸所述层状料带以产生微孔膜。
3.生产微孔膜的方法,所述方法包含的步骤有:
将被润滑剂部分饱和的第一高分子组合物挤压成料带,
将所述第一料带沿着至少一个方向进行定向,
将被润滑剂部分饱和的相同的或不同组成的第二高分子组合物挤压成料带,
在低于任一料带材料的熔点温度之下将所述第一料带压延粘接到第二料带上,
将所述润滑剂从料带中挥发出来,
拉伸所述层状料带以产生微孔膜,以及
加热微孔膜至其晶体熔点以上。
CN01139677A 1995-09-05 2001-12-05 原位产生的具有层状孔结构的微孔膜生产方法 Pending CN1403269A (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US08/523,278 US6235377B1 (en) 1995-09-05 1995-09-05 Microporous membrane with a stratified pore structure created in situ and process
US08/523,278 1995-09-05

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
CN96196775A Division CN1092561C (zh) 1995-09-05 1996-09-05 原位产生的具有层状孔结构的微孔膜及生产方法

Publications (1)

Publication Number Publication Date
CN1403269A true CN1403269A (zh) 2003-03-19

Family

ID=24084355

Family Applications (2)

Application Number Title Priority Date Filing Date
CN96196775A Expired - Fee Related CN1092561C (zh) 1995-09-05 1996-09-05 原位产生的具有层状孔结构的微孔膜及生产方法
CN01139677A Pending CN1403269A (zh) 1995-09-05 2001-12-05 原位产生的具有层状孔结构的微孔膜生产方法

Family Applications Before (1)

Application Number Title Priority Date Filing Date
CN96196775A Expired - Fee Related CN1092561C (zh) 1995-09-05 1996-09-05 原位产生的具有层状孔结构的微孔膜及生产方法

Country Status (12)

Country Link
US (2) US6235377B1 (zh)
EP (1) EP1019238B1 (zh)
JP (1) JPH11512349A (zh)
KR (1) KR19990044423A (zh)
CN (2) CN1092561C (zh)
AU (1) AU7017296A (zh)
BR (1) BR9610467A (zh)
CA (1) CA2231270A1 (zh)
DE (1) DE69627720T2 (zh)
ES (1) ES2197952T3 (zh)
MX (1) MX9801740A (zh)
WO (1) WO1997009167A1 (zh)

