CN107227536A - Compliance microporous fibre and the braided fabric containing the fiber - Google Patents

Compliance microporous fibre and the braided fabric containing the fiber Download PDF

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Publication number
CN107227536A
CN107227536A CN201710339191.8A CN201710339191A CN107227536A CN 107227536 A CN107227536 A CN 107227536A CN 201710339191 A CN201710339191 A CN 201710339191A CN 107227536 A CN107227536 A CN 107227536A
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CN
China
Prior art keywords
fiber
fabric
eptfe
braided fabric
times
Prior art date
Application number
CN201710339191.8A
Other languages
Chinese (zh)
Inventor
D·J·迈纳
R·B·迈纳
Original Assignee
W.L.戈尔及同仁股份有限公司
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
Priority to US14/029,250 priority Critical patent/US20150079865A1/en
Priority to US14/029,250 priority
Application filed by W.L.戈尔及同仁股份有限公司 filed Critical W.L.戈尔及同仁股份有限公司
Priority to CN201480062862.5A priority patent/CN105723022B/en
Publication of CN107227536A publication Critical patent/CN107227536A/en

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Classifications

    • DTEXTILES; PAPER
    • D03WEAVING
    • D03DWOVEN FABRICS; METHODS OF WEAVING; LOOMS
    • D03D15/00Woven fabrics characterised by the material or construction of the yarn or other warp or weft elements used
    • D03D15/0083Woven fabrics characterised by the material or construction of the yarn or other warp or weft elements used using threads having a particular sectional shape
    • AHUMAN NECESSITIES
    • A41WEARING APPAREL
    • A41DOUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
    • A41D19/00Gloves
    • A41D19/0006Gloves made of several layers of material
    • AHUMAN NECESSITIES
    • A41WEARING APPAREL
    • A41DOUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
    • A41D31/00Materials specially adapted for outerwear
    • A41D31/02Layered materials
    • AHUMAN NECESSITIES
    • A41WEARING APPAREL
    • A41DOUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
    • A41D31/00Materials specially adapted for outerwear
    • A41D31/04Materials specially adapted for outerwear characterised by special function or use
    • A41D31/10Impermeable to liquids, e.g. waterproof; Liquid repellent
    • A41D31/102Waterproof and breathable
    • AHUMAN NECESSITIES
    • A43FOOTWEAR
    • A43BCHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
    • A43B7/00Footwear with health or hygienic arrangements
    • A43B7/12Special watertight footwear
    • A43B7/125Special watertight footwear provided with a vapour permeable member, e.g. a membrane
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01DMECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00Formation of filaments, threads, or the like
    • D01D5/24Formation of filaments, threads, or the like with a hollow structure; Spinnerette packs therefor
    • D01D5/247Discontinuous hollow structure or microporous structure
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01DMECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00Formation of filaments, threads, or the like
    • D01D5/253Formation of filaments, threads, or the like with a non-circular cross section; Spinnerette packs therefor
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/02Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/08Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of halogenated hydrocarbons
    • D01F6/12Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of halogenated hydrocarbons from polymers of fluorinated hydrocarbons
    • DTEXTILES; PAPER
    • D03WEAVING
    • D03DWOVEN FABRICS; METHODS OF WEAVING; LOOMS
    • D03D1/00Woven fabrics designed to make specified articles
    • D03D1/0035Protective fabrics
    • DTEXTILES; PAPER
    • D03WEAVING
    • D03DWOVEN FABRICS; METHODS OF WEAVING; LOOMS
    • D03D13/00Woven fabrics characterised by the special disposition of the warp or weft threads, e.g. with curved weft threads, with discontinuous warp threads, with diagonal warp or weft
    • D03D13/008Woven fabrics characterised by the special disposition of the warp or weft threads, e.g. with curved weft threads, with discontinuous warp threads, with diagonal warp or weft characterised by weave density or surface weight
    • DTEXTILES; PAPER
    • D03WEAVING
    • D03DWOVEN FABRICS; METHODS OF WEAVING; LOOMS
    • D03D15/00Woven fabrics characterised by the material or construction of the yarn or other warp or weft elements used
    • D03D15/0083Woven fabrics characterised by the material or construction of the yarn or other warp or weft elements used using threads having a particular sectional shape
    • D03D15/0088Flat threads
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/224Esters of carboxylic acids; Esters of carbonic acid
    • D06M13/236Esters of carboxylic acids; Esters of carbonic acid containing halogen atoms
    • AHUMAN NECESSITIES
    • A41WEARING APPAREL
    • A41DOUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
    • A41D2500/00Materials for garments
    • A41D2500/20Woven
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16Synthetic fibres, other than mineral fibres
    • D06M2101/18Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/22Polymers or copolymers of halogenated mono-olefins
    • DTEXTILES; PAPER
    • D10INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10BINDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2321/00Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D10B2321/04Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polymers of halogenated hydrocarbons
    • D10B2321/042Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polymers of halogenated hydrocarbons polymers of fluorinated hydrocarbons, e.g. polytetrafluoroethene [PTFE]
    • DTEXTILES; PAPER
    • D10INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10BINDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2501/00Wearing apparel
    • D10B2501/04Outerwear; Protective garments
    • 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
    • Y10T428/29Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913Rod, strand, filament or fiber
    • Y10T428/2922Nonlinear [e.g., crimped, coiled, etc.]
    • 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
    • Y10T428/29Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913Rod, strand, filament or fiber
    • Y10T428/2933Coated or with bond, impregnation or core
    • Y10T428/2935Discontinuous or tubular or cellular core
    • 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
    • Y10T428/29Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913Rod, strand, filament or fiber
    • Y10T428/2973Particular cross section
    • Y10T428/2975Tubular or cellular
    • 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
    • Y10T442/00Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
    • Y10T442/2262Coating or impregnation is oil repellent but not oil or stain release
    • Y10T442/227Fluorocarbon containing
    • 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
    • Y10T442/00Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/30Woven fabric [i.e., woven strand or strip material]
    • Y10T442/3065Including strand which is of specific structural definition
    • Y10T442/3089Cross-sectional configuration of strand material is specified
    • Y10T442/3106Hollow strand material

Abstract

The present invention provides expanded polytetrafluoroethyl,ne (expanded polytetrafluoroethylene, ePTFE) single fiber silk fiber and by the fibroplastic braided fabrics of ePTFE.The ePTFE fibers have essentially rectangular construction, and density is below about 1.0g/cc and aspect ratio is more than 15.In addition, ePTFE fibers are micropores, and with node and fibrillar structure.EPTFE fibers can be woven into fabric, and first fiber need not be twisted.Polymer film and/or yarn fabric can be laminated in the braided fabric to manufacture laminate.EPTFE braided fabrics have high moisture percent of pass (highly-breathable) and high water entry pressure (waterproof) simultaneously.The braided fabric is plain, soft and can dangled, and makes it particularly suited for clothes, gloves and footwear applications.Processing can be applied on the surface of ePTFE fibers and/or braided fabric to assign one or more required functions, such as oleophobic property.

Description

Compliance microporous fibre and the braided fabric containing the fiber

The application is that international application no is that PCT/US2014/051420, international filing date are in August, 2014 PCT of 18 days International application enters national applications number after the Chinese stage and " compliance microporous fibre and contained for 201480062862.5 entitled Have the braided fabric of the fiber " Chinese patent application divisional application.

Invention field

The present invention relates generally to compliance microporous fibre, more particularly to the height with node and fibrillar structure The compliance microporous fibre of gas permeability.Braided fabric containing compliance microporous fibre is also provided.

Background of invention

The clothes of water-proof breathable properties are well-known in the art.These clothes are generally made up of multilayer, in the multilayer Each layer is respectively provided with specific function.For example, outer layer fabric layer, waterproof layer, ventilative film layer and internal layer yarn fabric can be used in clothes Constitute.Outer layer fabric layer and internal layer fabric layer provide protection to ventilative film layer.But, addition outer fabric layer and internal layer Tissue layer can not only increase the weight of clothing item, and the material with potential high water absorbing capacity can be also produced on the outer surface.Outer layer Absorption of the tissue layer to water can form by fabric and lead to the thermal conductivity of wearer and the temperature path of water.In dress In the case that person is in cold environment, this is probably unfavorable, and cold can be transferred to the body of wearer.In addition, water absorbs The condensation of inner can be caused, enable a wearer to feel moist.In addition, the color of outer fabric after absorbing water may fade or Deepen, so as to damage the aesthetic appearance of clothes.In addition, according to outer fabric, fabric may need long drying time in itself, Compel to enable a wearer to stand the longer time by water sucting belt Lai inconvenience.In addition, for internal layer and the fiber of the fabrics in general of outer layer It is made up of many filament fibers so that water and/or pollutant can be present between fibril.In addition, for gas permeability, many fibrils Fiber is loosely-packed in fabric, therefore the space that water can undesirably between fiberfill fibers.

Therefore, there is demand to following fiber in this area:It is used for making knitting for the braiding of highly-breathable clothes Thing, with high water entry pressure and with low water absorption.

The content of the invention

It is an object of the invention to provide following braided fabric:It includes warp-wise and broadwise expanded polytetrafluoroethyl,ne (ePTFE) fiber, the fiber has the microcellular structure of node and fibrillation, wherein, the width of ePTFE fibers, which exceedes, to be based on The width for propping up and distributing to ePTFE fibers through branch or latitude of braided fabric.The difference of the width cause ePTFE fibers its from Folded on body, to meet the braiding spacing between warp fiber and the intersection of weft fiber.EPTFE fibers can be single fiber Silk fiber.The density of the ePTFE fibers is below about 1.2 grams/cc and aspect ratio is greater than about 15, with essentially square The cross-sectional configuration of shape.Advantageously, ePTFE braided fabrics have high moisture vapor transmission rate and high water entry pressure simultaneously.Tool For body, the moisture vapor transmission rate of the braided fabric is greater than about 10,000 gram/m/24 hours, and water entry pressure Greater than about 1kPa.Therefore, the braided fabric is highly-breathable, with low water absorption and height waterproof.

It is another object of the present invention to provide following braided fabric:It includes multiple warp fibers and weft fiber, Wherein warp fiber and weft fiber each include expanded polytetrafluoroethyl,ne fiber, the density of the polytetrafluoroethylene fibre Below about 1.2 grams/cc, and with essentially rectangular cross-sectional configuration.EPTFE fibers can be single fiber silk fiber. The aspect ratio of at least one of the warp-wise ePTFE fibers and broadwise ePTFE fibers can be greater than about 15.Show at least one In example property embodiment, the width of ePTFE fibers is more than the weft yarn quantity on the braided fabric per inch.Further, it is described The mean rigidity of braided fabric is less than about 300g and water absorption rate is less than 30gsm.Warp fiber and weft fiber can have fluorination third Olefin(e) acid ester coating, to cause braided fabric to be in oleophobic property.Fluoro-containing copolymer film or other functional membranes or protective layer can be consolidated It is scheduled on the side opposite with fluorinated acrylic ester coating of braided fabric.In some embodiments, yarn fabric can be fixed on To form laminate on fluoro-containing copolymer film.In other embodiments, fluorine-containing it can will gather in the case where being not coated by coating Compound film and/or yarn fabric are fixed on braided fabric.

It is a further object to provide following braided fabric:It includes expanded polytetrafluoroethyl,ne fiber Warp fiber and weft fiber, the aspect ratio of the fiber is greater than about 15 and the basic cross-sectional configuration having for rectangle.Institute The water entry pressure greater than about 1kPa of braided fabric is stated, and moisture vapor transmission rate is greater than about 10,000 gram/m/24 hours. EPTFE fibers can be single fiber silk fiber.In addition, thickness is less than about 100 microns, width before braiding before the braiding of the fiber It is less than about 1.0 grams/cc less than about density before 4.0mm, and braiding.Further, the ePTFE fibers have node and Fibrillar structure, its interior joint is connected with each other by limiting the fibrillation of the path through the fiber.The fibrillation Length can be about 5 microns-about 120 microns.

Another object of the present invention also resides in the following braided fabric of offer:It includes warp-wise and broadwise fluoropolymer Fibres, wherein at least one of warp-wise fluorine-contained polymerisate fibre and broadwise fluorine-contained polymerisate fibre present long along fiber The folded structure of degree.In at least one illustrative embodiments, fluorine-contained polymerisate fibre is ePTFE fibers, and its density is less than About 1.2 grams/cc and essentially rectangular construction.In the exemplary embodiment, it is close before the braiding of the ePTFE fibers Degree is below about 0.85 gram/cc.It is small that the moisture vapor transmission rate of the braided fabric is greater than about 10,000 grams/m/24 When, and water entry pressure is greater than about 1kPa.In addition, the tearing strength of the braided fabric is at least 30N and mean rigidity is less than About 300g.In at least one illustrative embodiments, the width of fluorine-contained polymerisate fibre, which exceedes, is based on the braided fabric Propped up through branch or latitude and distribute to the width of fluorine-contained polymerisate fibre.

Another object of the present invention also resides in the following braided fabric of offer:It includes compliance warp-wise and broadwise contains Fluoropolymer fibers, wherein at least one of warp fiber and weft fiber have the node for the path for forming perforating fiber And fibrillar structure.The length of the fibrillation can be about 5 microns-about 120 microns.In at least one embodiment, contain Fluoropolymer fibers are ePTFE fibers, and density is in other embodiments, low below about 1.0 grams/cc before it weaves In about 0.85 gram/cc.The compliance of the fiber can make fiber itself crimp and/or fold, to meet braiding structure Make the braiding spacing between warp fiber and the intersection of weft fiber.In addition, functional membrane or protective layer, such as fluorine-containing poly- Compound film, can be fixed on ePTFE braided fabrics.In some embodiments, yarn fabric is fixed on fluoropolymer To form laminate on film.

It is another object of the present invention to provide the single fiber silk fiber including expanded polytetrafluoroethyl,ne.EPTFE single fibers The density of silk fiber is less than or equal to about 1.0 grams/cc, and thickness is below about 100 microns, and width is below about 4.0mm, indulges Horizontal ratio greater than about 15, and essentially rectangular cross-sectional configuration.In addition, the toughness of the fiber is greater than about 1.6cN/dtex, fracture Intensity is at least about 1.5N.Can have fluorinated acrylic ester coating, or other oleophobic properties on the ePTFE single fibers silk fiber Processing.In addition, the ePTFE single fibers silk fiber has node and fibrillation construction, its interior joint and fibrillation, which are limited, runs through institute State the path of fiber.The length of the fibrillation can be about 5 microns-about 120 microns.Further, the ePTFE monofilaments Fiber is compliance, so that in knitting structure, ePTFE single fiber silk fibers fold to meet braided fabric on itself Braiding spacing between middle warp fiber and the intersection of weft fiber.This ePTFE single fibers silk fiber is used for the example of the present invention In property embodiment, to form following braided fabric:It can be eventually for the high moisture percent of pass of needs and high water entry pressure The product of (i.e. highly-breathable and height waterproof).

It is one of the advantages of the invention that in the case that even if ePTFE fibers are close weave, ePTFE braided fabrics With highly-breathable and high water entry pressure.

The present invention another advantage is that, ePTFE fibers can by close weave into highly breathable but have low latitude air infiltration The braided fabric of saturating rate.

It is also an advantage of the invention that braided fabric is plain (quiet), softness and can dangled.

The present invention another advantage is that, the high aspect ratio of ePTFE fibers causes the weight per unit area of fabric to become It is low, it can be easier and more efficiently remold shape, and can be in filling density (picks per inch) and through close (ends per Inch) high water proofing property is obtained in smaller braided fabric.

The characteristic of the present invention is that the ePTFE fibers itself are crimped and/or folded, to meet in braided fabric Braiding spacing between warp fiber and the intersection of weft fiber.

The characteristic of the present invention is also resided in, and the braided fabric being made up of ePTFE fibers has smooth or substantially smooth braiding Style, and with corresponding smooth surface.

The characteristic of the present invention is also resided in, and ePTFE fibers have essentially rectangular cross-sectional configuration, particularly in braiding Before.

Brief Description Of Drawings

Described in detail in view of of the invention below, especially in conjunction with accompanying drawing, can more clearly understand that the present invention's is excellent Point, wherein:

Fig. 1 is fine in 1000 times of exemplary ePTFE shot under amplifying according to an exemplary embodiment of the present invention The scanning electron micrograph (SEM) of the top surface of dimension;

Fig. 2 is the scanning electron micrograph in the side of the ePTFE fibers shown in 1000 times of Fig. 1 shot under amplifying;

Fig. 3 is sweeping for the top surface of 2/2 twill weave fabric of the fiber shown in the Fig. 1 shot under 150 times of amplifications Retouch electron micrograph;

Fig. 4 is the scanning electron micrograph in the side of the braided fabric shown in 150 times of Fig. 3 shot under amplifying;

Fig. 5 is compiled in 2/2 twill with fluorinated acrylic ester coating thereon shown in 150 times of Fig. 3 shot under amplifying The scanning electron micrograph of the top surface of woven fabric;

Fig. 6 is the scanning electron micrograph in the side of the braided fabric shown in 150 times of Fig. 5 shot under amplifying;

Fig. 7 is in the 2/2 twill weave fabric for being laminated with ePTFE membrane thereon shown in 150 times of Fig. 5 shot under amplifying Top surface scanning electron micrograph;

Fig. 8 is the scanning electron micrograph in the side of the product shown in 100 times of Fig. 7 shot under amplifying;

Fig. 9 is the scanning electron micrograph in the side of the fabric shown in 1000 times of Fig. 7 shot under amplifying;

Figure 10 is to be laminated in weaving according to what another illustrative embodiments of the present invention were shot under 150 times of amplifications The scanning electron micrograph of the top surface of braided fabric shown in Fig. 5 of thing;

Figure 11 is the scanning electron micrograph in the side of the product shown in 100 times of Figure 10 shot under amplifying;

Figure 12 is the scanning electron micrograph in the side of the product shown in 500 times of Figure 10 shot under amplifying;

Figure 13 is laminated with thereon according to what an exemplary embodiment of the present invention was shot under 150 times of amplifications The scanning electron micrograph of the top surface of the braided fabric of ePTFE membrane;

Figure 14 is the scanning electron micrograph in the side of the product shown in 100 times of Figure 13 shot under amplifying;

Figure 15 is the scanning electron micrograph in the side of the product shown in 300 times of Figure 13 shot under amplifying;

Figure 16 is in 150 times of plain weave fabrics shot under amplifying according to an exemplary embodiment of the present invention Top surface scanning electron micrograph;

Figure 17 is the scanning electron micrograph in the side of the fabric shown in 250 times of Figure 16 shot under amplifying;