Families Citing this family (54)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6139883A (en) * 1995-07-29 2000-10-31 J. R. Crompton Limited Porous web material
GB9702857D0 (en) 1997-02-12 1997-04-02 Crompton J R Plc Porous web material
GB9723140D0 (en) * 1997-11-04 1998-01-07 British Nuclear Fuels Plc Improvements in and relating to material separations
US6846382B1 (en) 1998-02-04 2005-01-25 Ahlstrom Windsor Locks, Llc Nonwoven web material for infusion packaging and method of making same
EP1153969B1 (en) * 1998-10-01 2004-02-25 Tonen Chemical Corporation Microporous polyolefin film and process for producing the same
US7083849B1 (en) 1999-06-04 2006-08-01 3M Innovative Properties Company Breathable polymer foams
US6342294B1 (en) * 1999-08-12 2002-01-29 Bruce G. Ruefer Composite PTFE article and method of manufacture
US6770086B1 (en) * 2000-11-02 2004-08-03 Scimed Life Systems, Inc. Stent covering formed of porous polytetraflouroethylene
US8283029B2 (en) * 2001-08-13 2012-10-09 Clopay Plastic Products Company, Inc. Multilayer microporous films and composites for barrier protective materials, and methods
TWI296571B (en) * 2001-08-13 2008-05-11 Clopay Corp Mulyilayer microporous films and methods
US6790213B2 (en) 2002-01-07 2004-09-14 C.R. Bard, Inc. Implantable prosthesis
US8895139B2 (en) * 2003-03-27 2014-11-25 Robert Roberts Isotropic nano crystallites of polytetrafluoroethylene (PTFE) resin and products thereof that are biaxially planar oriented and form stable
JP4101100B2 (ja) * 2003-04-02 2008-06-11 宇明泰化工股▲ふん▼有限公司 衣料用非対称性多孔質ポリテトラフルオロエチレン膜
JP3795027B2 (ja) * 2003-04-02 2006-07-12 宇明泰化工股▲ふん▼有限公司 フィルター用非対称性多孔質ポリテトラフルオロエチレン膜
PL1687133T3 (pl) * 2003-11-04 2011-05-31 Porex Corp Porowate materiały kompozytowe oraz sposoby ich wytwarzania i zastosowania
US20060292324A1 (en) * 2004-03-26 2006-12-28 Robert Roberts Uniaxially and biaxially-oriented polytetrafluoroethylene structures
CN101065424B (zh) 2004-11-24 2011-09-14 唐纳森公司 Ptfe薄膜
EP1833597B1 (en) * 2004-12-22 2011-03-23 Entegris, Inc. Multilayer porous membrane and process of manufacture
US7306729B2 (en) * 2005-07-18 2007-12-11 Gore Enterprise Holdings, Inc. Porous PTFE materials and articles produced therefrom
KR20150001712A (ko) 2006-04-03 2015-01-06 엔테그리스, 아이엔씨. 대기압 마이크로파 플라즈마 처리된 다공성 막
JP2009536573A (ja) * 2006-05-09 2009-10-15 ポーレックス コーポレイション 多孔質複合膜材料及びその適用
JP5204384B2 (ja) * 2006-05-19 2013-06-05 富士フイルム株式会社 結晶性ポリマー微孔性膜とその製造方法、および濾過用フィルター
US9795897B2 (en) * 2006-11-08 2017-10-24 Donaldson Company, Inc. Systems, articles, and methods for removing water from hydrocarbon fluids
US7811359B2 (en) * 2007-01-18 2010-10-12 General Electric Company Composite membrane for separation of carbon dioxide
SG182176A1 (en) * 2007-07-03 2012-07-30 Sumitomo Elec Fine Polymer Inc Flat sheet membrane element for filtration and flat sheet membrane filtration module
JP5220369B2 (ja) * 2007-09-04 2013-06-26 富士フイルム株式会社 結晶性ポリマー微孔性膜及びその製造方法、並びに濾過用フィルタ
JP4863970B2 (ja) * 2007-11-16 2012-01-25 富士フイルム株式会社 結晶性ポリマー微孔性膜及びその製造方法、並びに濾過用フィルタ
JP4937977B2 (ja) * 2008-09-02 2012-05-23 富士フイルム株式会社 結晶性ポリマー微孔性膜及びその製造方法、並びに濾過用フィルタ
CA2739279C (en) 2008-10-03 2017-07-25 C.R. Bard, Inc. Implantable prosthesis
US8267681B2 (en) 2009-01-28 2012-09-18 Donaldson Company, Inc. Method and apparatus for forming a fibrous media
KR20110120202A (ko) * 2009-02-16 2011-11-03 스미토모덴코파인폴리머 가부시키가이샤 다공질 복층 필터 및 그 제조 방법
US8118910B2 (en) * 2009-03-23 2012-02-21 General Electric Company Layered filtration membrane and methods of making same
JP5518442B2 (ja) * 2009-11-25 2014-06-11 富士フイルム株式会社 濾過フィルタ用結晶性ポリマー微孔性膜及びその製造方法、並びに濾過用フィルタ
JP5528070B2 (ja) * 2009-11-25 2014-06-25 富士フイルム株式会社 濾過フィルタ用結晶性ポリマー微孔性膜及びその製造方法、並びに濾過用フィルタ
US8728369B2 (en) 2009-12-30 2014-05-20 3M Innovative Properties Company Method of making an auxetic mesh
BR112012016094A2 (pt) 2009-12-30 2016-08-16 3M Innovative Properties Co respirador com peça facial filtrante tendo uma malha auxética no corpo da máscara
EP2519327B1 (en) * 2009-12-30 2016-04-06 3M Innovative Properties Company Molded auxetic mesh and manufacturing method
US9944044B2 (en) * 2010-05-06 2018-04-17 W. L. Gore & Associates, Inc. Contamination resistant air permeable fabric laminate and garments made therefrom
JP2012011369A (ja) * 2010-06-01 2012-01-19 Fujifilm Corp 結晶性ポリマー微孔性膜及びその製造方法、並びに濾過用フィルタ
US9132616B2 (en) * 2010-08-31 2015-09-15 Bha Altair, Llc Multi-layer composite membrane materials and methods therefor
BR112013018772B1 (pt) 2011-01-28 2021-01-19 Donaldson Company, Inc. método e aparelho para formação de meios fibrosos
CN103328720B (zh) 2011-01-28 2016-12-07 唐纳森公司 用于形成纤维介质的方法和设备
KR101907725B1 (ko) * 2011-09-23 2018-10-12 더블유.엘. 고어 앤드 어소시에이트스, 인코포레이티드 표면 개질된 플루오로 중합체 막 및 이의 제조 방법
US20130112621A1 (en) * 2011-11-03 2013-05-09 Lei Zheng Water filtration article and related methods
CN103101195B (zh) * 2013-01-18 2015-04-29 浙江国泰密封材料股份有限公司 一种软性密封板用ptfe膜的制备方法
CN103102626B (zh) * 2013-01-18 2015-06-17 浙江国泰密封材料股份有限公司 一种自粘结软性ptfe膜带的制备方法
US9573339B2 (en) 2013-01-18 2017-02-21 W. L. Gore & Associates, Inc. Low gloss, air permeable, abrasion resistant, printable laminate containing an asymmetric membrane and articles made therefrom
JP6161124B2 (ja) * 2013-03-29 2017-07-12 富士フイルム株式会社 酸性ガス分離複合膜の製造方法及び酸性ガス分離膜モジュール
CN104096489B (zh) * 2013-12-24 2016-01-06 广州中国科学院先进技术研究所 一种无机-有机功能化聚四氟乙烯微孔膜的制备方法
CN103937131B (zh) * 2014-03-26 2016-08-24 上海同晋环保科技有限公司 氟碳膜及其制备方法
CN105013349B (zh) * 2014-04-22 2018-02-23 四川百途环保材料科技有限公司 一种超疏水聚四氟乙烯膜的制备方法
US9932429B2 (en) * 2014-07-29 2018-04-03 W. L. Gore & Associates, Inc. Method for producing porous articles from alternating poly(ethylene tetrafluoroethylene) and articles produced therefrom
US10987638B2 (en) * 2015-06-19 2021-04-27 W. L. Gore & Associates, Inc. Asymmetric polytetrafluoroethylene composite having a macro-textured surface and method for making the same
KR20230128405A (ko) * 2018-10-04 2023-09-04 더블유.엘. 고어 앤드 어소시에이트스, 인코포레이티드 치수 안정성을 갖는 비소결의 팽창된 폴리테트라플루오로에틸렌 복합 막