Figure 18 is compiled in the plain weave with fluorinated acrylic ester coating thereon shown in 150 times of Figure 16 shot under amplifying The scanning electron micrograph of the top surface of woven fabric;

Figure 19 is the scanning electron micrograph in the side of the braided fabric shown in 250 times of Figure 18 shot under amplifying;

Figure 20 is to be laminated with ePTFE membrane according to what an exemplary embodiment of the present invention was shot under 150 times of amplifications With the scanning electron micrograph of the top surface of the braided fabric shown in Figure 16 of yarn fabric;

Figure 21 is the scanning electron micrograph at the side view visual angle of the product shown in 250 times of Figure 20 shot under amplifying;

Figure 22 be according to the present invention another illustrative embodiments 1000 times amplify under shoot it is exemplary The scanning electron micrograph of the top surface of ePTFE fibers;

Figure 23 is that the scanning electron microscopy in the side of the ePTFE fibers shown in 1000 times of Figure 22 shot under amplifying shines Piece;

Figure 24 is the 2/2 twill top surface in the ePTFE fibers shown in 150 times of Figure 22 shot under amplifying Scanning electron micrograph;

Figure 25 is the scanning electron micrograph in the side of the fabric shown in 200 times of Figure 24 shot under amplifying;

Figure 26 is compiled in the twill with fluorinated acrylic ester coating thereon shown in 150 times of Figure 16 shot under amplifying The scanning electron micrograph of the top surface of woven fabric;

Figure 27 is the scanning electron micrograph in the side of the fabric shown in 200 times of Figure 26 shot under amplifying;

Figure 28 is fine in 1000 times of exemplary ePTFE shot under amplifying according to the further embodiment of the present invention The scanning electron micrograph of the top surface of dimension;

Figure 29 is the scanning electron micrograph in the side of the fiber shown in 1000 times of Figure 28 shot under amplifying;

Figure 30 is at the top of 2/2 twill weave fabric of the ePTFE fibers shown in 150 times of Figure 26 shot under amplifying The scanning electron micrograph on surface;

Figure 31 is the scanning electron micrograph in the side of the fabric shown in 150 times of Figure 30 shot under amplifying;

Figure 32 is the scanning electron in the top surface of 1000 times of comparative ePTFE fibers of high density shot under amplifying Microphoto;

Figure 33 is that the scanning electron in the side of the braided fabric of the fiber shown in 1000 times of Figure 32 shot under amplifying shows Micro- photo;

Figure 34 is comparative 2/2 twill in 150 times of comparative high density ePTFE of utilization shot under amplifying fiber The scanning electron micrograph of the top surface of braided fabric;

Figure 35 is the scanning electron micrograph in the side of the fabric shown in 150 times of Figure 34 shot under amplifying;

Figure 36 is the scanning electron micrograph in the top surface of 1000 times of exemplary fibers shot under amplifying;

Figure 37 is the scanning electron micrograph in the side of the fiber shown in 1000 times of Figure 36 shot under amplifying;

Figure 38 is the scanning electricity in the top surface of the braided fabric of the fiber shown in 150 times of Figure 36 shot under amplifying Sub- microphoto;

Figure 39 is the scanning electron micrograph in the side of the fabric shown in 150 times of Figure 38 shot under amplifying;

Figure 40 is to depict to be folded into folded structure in knitting structure with the exemplary fibre in the space for adapting to distribute to fiber The schematic side view of dimension;

Figure 41 is to depict to be folded into folded structure in knitting structure with the exemplary fibre in the space for adapting to distribute to fiber The schematic top plan view of dimension;

Figure 42 is on the top of 150 times of schematic plain weave fabrics with 40 × 40 thread counts shot under amplifying The scanning electron micrograph on portion surface;

Figure 43 is the scanning electron micrograph in the side of the braided fabric shown in 150 times of Figure 42 shot under amplifying;

Figure 44 is the scanning electron micrograph in the side of the braided fabric shown in 300 times of Figure 42 shot under amplifying;

Figure 45 is the scanning electron micrograph in the side of the braided fabric shown in 400 times of Figure 42 shot under amplifying;

Figure 46 is that the scanning electron of the top surface of the comparative non-porous ePTFE fibers shot under 1000 times of amplifications shows Micro- photo;

Figure 47 is the scanning electron micrograph in the side of the fiber shown in 1000 times of Figure 46 shot under amplifying;

Figure 48 is the scanning electron micrograph in the braided fabric of the fiber shown in 150 times of Figure 46 shot under amplifying;

Figure 49 is the scanning electron micrograph in the side of the braided fabric shown in 150 times of Figure 48 shot under amplifying;

Figure 50 is on the top of the comparative braided fabric of 150 times of comparative high density ePTFE shot under amplifying fiber The scanning electron micrograph on portion surface;

Figure 51 is the scanning electron microscopy in the side surfaces of the braided fabric shown in 150 times of Figure 50 shot under amplifying Photo;And

Figure 52 is the scanning electron micrograph for illustrating the measurement of gap width.

Definition

Terms used herein " single fiber silk fiber " and " monofilament ePTFE fibers " are used to describe that fabric can be woven into Continuous or substantially continuous in itself ePTFE fibers.

Terms used herein " fiber " and " ePTFE fibers " include monofilament ePTFE fibers and multiple monofilaments The fiber of the fiber of ePTFE fibers, such as side-by-side configuration, the fiber of sheaf structure or twisting or other intertexture forms.

Terms used herein " compliance " and " compliance fiber " be used to describing itself can crimping and/or fold with Meet filling density (picks per between warp fiber and the intersection of weft fiber, by warp fiber and weft fiber Inch the braiding spacing) and/or through close (ends per inch) quantity determined.

" high water entry pressure " used herein is used to describe the braided fabric that water entry pressure is greater than about 1kPa.

Terms used herein " low water absorption " is used for the braided fabric for representing that water absorption rate is below about 50gsm.

Terms used herein " essentially rectangular construction " is used to represent with rectangle or approximate rectangular cross section, tool Have or the compliance porous fibre without circular edge or sharp edges (or sidepiece).

Detailed description of the invention

The present invention relates to the compliance microporous fibre with node and fibrillar structure, and manufactured by the fiber Braided fabric.Polymer film and/or yarn fabric can be laminated in the braided fabric to manufacture laminate.It is described to knit Thing has high moisture percent of pass (i.e. highly-breathable), high water entry pressure and low water absorption simultaneously.The braided fabric can lead to Cross and for example print and colour.In addition, the braided fabric is plain, soft and can dangled, make it particularly suited for clothes, Gloves and footwear applications.It should be noted that term " braided fabric " and " fabric " can used interchangeablies herein.In addition, art Language " ePTFE fibers " and " fiber " can used interchangeablies in this application.

The compliance fiber has node and fibrillar structure, and its interior joint is connected with each other by fibrillation, described Interfibrillar space limits the path of perforating fiber.In addition, the compliance fiber is micro porous.This paper microporosity It is defined as with the sightless hole of bore hole.Intrastitial node and fibrillar structure make fiber and the fabric by fibrage Can highly breathable, and can permeate colouring agent and oleophobic property composition.In addition, the matrix provided by node and fibrillation Allow to include required filler and/or additive.

It should be understood that on compliance microporous fibre;It is for ease of retouching herein with reference to expanded polytetrafluoroethyl,ne (ePTFE) State.It should be understood, however, that any appropriate compliance fluoropolymer with node and fibrillar structure can with the application EPTFE used interchangeablies.The non-limiting example of fluoropolymer include but is not limited to intumescent PTFE, intumescent modified ptfe, Intumescent PTFE copolymers, PEP (FEP) and perfluoroalkyl alkoxy copolymer resin (PFA).Expandable PTFE mixes Mixed thing, expandable modified ptfe and intumescent PTFE copolymers have been granted by patent, such as, but not limited to the Branca U.S. Patent the 5,708,044th;Baillie U.S. Patent No. 6,541,589;Sabol etc. U.S. Patent No. 7,531, No. 611;Ford U.S. Patent Application No. 11/906,877;With Xu etc. U.S. Patent Application No. 12/410,050. The fibrillation length range of ePTFE fibers is about 5 microns-about 120 microns, about 10 microns-about 100 microns, about 15 microns-about 80 microns or about 15 microns-about 60 microns.

In addition, the ePTFE fibers have essentially rectangular construction.At least Fig. 4 in the application, 6,12,14,17, 19,21,27,30,39,43,44,45 describe the exemplary ePTFE fibers with essentially rectangular construction.Such as this paper institutes With term " essentially rectangular construction " is used to represent that fiber has rectangle or approximate rectangular section.That is, the width of ePTFE fibers Degree is more than its height (thickness).It should be noted that fiber can have circular edge or sharp edges (or sidepiece).Before braiding The conventional fibre institute that must be twisted is different, and ePTFE fibers are woven in the case of can first being twisted in formation state and not. EPTFE fibers can carry out favourable braiding in the case of the width orientation of fiber, so as to form the top table of braided fabric Face.Therefore, the braided fabric being made up of invention ePTFE fibers has smooth or substantially smooth patterns for knitting and corresponding Smooth surface.The smooth and even curface of the fabric enhances the pliability of braided fabric.

In addition, ePTFE fibers used herein have low-density.More specifically, density is low before the braiding of the fiber In about 1.0 grams/cc.In the exemplary embodiment, density is below about 0.9 gram/cube li before the braiding of the fiber Rice, below about 0.85 gram/cc, below about 0.8 gram/cc, below about 0.75 gram/cc, be below about 0.7 gram/cc, below about 0.65 gram/cc, below about 0.6 gram/cc, below about 0.5 gram/cube li Rice, below about 0.4 gram/cc, below about 0.3 gram/cc or below about 0.2 gram/cc.For making The technique of fabric, for example, woven, and ePTFE fibers are folded and can increase the density of fiber, while keeping whole braided fabric Gas permeability.As a result, after the braiding of the fiber density less than or equal to about 1.2 grams/cc.The fiber is (before braiding After braiding) low-density also can reinforcing fiber gas permeability.

In addition, the unit weight of the fiber can be about 50dtex- about 3500dtex, about 70dtex- about 1000dtex, about 80dtex- about 500dtex, about 90dtex- about 400dtex, dtex of about 100dtex- about 300 or about 100dtex- about 200dtex.It should be noted that lower dtex provides weight/area lower fabric, this can increase by the fabric The comfortableness of the clothes of formation.In addition, low denier (denier) value of ePTFE fibers can make braided fabric have high resist Viscosity.Resistance to bond refers to the ability that fabric resists grasping and movement of the independent fiber in fabric.Generally, fiber is finer (for example, lower danier or dtex) then braid more compacts, and obtains more preferable resistance to bond.

EPTFE fibers also have the height (thickness) below about 200 microns (before braiding or after braiding).In some implementations In mode, the scope of thickness is about 20 microns-about 150 microns, 20 microns-about 100 microns, about 20 microns-about 70 microns, about 20 microns -50 microns, about 20 microns -40 microns or about 26 microns -36 microns.Before the braiding of the ePTFE fibers or weave Height (thickness) afterwards can less than 100 microns, less than 75 microns, less than 50 microns, less than 40 microns, less than 30 microns or Less than 20 microns.The fiber also has the width less than about 4.0mm (before braiding or after braiding).It is exemplary at least one In embodiment, before the braiding of fiber and braiding after width can be about 0.5mm to about 4.0mm, about 0.40mm to about 3.0mm, about 0.45mm to about 2.0mm or about 0.45mm to about 1.5mm.The gained aspect ratio (i.e. the ratio between width and height) of ePTFE fibers Greater than about 10.In some embodiments, the aspect ratio is greater than about 15, is greater than about 20, is greater than about 25, is greater than about 30, is more than About 40 or greater than about 50.The high aspect ratio of high aspect ratio, such as ePTFE fibers so that the weight per unit area of fabric becomes It is low, it can be easier and more efficiently remold shape, and high waterproof can be obtained in filling density and through close lower braided fabric Property.

Further, the toughness of ePTFE fibers is greater than about 1.4cN/dtex.In at least one embodiment of the present invention, The toughness of ePTFE fibers is about 1.6cN/dtex- about 5cN/dtex, the cN/dtex of about 1.8cN/dtex- about 4 or about 1.9cN/ Dtex- about 3cN/dtex.In addition, the fibrous fracture intensity of ePTFE fibers is at least about 1.5N.In one or more embodiment party In formula, the fibrous fracture intensity of ePTFE fibers is about 2N to about 20N, about 2N to about 15N, about 2N to about 10N or about 2N to about 5N。

EPTFE fibers described herein can be used for forming braided fabric, and the braided fabric has warp fiber and broadwise The repetition Weaving pattern of fiber weaving each other.Any Weaving pattern, such as, but not limited to plain weave, satin weave are compiled Knit, twill weave and square flat sennit are knitted, and braided fabric is formed available for ePTFE fibers are caused.When the width of ePTFE fibers is less than Quantity based on per inch weft yarn and/or warp thread and when distributing to the space of the fiber, ePTFE fibers can be with without folding line Or the smooth braiding of mode of wrinkle.When this fiber loose weave, in warp fiber and the intersection of weft fiber (crosspoint) Between have visible gap.As such, fiber is highly breathable, but it is non-watertight.Wide arc gap in this fiber, in example It is acceptable such as to be provided by another layer in the application of water proofing property, or usually require covering and water proofing property do not weigh It is acceptable in the case of wanting.

In other embodiments, for example when the width of ePTFE fibers exceedes based on per inch weft yarn or warp thread quantity During the space distributed in braided fabric, fiber is more close weave.It is no or basic between intersection in this fiber It is very close to each other.Relative to the space that fiber is supplied to based on per inch weft yarn and/or warp thread quantity, the width of ePTFE fibers The former 1 times can be higher than, be greater than about 1.5 times, be greater than about 2 times, be greater than about 3 times, be greater than about 4 times, be greater than about 4.5 times, be greater than about 5 times, greater than about 5.5 times or greater than about 6 times (or more).In other words, ePTFE fibrages must than ePTFE fiber width It is more close.In this embodiment, ePTFE fibers are taken up one's knitting process with essentially rectangular construction.However, due to The size of fiber is than filling density and/or the space through close offer is bigger, so ePTFE fibers itself curling and/or folding, to accord with Close the braiding spacing that the weft yarn and/or warp thread quantity of the per inch of warp fiber and weft fiber are determined.Generally, the width of fiber Folding line or curling are produced on degree, so that the width of each single fiber diminishes with the folding line of fiber or the generation of curling.Institute It is in folded structure with length direction of the fiber along fiber.

The compliance of ePTFE fibers is schematically depicted in Figure 40 and 41.In Figure 40 and 41, fiber 10 will be positioned in compiling In the space (S) of woven fabric.As shown in Figure 40 and 41, the width (W) of fiber 10, which is more than in braided fabric, distributes to fiber 10 Space (S).In order to meet the space (S) for distributing to fiber 10, fiber 10 folds or crimped the construction 15 to fold, such as Figure 40 It is shown.

" foldability " or " folded structure " of ePTFE fibers represented by the line 20 extended along fibre length, at least such as Shown in Fig. 3,5,7,10,13,16,18,20,24,26,30 and 38.Figure 44 and 45 is the section SEM of exemplary braided fabric Photo, illustrates the compliance of ePTFE fibers, the folding (and/or curling) for the fiber itself clearly described in such as these figures. Figure 41 is the top schematic view of the fiber of crimped configuration.The fiber itself can be rolled in warp direction and/or weft direction It is folded.As shown in figure 41, the fiber is adapted with space (S).In the fabric including warp fiber and weft fiber, warp-wise At least one of fiber and weft fiber along or substantially along fiber folded lengthwise.So as to which ePTFE fibers are in braiding Folding and/or crimping in fabric is smaller width.As predictive embodiment, in the epi braided fabrics of 88ppi × 88 and width Spend in the ePTFE fibers for 1mm, 1/3.5 folding that ePTFE fibers itself can be folded to generate less than its original width is wide Degree, to adapt to the space (for example, 88ppi divided by 25.4mm (1 inch) are the every mm of 3.5 weft yarns) provided in braid construction.

The performance of complying with of ePTFE fibers makes larger sized ePTFE fibers be used for smaller braiding spacing.Relative to fibre The width increase per inch weft yarn and/or the quantity of warp thread of dimension, can be reduced or even eliminated warp fiber and weft fiber intersects The gap at place.The fabric of this close weave goes back waterproof (for example, with high water entry pressure) while highly breathable.Should Work as attention, the fabric is not only ventilative by any gap that may be present, also ventilative by ePTFE fibers itself.Even if no There is gap, the braided fabric is also breathable.In contrast, conventional braided fabric becomes not in close weave It is ventilative.

It is not intended to be limited to theory, it is believed that the compliance and node and fibrillar structure of ePTFE fibers cause braided fabric Result in many (if not all) characteristics described herein and advantage.For example, in braided fiber, ePTFE fibers Node helps fiber to keep the fibrillation of open to the outside world to construct.The hole of the opening of ePTFE fibers greatly enhances braided fabric Gas permeability.The fineness of stomata prevents water from entering fibre structure, while keeping highly-breathable.As described above, ePTFE fibers Compliance enable fiber to be woven to close construction, so as to also be breathed freely while braided fabric waterproof.

Processing can be provided to assign braided fabric one or more required functions, such as, but not limited to oleophobic property.When carrying During for oleophobic property coating, such as, but not limited to fluorinated acrylic ester oleophobic property coating is carried out according to oily level test described herein During test, the oily level of braided fabric is more than or equal to 1, more than or equal to 2, more than or equal to 3, more than or equal to 4, be more than or Equal to 5 or more than or equal to 6.Coating or processing, such as fluorinated acrylic ester coating, can be coated on a face of braided fabric Or two sides, and penetrate or only partial penetration braided fabric.It should be understood that arbitrary waterproof and ventilative nonfunctional protective layer, function Property coating or functional membrane, such as, but not limited to polyamide, polyester, polyurethane, cellophane, non-fluoropolymer film, can be attached Or otherwise fix or be laminated on braided fabric.

The braided fabric can be coloured through suitable dye compositions.EPTFE fibers have micro-structural, wherein The hole of ePTFE fibers is close enough to provide water proofing property, and opens to provide moisture permeability and colouring agent painting enough The property of the infiltration of material.EPTFE fibers have surface, and it provides lasting aesthetic property in printing.In some embodiments In, persistence attractive in appearance can be realized with colouring agent coating composition, the composition includes with sufficiently small to be contained in The pigment of granularity in the hole of ePTFE fibers and/or in braided fabric.A variety of pigment can be used and a kind of or many by changing Plant the concentration of pigment or multiple color is applied by the combination of these technologies.Furthermore it is possible to such as solid, pattern or impression Form apply coating composition.Coating composition can be applied over by braided fabric by conventional printing process.For coloring Method of application includes but is not limited to transfer coated, silk-screen printing, intaglio printing, ink jet printing and blade coating.