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3315020A (en) 1962-03-21 1967-04-18 Gore & Ass Process for preparing biaxially fibrillated sheets
CA962021A (en) 1970-05-21 1975-02-04 Robert W. Gore Porous products and process therefor
US3975455A (en) * 1973-08-03 1976-08-17 Dow Corning Corporation Altering gas permeabilities of polymeric material
JPS603842B2 (ja) * 1976-09-03 1985-01-31 住友電気工業株式会社 非対称孔径薄膜材料とその製造方法
US4385093A (en) * 1980-11-06 1983-05-24 W. L. Gore & Associates, Inc. Multi-component, highly porous, high strength PTFE article and method for manufacturing same
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
US5157058A (en) 1987-01-05 1992-10-20 Tetratec Corporation Microporous waterproof and moisture vapor permeable structures, processes of manufacture and useful articles thereof
US5066683A (en) 1987-01-05 1991-11-19 Tetratec Corporation Microporous waterproof and moisture vapor permeable structures, processes of manufacture and useful articles thereof
EP0274010B1 (en) * 1987-01-09 1992-01-29 Nichias Corporation Use of a composition for a gasket
US4863604A (en) * 1987-02-05 1989-09-05 Parker-Hannifin Corporation Microporous asymmetric polyfluorocarbon membranes
US4832009A (en) 1987-12-23 1989-05-23 Bio Med Sciences, Inc. Semi-interpenetrating network polymer backsheet bandage
US4863792A (en) * 1988-10-14 1989-09-05 Minnesota Mining And Manufacturing Company Multi-layer laminates of microporous films
US5094895A (en) * 1989-04-28 1992-03-10 Branca Phillip A Composite, porous diaphragm
EP0527913B2 (en) * 1990-05-09 2000-07-05 Memtec Limited Method for making pvdf hollow fibre membranes