Different from conventional braided fabric, ePTFE braided fabrics can be by forming the fiber (that is, ePTFE fibers) of fabric Ventilative, the gap formed when also can be by weaving between ePTFE fibers is breathed freely.As discussed above, ePTFE fibers have Node and fibrillar structure, the path of structure formation perforating fiber, make ePTFE fibers breathable.Weave ePTFE fibers When, node and fibrillar structure maintain open path.Therefore, even if ePTFE fibre compacts weave in braiding structure not When forming gap or not forming gap substantially, ePTFE braided fabrics maintain its highly-breathable.The ePTFE braided fabrics according to Its moisture vapor transmission rate (MVTR) is greater than about when moisture vapor transmission rate (MVTR) method of testing as described herein is tested 3000 grams/m/24 hours, greater than about 5000 grams/m/24 hours, greater than about 8000 grams/m/24 hours, Greater than about 10000 grams/m/24 hours, greater than about 12000 grams/m/24 hours, greater than about 20000 grams/square Rice/24 hours or greater than about 25000 grams/m/24 hours.As used herein, term " breathable " " gas permeability " is Refer to braided fabric or layered product that moisture vapor transmission rate (MVTR) is at least about 3000 grams/m/24 hours.Moisture infiltration Speed or gas permeability provide cooling to garment wearer, and the clothes are for example made up of the braided fabric.

The air permeability of braided fabric be less than about 500cfm, less than about 300cfm, less than 100cfm, be less than about 50cfm, less than about 25cfm, less than about 20cfm, less than about 15cfm, less than about 10cfm, less than about 5cfm, less than about 3cfm, Even less than about 2cfm.It should be understood that low air permeability is related to the windproof of fabric improved.

The water absorption rate of ePTFE braided fabrics described herein is less than or equal to about 50 grams/m, less than or equal to 40 Gram/m, less than or equal to about 30 grams/m, less than or equal to about 25 grams/m, less than or equal to about 20 grams/ Square metre, less than or equal to about 15 grams/m or less than or equal to about 10 grams/m, and water entry pressure is at least About 1kPa, at least about 1.5kPa, at least about 2kPa, at least about 3kPa, at least about 4kPa, at least about 5kPa or At least about 6kPa.EPTFE fibers limit water entry into braided fabric and (enter such as fibre structure and through between braided fabric Gap) so that the problem of eliminating relevant with conventional braided fabric, described problem is that braided fabric absorbs water, and then become fiber Weight, and cause the temperature of water to carry out heat transfer through fabric.In the case where wearer is in cold environment, this thermal conductivity It is probably unfavorable, and cold can be transferred to the body of wearer.

In addition, braided fabric is thin and light amount so that end user is easily carried and/or transported by braided fabric shape Into product.The weight of braided fabric can be about 50 grams/m-about 500 grams/m, about 80 grams/m-about 300 grams/m or about 90 grams/m-about 250 grams/m.In addition, the weight of braided fabric unit area can be low In about 1000 grams/m, below about 500 grams/m, below about 400 grams/m, below about 300 grams/m, Below about 200 grams/m, below about 150 grams/m or below about 100 grams/m.Further, braided fabric Highly (thickness) can be about 0.05mm- about 2mm, about 0.1mm- about 1mm, about 0.1mm- about 0.6mm, about 0.1mm- about 0.5mm, About 0.1mm- about 0.4mm, about 0.15mm- about 0.25mm or about 0.1mm- about 0.3mm.Braided fabric is thin so that knitted by braiding The product of thing formation is closely folded.Thin and light characteristic is also contributed to the overall comfort of garment wearer, particularly During wearer movement, wearer is limited by less motion.

Further, it braided fabric soft and can dangle, it is applied to clothes, gloves and footwear.Braided fabric Mean rigidity be less than about 1000g, less than about 500g, less than about 400g, less than about 300g, less than about 250g, be less than about 200g, less than about 150g, less than about 100g, be even less than about 50g.It was surprisingly found that except soft feel, braiding The noise of reduction is presented in bending or folding for fabric.Even if it has furthermore been found that addition porous polymer film, the institute as after State, noise is also reduced, when particularly compared with conventional ePTFE layered products.

Braided fabric also tear-proof.For example, being carried out by Elmendorf as described herein (Elemendorf) tear test During measurement, the tearing strength of braided fabric is about 10N- about 200N (or bigger), about 15N- about 150N or about 20N- about 100N. This high-tear strength causes braided fabric more robust.

In at least one embodiment, porous or microporous polymer membranes are stacked or are bound to braided fabric.It is porous Property film non-limiting example include intumescent PTFE, intumescent modified ptfe, intumescent PTFE copolymers, ethylene fluoride third Alkene (FEP) and perfluoroalkyl alkoxy copolymer resin (PFA).It is polymeric material such as polyolefin (for example, polypropylene and polyethylene), poly- Urethane and polyester are deemed within the scope of the present invention, on condition that the polymeric material may be machined to form porous or microporous barrier knot Structure.Even if it should be understood that when invention braided fabric is stacked or be bound to porous or microporous barrier, gained layered product also keeps high Degree is ventilative and maintains the gas permeability of braided fabric substantially.In other words, the porous or microporous barrier of braided fabric is laminated in even in volume When woven fabric is stacked, also the gas permeability of braided fabric is not produced influences or only produces minimum influence.

Perforated membrane can be asymmetric membrane.Multilayer is included in " asymmetric " film for representing membrane structure used herein The micro-structural of at least one layer is different from the micro-structural of second layer in the film in ePTFE, the film.Can be by such as aperture difference The difference, and/or density variation of different, node and/or fibrillation geometry or size cause the first micro-structural and second micro- knot Difference between structure.

In further embodiment, yarn fabric can be attached to microporous barrier or be attached directly to braided fabric.Herein Term " yarn fabric " used is used to representing any braided fabric, adhesive-bonded fabric, felt (felt) fabric, grabs suede (fleece) and knit Thing or knitting fabric, can be made up of natural and/or composite fibre materials and/or other fibers or flocked material.For example, can The material for constituting yarn fabric is such as but not limited to cotton, artificial silk, nylon, polyester or its blend.Except the application requirement with Outside, the weight for forming the material of yarn fabric is not particularly limited.In the exemplary embodiment, the yarn fabric is that air can Passing through and ventilative.

It can be used and film and/or yarn fabric are connected to any appropriate of braided fabric (and yarn fabric is connected into film) Method, such as gravure lamination method (gravure lamination), fusion mull technique (fusion bonding), glue spraying bond Method (spray adhesive bonding) etc..Adhesive can discontinuously or be continuously applied, on condition that saturating in retaining layer stack Gas.For example, the form application adhesive that can discontinuously connect, such as discrete point or lattice, or with the shape of adhesive network Formula sticks together the layer of layered product.

EPTFE braided fabrics be applied to a variety of applications, including but not limited to clothes, tent, cover, camping bag, footwear, Gloves etc..Braided fabric has highly-breathable and water proofing property simultaneously.Due to the high aspect ratio of ePTFE fibers, at least acquisition or portion Separately win to obtain these favourable characteristics.EPTFE braided fabrics can be used alone, or it can be with fluoro-containing copolymer film and/or yarn fabric It is applied in combination.The surface of the ePTFE braided fabrics can be coloured for example, by printing.In addition, oleophobic property coating group can be used Compound coats the surface of ePTFE fabrics and/or ePTFE fibers to obtain oleophobic property.It should be understood that benefit as described herein and excellent Gesture is equally applicable to knitting fabric and product, and the braided fabric and product that text is discussed.

Method of testing

It should be understood that although some methods and apparatus are described below, those of ordinary skill in the art determine that what is be applicable appoints Where method or equipment are also optionally used.

The fibre weight of unit length

45 meters of long fibers have been obtained using skein reeling machine (skein reel).Then service precision is 0.0001 gram The balance fiber long to 45 meters is weighed.Weight is amplified 200 times afterwards, unit is provided with danier (gram/9000 meters) The weight of length.The value is amplified 10 times again divided by 9 afterwards, the weight of unit length is provided with dtex (gram/ten thousand metres).

Fiber width

In a usual manner fiber width is measured using 10 × eye thimble with 0.1mm scales.Three times are carried out to measure and take Average, to determine the width for being accurate to 0.05mm.

Fiber thickness

Fiber thickness is measured using the calliper for being accurate to 0.0001 inch.It is careful to measure to avoid calliper conpressed fibers. Carry out three times to measure and take the mean, then change to 0.0001mm.

Fibre density

By below equation, calculated using the fibre weight of the unit length measured before, fiber width and fiber thickness Fibre density:

Fibrous fracture intensity

Fibrous fracture intensity is to make the measured value of the peak load needed for fibrous fracture (rupture).Pass through tester for elongation (such as Massachusetts Canton cityMechanology Inc.) measure fracture strength.Automatic manual transmission has It is suitable to anchoring fiber in tensile load measurement and is detained fiber (trumpet type) intermediate plate of article.The crosshead speed of tester for elongation Degree is 25.4cm per minute.Gauge length is 25.4cm.Various types of fibers are carried out with five measurements, in units of newton Report average value.