Also Published As

Publication number Publication date
BR9610467A (pt) 2000-05-09
WO1997009167A1 (en) 1997-03-13
AU7017296A (en) 1997-03-27
EP1019238A1 (en) 2000-07-19
KR19990044423A (ko) 1999-06-25
MX9801740A (es) 1998-11-30
ES2197952T3 (es) 2004-01-16
CN1195315A (zh) 1998-10-07
DE69627720D1 (de) 2003-05-28
JPH11512349A (ja) 1999-10-26
CN1092561C (zh) 2002-10-16
US6235377B1 (en) 2001-05-22
CA2231270A1 (en) 1997-03-13
DE69627720T2 (de) 2004-04-29
EP1019238B1 (en) 2003-04-23
US20020045041A1 (en) 2002-04-18
EP1019238A4 (en) 2000-07-19

Similar Documents

Publication Publication Date Title
CN1092561C (zh) 原位产生的具有层状孔结构的微孔膜及生产方法
WO1997009167A9 (en) Microporous membrane with a stratified pore structure created in situ and process
US6712919B2 (en) Composite PTFE article method of manufacture
US4973609A (en) Porous fluoropolymer alloy and process of manufacture
DE69630521T2 (de) Verfahren zur herstellung von porösen fluoropolymerfolien
US3953566A (en) Process for producing porous products
US4096227A (en) Process for producing filled porous PTFE products
US7976751B2 (en) Expanded porous polytetrafluoroethylene film having elastic recovery property in thickness-wise direction of the film, production process thereof, and use of the porous film
DE2417901A1 (de) Poroeses material
US20060292324A1 (en) Uniaxially and biaxially-oriented polytetrafluoroethylene structures
CN103786349A (zh) 一种制备多层聚烯烃微孔膜的方法
US7060210B2 (en) Method of processing colloidal size polytetrafluoroethylene resin particles to produce biaxially-oriented structures
KR102031506B1 (ko) 마크로 텍스쳐 표면을 갖는 비대칭 폴리테트라플루오로에틸렌 복합체 및 이의 제조 방법
KR20150079108A (ko) Ptfe 중공사막 및 그 제조 방법
KR20140074755A (ko) 다층 ptfe 분리막 및 이의 제조방법
KR20130114906A (ko) 발포제를 이용한 다공성 ptfe 분리막의 제조방법
AU1949300A (en) Microporous membrane with a stratified pore structure created in situ and process
US7211210B2 (en) Dry fibrillated PTFE film and its method of manufacture
KR102308711B1 (ko) 에어필터용 고분자 필름 및 이의 제조 방법
KR20210061777A (ko) 불소계 수지 다공성 막 및 이의 제조 방법
KR102267597B1 (ko) 불소계 수지 다공성 막 및 이의 제조방법
KR20140074694A (ko) 다공성 ptfe 분리막 및 그 제조방법
CN116806164A (zh) 空气过滤器滤材、空气过滤器滤材的制造方法、口罩用滤材及褶裥状口罩用滤材
KR20190061921A (ko) 불소계 수지 다공성 막 및 이의 제조 방법
KR20130097923A (ko) 발포제를 이용한 다공성 ptfe 중공사 분리막의 제조방법

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C02 Deemed withdrawal of patent application after publication (patent law 2001)
WD01 Invention patent application deemed withdrawn after publication