Tenacity of fibre

Tenacity of fibre is the fracture strength of the fiber for the unit weight for being standardized as fiber.Calculated with below equation Tenacity of fibre:

The thickness of fiber and film

By the way that film or fabric layer stack are placed between the two boards of three rich (Mitutoyo) 543-252BS callipers and Measure the thickness of fabric and film.Use the average value of three measurements.It should be understood that the thickness of fiber and/or film can pass through ability Any appropriate method that field technique personnel determine is measured.

The matrix tensile strength (MTS) of film

Using equipped with level clamp (flat-faced grip) and 0.445 thousand Ns of pressure load units 1122 tester for elongation measure the matrix tensile strength of film.Gauge length is 5.08cm, and crosshead speed is 50.8cm/ minutes. The size of sample is 2.54cm × 15.24cm.In order to ensure suitable result, laboratory temperature is maintained at 68 °F (20 DEG C) To ensure suitable result between 72 °F (22.2 DEG C).If sample is broken at grip interface, data are abandoned.

For longitudinal MTS measurements, along machine direction, " off line (down web) " direction takes the large-size of sample in other words To.For horizontal MTS tests, the large-size of sample is orientated perpendicular to machine direction, also referred to as " crossing net " direction.Use Plum Teller-support benefit AG204 types balance is weighed to each sample.Then measured using Kafer FZ1000/30 callipers The thickness of sample.Then each sample is tested respectively on tester for elongation.Each sample measures three different parts.Use The average value of three peak load (i.e. peak force) measurements.

The MTS of vertical and horizontal is calculated using following formula:

MTS=(peak load/cross-sectional area) × (PTFE bulk density)/porous film density),

Wherein PTFE bulk density is 2.2 gram per centimeters3

The average value of three crossing net measurements is recorded as vertical and horizontal MTS.

The density of film

In order to calculate the density of film, the measured value for having used matrix tensile to test.As described above, the size of sample is 2.54cm×15.24cm.Use plum Teller-Tuo Luntuo AG204 models balance (Mettler Toledo Scale Model AG204) each sample is weighed, the thickness of sample is then measured using Kafer FZ1000/30 gauges.Using the data, according to Following formula calculates the density of sample:

Wherein:ρ=density (gram/cc)

M=mass (g)

W=width (1.5cm)

L=length (16.5cm)

T=thickness (cm)

The result reported is the average value of 3 calculating.

The lattice empty profit air-flow of film

The test measurement of Ge Li (Gurley) air mass flow depresses 100 centimetres in 12.4 cm of water3Air stream passes through 6.45 lis Rice2The time (in seconds) of sample.Gree automatic air permeability tester (Gurley of the sample in model 4340 Densometer Model 4340Automatic Densometer) in tested.It is multiple when being carried out in same sample During test, it is necessary to careful to ensure that the edge of test zone is not overlapping.(when being clamped during lattice profit test to produce sealing Material compresses along the edge of test zone, and this may influence air flow result).The result reported is 3 measurements Average value.

Moisture vapor transmission rate test-(MVTR)

The MVTR of each sample fabric is determined according to ISO 15496 general teaching, and difference is, based on device Vapor permeability (WVPapp) simultaneously utilizes following transfer equation, the water vapor permeability rates (WVP) of sample is scaled wet Impervious speed (MVTR).

MVTR=(Δ P value × 24)/((1/WVP)+(1+WVPapp values))

In order to ensure suitable result, before testing by sample in 73.4 ± 0.4 °F and the bar of 50 ± 2% relative humidity Nursed one's health 2 hours under part, and the water of water-bath is constantly maintained at 73.4 °F ± 0.4 °F.

A MVTR is measured each sample, and result is expressed as gram/m/24 hours.

Mass/area

In order to measure mass/area, area at least 100cm is prepared for2Fabric sample.Karr Schroeder can be used (Karl Schroder)100cm2Circle cutter.Each sample is weighed using plum Teller-support benefit AB204 types balance. Balance is recalibrated before being weighed to sample, and result is reported with gram/m (gsm).For film Sample, the result reported is the average value of 3 measurements.For the laminate sample of printing, the data reported are that single is surveyed The result of amount.

Oily level test

Measure the oily level of film and layered product.General teaching according to AATCC method of testings 118-1997 is tested. Oily series is the oil of the maximum number of nonwetting material within the test open-assembly time of 30 ± 2 seconds.The result reported is 3 surveys The average value of amount.

SEM sample preparation methods

Prepare section SEM samples in the following manner:Sample is sprayed with liquid nitrogen, Leica ultracut are then used Diamond knife in UCT (being purchased from Germany Wei Silai Leica Microsystems Inc) cuts the sample of the sprinkling.

Fibrillation linear measure longimetry

Fibrillation length is measured using surface SEM image.Multiplication factor is selected so as to see many fibrillation, The clear view of the point of node is connected to including fibrillation.Each sample to measurement uses identical multiplication factor.Due to these Node and fibrillar structure are irregular, recognize that 15 different fibrillation of the random distribution in each image are used to measure.

In order to accurately measure each fibrillation, two ends for make it that they are connected in fibrillation with node of being rule with cursor End is perpendicular to fibrillation.Measure and record the distance between cursor setting-out of each fibrillation.To each surface image of each sample As a result it is averaged.The report value of fibrillation length represents the average value of 15 samples measurement on SEM image.

Liquid-proof tests (Su Te, Suter) and water absorption rate

Liquid-proof is tested and water absorption rate is carried out as follows.Using improvement suter test equipment and be used as representative test with water Liquid, tests the liquid repellency of layered product.Water is crushed on about 41/4 inch of 2 rubber ring seals in the setting clamped In the sample area of (10.8cm) diameter.Carry out test sample in the following manner:Sample is orientated so that outside sample Film surface is by the surface of hydraulic pressure.Hydraulic pressure on sample is increased to by about 0.7psi by the pump that is connected with cistern (6.94.81KPa), is such as indicated by suitable scale and by the online valve regulation hydraulic pressure.Test sample is located at certain angle On, and recycle water to ensure that water, rather than air are contacted with the relatively low surface of sample.Continue observation in 3 minutes and sample Whether the opposite surface of outer membrane face there is any water by pressure through sample.The liquid water seen on the surface is considered as The water of seepage.

In the case of there is no visible aqueous water on sample surfaces in 3 minutes, give by level (liquid-proof).If sample Product are by the test, and it is considered as being " liquid-proof " when sample is used.There is any visible aqueous water leakage (such as leakage, pin The form of eye leakage etc.) sample be not qualified as liquid-proof, and be test crash.

Sample is carried out afterwards before testing to be weighed to determine water absorption rate.The circular sample of 10.8cm diameters gram difference It is converted into gram/m, so as to provide water suction and increased weight.The result reported is the average value of 3 measurements.

The measurement in gap between fiber

Interfibrous gap is measured using surface SEM image.Multiplication factor is selected to see at least 10 fibres Dimension is intersected, and includes the clear view in fiber overlapping gap.For each gap, the fiber at intersection 30 as shown in Figure 52 Between distance (D), measure in radial directions, be accurate to micron.At least ten infalls in the visual field are to the distance (D) Measure and be averaged.It should be noted that only showing that two intersect 30 in Figure 52, for illustration purpose.In addition, to each For gap, intersect the distance (D ') on direction vertical with the direction of the distance between fiber at 30, surveyed on weft direction Amount, is accurate to micron.At least ten infalls in the visual field are measured and are averaged apart from D ' to this.Report broadwise The mean gap distance (D ') in mean gap distance (D) and warp direction on direction, and larger value is reported first.

Water entry pressure (WEP)

Water entry pressure provides a kind of method immersed for the water tested through film and/or fabric.One test specimens Product are sandwiched between a pair of test pieces.Relatively low piece has applies stressed ability using water to a part for sample.Will be a piece of PH test paper, which is placed at the top of the sample between test piece, does not apply side of pressure, and the evidence entered as water is indicated.Then with small Amplification sample is pressed, after each pressure change wait 10 seconds until pH test paper color change indicate water enter First appearance.It will penetrate or enter fashionable hydraulic pressure and be recorded as water entry pressure.Test knot is obtained from the center of test sample Really, with avoid may caused by the edge damaged error result.

Tearing strength

The test is designed to determine the tongue type crack (single-rip from the incision extension single tear of braided fabric Tongue-type tear) needed for mean force.Thwing-Albert heavy types Ai Lemanduofu has been used to tear tester (MAI227).In calibrator (-ter) unit and after selecting correct pendulum weight, flicker asterisk on the left of display can instruction equipment can use In test.Pendulum is raised to original position.Sample is placed between intermediate plate, and uses the pneumatic clamps positioned at the lower right side of equipment Tool is clamped.Air pressure is 414KPa-621 KPa.Sample is placed in center, and bottom margin is carefully against backing pin.The higher area of sample Domain should be towards pendulum, to ensure shear action.Tested, until reaching a complete tear.Digital reading is with newton Recorded for unit.One group (1 warp-wise and 1 broadwise) of completion is repeated up to it.The result reported is one group of measurement Average value.

Rigidity

Using Thwing Albert pliabilitys testers (Handle-O-Meter) in 1000g crossbeams and 1/4 " well width Under conditions of measurement feel (rigidity).The sample of 4 " × 4 " sizes is cut out from fabric.Sample is face-up, is placed in sample bench On.Sample is flattened expansion, so that measurement direction is vertical with groove to test warp direction.Pressing starts/and testing button is until listen To the sound, then unclamp.After the rising tone sound is heard, the numeral shown on record digital display.Reading will not be zeroed, But each peakreading individually tested can be shown.Upset sample is tested again, records reading.Then sample is rotated by 90 ° To test weft direction, reading is recorded.Finally, upset sample is tested again, records reading.Four numerals recorded are added (1 warp-wise surface, 1 through rearwardly, 1 broadwise surface, a broadwise back side) to calculate sample in grams Global stiffness.For a sampling report result.

Air permeability-frazier number (Frazier number) method

Air permeability is measured in the following manner:About 6 square inches of (2.75 inches of diameter) border circular areas are being provided For clamping test sample in the gasket flange fixture of gas flow measurement.The upstream side of sample clamp is connected with flowmeter, the stream Gauge is docked with source of dry compressed air.The downstream of sample clamp is communicated with air.

Pass through online flowmeter (ball float rotor by applying 0.5 inch of hydraulic pressure in the upstream side of sample and recording air Flowmeter) flow velocity and complete test.

Before test, sample is nursed one's health 4 hours under 70 °F (21.1 DEG C) and 65% relative humidity.

With frazier number report result, the frazier number be sample under 0.5 inch of water with cubic feet/min/ Square feet is the air mass flow of unit.

Embodiment

Embodiment 1a

Obtaining PTFE resin, (Teflon 669X are purchased from the E.I. E.I.Du Pont Company (E.I.du of Delaware State Wilmington Pont de Nemours, Inc., Wilmington, DE) fine powder.The resin withK is with 0.184g/g (with powder Last weight meter) ratio mixing.Powder through lubrication is compressed in cylinder, and stands 18 hours at room temperature.Then with 169/1 drawdown ratio carries out plunger type extrusion to piece, to make the ribbon that about 0.64mm is thick.Afterwards by the ribbon of extrusion Boil down to 0.25mm thickness.Then the ribbon of compression is stretched between two groups of rollers in a longitudinal direction.Second group of roller and Speed ratio (i.e. draw ratio) between first group of roller is 1.4:1, extensibility is 30%/second.Then the ribbon of stretching is carried out Limit and dried at 200 DEG C.Then dry ribbon temperature for two groups of heating in 300 DEG C of heating chamber roller it Between, it is expanded to 1.02 with the rate of extension of 0.2%/second:1 ratio, is expanded in addition with the rate of extension of 46%/second afterwards 1.75:1 expansion rate, is then expanded to other 1.02 with the rate of extension of 0.5%/second:1 expansion rate.The mistake Journey has made the ribbon that thickness is 0.24mm.

Then the ribbon is cut open, using produce 1.78mm is wide, 0.24mm is thick section and unit weight as 3494dtex.Then the ribbon of the incision is with 6.25:1 draw ratio and the rate of extension of 65%/second are being set to 390 DEG C Heating plate on expand.Afterwards further with 2.50:1 draw ratio and the rate of extension of 66%/second is by being set to 390 DEG C the plate of heating expanded.Then further with 1.30:1 draw ratio and the rate of extension of 23%/second is by being set to The plate of 390 DEG C of heating is expanded.Afterwards with 1.00 in 1.6 seconds:1 draw ratio process is set to 390 DEG C of heating Plate, produces the intumescent PTFE fiber of amorphous state locking (amorphously locked).

The ePTFE fibers of final amorphous state locking (amorphously locked) measure the unit with 172dtex Length weight, the section with rectangle simultaneously has the following properties that:Width=1.0mm, height=0.0356mm, density=0.48 Gram/cc, fracture strength 3.51N, toughness 2.04cN/dtex, and fibrillation length=53.7 micron.

Fig. 1 shows the scanning electron micrograph (SEM) in the side of 1000 times of gained fibers shot under amplifying. Fig. 2 is the scanning electron micrograph in the top surface of 1000 times of fibers shot under amplifying.

Then the fiber is used to make braided fabric.Weaving pattern be using 88 × 88 yarns/inch thread count and 2/2 twill obtained.The braided fabric has the following properties that:Thickness=0.20mm, MVTR=27860 grams/m/24 hours, Water absorption rate=13gsm, feel (hand)=71g, tearing strength=75.6N, WEP=5.38kPa, air permeability= 0.81cfm, and oily level=<1.Fig. 3 shows that the scanning electron microscopy on the surface of 150 times of fabrics shot under amplifying shines Piece.Fig. 4 shows the scanning electron micrograph at the side view visual angle of 150 times of fabrics shot under amplifying.Warp fiber and latitude It is less than 0.01mm to the length and width in the gap between fiber.The weight of fabric is 135 grams/m.

Fiber (172dtex) is taken out from braided fabric and complying with after its braiding carries out dimensional measurement under state, with Show the compliance of fiber.It is 0.30mm to measure folding width after the braiding of fiber, and fold height is 0.0699mm after braiding, Aspect ratio is 4.3 after braiding, and density is 0.82 gram/cc after braiding.The folding width after width and braiding before braiding The ratio between be 3.3:1.

Embodiment 1b

Fluorinated acrylic ester coating is applied over to make it have oleophobic property on embodiment 1a braided fabric, protected simultaneously Stay porous and microcellular structure.

Resulting oleophobic braided fabric has the following properties that:Thickness=0.20mm, MVTR=21206 grams/m/24 Hour, water absorption rate=13gsm, feel (hand)=131g, tearing strength=63.8N, WEP=6.11KPa, air permeability =1.72cfm, and oily level=6.Fig. 5 shows that the scanning electron on the surface of 150 times of braided fabrics shot under amplifying shows Micro- photo.Fig. 6 shows the scanning electron micrograph at the side view visual angle of 150 times of fabrics shot under amplifying.Between fiber Gap length and width be less than 0.01mm.The weight of fabric is 158 grams/m.

Embodiment 1c

The ePTFE membrane for the amorphous state locking being had the following properties that:Thickness=0.04mm, the g/cc of density=0.47, most Matrix tensile strength on matrix tensile strength=105.8MPa on strong direction, the direction vertical with most strong direction= 49.9MPa, gas permeability (Gurley, Ge Li)=16.2s, MVTR=64168 grams/m/24 hours.

Embodiment 1b braided fabric is laminated on ePTFE membrane in the following manner.By applying dot pattern on film Fusing polyurethane binder fabric and ePTFE membrane are combined together., will in the case where polyurethane binder point melts Fabric is placed on the top of adhesive side of film.Make structure (product) the spontaneous cooling.

Resulting product has the following properties that:Thickness=0.22mm, MVTR=12845 grams/m/24 hours, water absorption rate =12gsm, feel (hand)=196g, tearing strength=46.19N, and oily level=6.Fig. 7 is shown in the case where 150 times are amplified The scanning electron micrograph of the top surface of the product of shooting.Fig. 8 is shown in the side of 100 times of products shot under amplifying View.Fig. 9 shows the side view in 1000 times of products shot under amplifying.The length and width in the gap between fiber is small In 0.01mm.The weight of fabric is 192 grams/m.

Embodiment 1d

Embodiment 1b braided fabric is laminated in plain weave nylon shioze fabric (gram/square of weight 18 in the following manner Rice, 150 warp thread per inch, and 109 weft yarn per inch, 17dtex (5 fibrils)).By applying dot pattern on fabric Fabric and yarn fabric are combined together by fusing polyurethane binder.In the case where polyurethane binder point melts, it will weave Thing is placed on the top of adhesive side of fabric.Make the spontaneous cooling of the structure.

Resulting product has the following properties that:Thickness=0.25mm, MVTR=14407 grams/m/24 hours, water absorption rate =54gsm, feel (hand)=288g, tearing strength=43.18N, WEP=5.72KPa, air permeability=0.86cfm, And oily level=6.Figure 10 shows the scanning electron micrograph in the top surface of 150 times of products shot under amplifying.Figure 11 show the scanning electron micrograph at the side view visual angle of 100 times of products shot under amplifying.Figure 12 is shown 500 Amplify the scanning electron micrograph at the side view visual angle of the lower product shot again.The length and width in the gap between fiber is small In 0.01mm.The weight of fabric is 192 grams/m.

Embodiment 1e

Laminate is built in the following manner.By on film using fusing polyurethane binder of dot pattern by film It is combined together with the embodiment 1a yarn fabrics described.In the case where polyurethane binder point melts, yarn fabric is placed in and knitted On the top of the adhesive side of thing.Make the spontaneous cooling of the structure.Then, the melting using dot pattern on film is passed through Change polyurethane binder by fabric and film combination.In the case where polyurethane binder point melts, fabric is placed in the top of film On.Make the spontaneous cooling of the structure.

Resulting product has the following properties that:Thickness=0.26mm, MVTR=8708 grams/m/24 hours, water absorption rate =11gsm, feel (hand)=526g, tearing strength=37.78N, and oily level=6.Figure 13 is shown in 150 times of amplifications The scanning electron micrograph of the top surface of the product of lower shooting.Figure 14 is shown in 100 times of products shot under amplifying The scanning electron micrograph at side view visual angle.Figure 15 shows the scanning at the side view visual angle of 300 times of products shot under amplifying Electron micrograph.The length and width in the gap between fiber is less than 0.01mm.The weight of fabric is 216 grams/m.

Embodiment 2a

In addition to Weaving pattern is plain weave, braided fabric is constructed in the same manner as the mode that embodiment 1a is described. The braided fabric has the following properties that:Thickness=0.15mm, MVTR=21336 grams/m/24 hours, water absorption rate= 4gsm, feel (hand)=83g, oily level=<1, WEP=3.13KPa, air permeability=0.44cfm, tearing strength= 36.3N.Figure 16 shows the scanning electron micrograph in the top surface of 150 times of fabrics shot under amplifying.Figure 17 is shown Scanning electron micrograph at the side view visual angle of 250 times of products shot under amplifying.The length in the gap between fiber and Width respectively may be about 0.01mm and 0.01mm.The weight of fabric is 142 grams/m.

Fiber (172dtex) is taken out from braided fabric and complying with after its braiding carries out dimensional measurement under state, with Show the compliance of fiber.It is 0.25mm to measure folding width after the braiding of fiber, and fold height is 0.0736mm after braiding, Aspect ratio is 3.4 after braiding, and density is 0.94 gram/cc after braiding.The folding width after width and braiding before braiding The ratio between be 4.0:1.

Embodiment 2b

Cause embodiment 2a braided fabric that there is oleophobic property in the same manner as the mode that embodiment 1b is described.

The oleophobic property braided fabric has the following properties that:Thickness=0.16mm, MVTR=13265 grams/m/24 is small When, water absorption rate=7gsm, feel (hand)=141g, tearing strength=30.3N, WEP=4.01 KPa, air permeability= 0.49cfm, and oily level=6.Figure 18 shows that the scanning electron in the top surface of 150 times of fabrics shot under amplifying shows Micro- photo.Figure 19 shows the scanning electron micrograph at the side view visual angle of 250 times of fabrics shot under amplifying.Fiber it Between the length and width in gap respectively may be about 0.01mm and 0.02mm.The weight of fabric is 158 grams/m.

Embodiment 2c

Oleophobic property laminate is built in the following manner.By the fusing polyurethane sticking that dot pattern is applied on film Film and yarn fabric are combined together by agent.In the case where polyurethane binder point melts, yarn fabric is placed in the bonding of fabric The top of agent side.Make the spontaneous cooling of the structure.Then, the fusing polyurethane sticking on film using dot pattern is passed through Agent is by fabric and film combination.In the case where polyurethane binder point melts, fabric is placed in the top of film.Make the structure Spontaneous cooling.

Resulting product has the following properties that:Thickness=0.24mm, MVTR=8274 grams/m/24 hours, water absorption rate =10gsm, feel (hand)=465g, tearing strength=20.59N, and oily level=6.Figure 20 is shown in 150 times of amplifications The scanning electron micrograph of the top surface of the product of lower shooting.Figure 21 is shown in 250 times of products shot under amplifying The scanning electron micrograph at side view visual angle.The length and width in the gap between fiber respectively may be about 0.01mm and 0.03mm. The weight of fabric is 214 grams/m.

Embodiment 3a

Ribbon has been made in the same manner as the mode that embodiment 1a is described.Then the ribbon is cut open, to produce The cross section that 1.14mm is wide, 0.24mm is thick, and unit weight is 2184dtex.Then the ribbon of the incision is with 6.00: Plate of 1 draw ratio and the rate of extension of 70%/second by the heating for being set to 390 DEG C is expanded.Afterwards with 2.50:1 Plate of the rate of extension of draw ratio and 74%/second by the heating for being set to 390 DEG C is expanded.Then further with 1.30: Plate of 1 draw ratio and the rate of extension of 26%/second by the heating for being set to 390 DEG C is expanded.Afterwards in 1.4 seconds With 1.00:1 draw ratio passes through the plate for the heating for being set to 390 DEG C, produces amorphous state locking (amorphously locked) Intumescent PTFE fibers.

The ePTFE fibers of amorphous state locking (amorphously locked) measure 112dtex unit weight, With rectangular cross section and have the following properties that:Width=0.7mm, height=0.0356mm, density=0.45 gram/cube li Rice, fracture strength 2.14N, toughness 1.92cN/dtex, and fibrillation length=57.2 micron.

Figure 22 shows the scanning electron micrograph in 1000 times of fibers shot under amplifying.Figure 23 is shown The scanning electron micrograph at the side view visual angle of the lower fiber shot of 1000 times of amplifications.

The fiber is used to make braided fabric.Weaving pattern is 2/2 twill, and thread count is 100 × 100 yarns/English It is very little.The braided fabric has the following properties that:Thickness=0.15mm, MVTR=32012 grams/m/24 hours, water absorption rate= 21gsm, feel (hand)=47g, oily level=<1, WEP=2.15KPa, air permeability=1.17cfm, tearing strength= 57.8N.Figure 24 shows the scanning electron micrograph in 150 times of braided fabrics shot under amplifying.Figure 25 is shown The scanning electron micrograph at the side view visual angle of the lower fabric shot of 200 times of amplifications.The length and width in the gap between fiber Less than 0.01mm.The weight of fabric is 102 grams/m.

Fiber (112dtex) is taken out from braided fabric and complying with after its braiding carries out dimensional measurement under state, with Show the compliance of fiber.Folding width is 0.25mm after the braiding of fiber, and fold height is 0.0559mm, braiding after braiding Aspect ratio is 4.5 afterwards, and density is 0.80 gram/cc after braiding.The ratio between folding width after width and braiding before braiding For 2.8:1.

Embodiment 3b

Cause embodiment 3a braided fabric that there is oleophobic property in the same manner as the mode that embodiment 1b is described.The product has There is following property:Thickness=0.15mm, MVTR=20526 grams/m/24 hours, water absorption rate=15gsm, feel (hand) =86g, tearing strength=48.2N, WEP=5.45KPa, air permeability=1.85cfm, and oily level=6.Figure 26 is shown In the scanning electron micrograph of 150 times of fabrics shot under amplifying.Figure 27 shows that what is shot under 200 times of amplifications knits The scanning electron micrograph at the side view visual angle of thing.The length and width in the gap between fiber is less than 0.01mm.The weight of fabric Measure as 120 grams/m.

Embodiment 4

Obtaining PTFE resin, (Teflon 669X are purchased from the E.I. E.I.Du Pont Company (E.I.du of Delaware State Wilmington Pont de Nemours, Inc., Wilmington, DE) fine powder.The resin withK is with 0.184g/g (with powder Last weight meter) ratio mixing.Powder through lubrication is compressed in cylinder, in an oven in placement 18 hours at 49 DEG C.So Piece is extruded by plunger type with 169/1 drawdown ratio afterwards, to make the ribbon that about 0.64mm is thick.Afterwards by the band of extrusion Shape thing boil down to 0.25mm thickness.Then the ribbon of compression is stretched between two groups of rollers in a longitudinal direction.Second group Speed ratio (i.e. draw ratio) between roller and first group of roller is 1.4:1, rate of extension is 30%/second.Then to the banding of stretching Thing is limited and dried at 200 DEG C.Then two groups in room of the temperature for 300 DEG C of heating of dry ribbon add Between the roller of heat, 1.02 are expanded to the rate of extension of 0.2%/second:1 ratio, it is swollen with the rate of extension of 46%/second afterwards It is swollen to 1.75:1 other expansion rate, is then expanded to 1.02 with the rate of extension of 0.5%/second:1 other expansion Ratio.The process has made the ribbon that thickness is 0.24mm.

Then the ribbon is cut open, to produce the cross section that 1.14mm is wide, 0.24mm is thick, and unit weight is 2373dtex.Then the ribbon of the incision is with 6.00:1 draw ratio and the rate of extension of 69%/second is by being set to 390 DEG C the plate of heating expanded.Afterwards further with 2.20:1 draw ratio and the rate of extension of 32%/second is by being set to The plate of 390 DEG C of heating is expanded.Further with 1.40:1 draw ratio and the rate of extension of 19%/second is by being set to The plate of 390 DEG C of heating is expanded.Further with 1.20:1 draw ratio and the rate of extension of 12%/second is by being set to The plate of 390 DEG C of heating is expanded.Afterwards with 1.00 in 2.1 seconds:1 draw ratio process is set to 390 DEG C of heating Plate, produces the intumescent PTFE fiber of amorphous state locking (amorphously locked).

The ePTFE fibers of final amorphous state locking (amorphously locked) measure 107dtex unit length Weight, the cross section with rectangle simultaneously has the following properties that:Width=0.45mm, height=0.0279mm, density=0.85 Gram/cc, fracture strength 3.20N, toughness 3.01cN/dtex, and fibrillation length=16.1 micron.

Figure 28 shows the scanning electron micrograph in the top surface of 1000 times of fibers shot under amplifying.Figure 29 It is the scanning electron micrograph at the side view visual angle of 1000 times of fibers shot under amplifying.

The fiber is used to make braided fabric.Weaving pattern is 2/2 twill and thread count is 100 × 100 yarns/English It is very little.The braided fabric has the following properties that:Thickness=0.13mm, MVTR=28497 grams/m/24 hours, water absorption rate= 5gsm, feel (hand)=72g, oily level=<1, WEP=1.96KPa, air permeability=2.4cfm, tearing strength= 71.2N.Figure 30 shows the scanning electron micrograph in the top surface of 150 times of fabrics shot under amplifying.Figure 31 is shown In the side view of 150 times of fabrics shot under amplifying.The length and width in the gap between fiber is less than 0.01mm.Fabric Weight be 93 grams/m.

Fiber (107dtex) is taken out from braided fabric and complying with after its braiding carries out dimensional measurement under state, with Show the compliance of fiber.Folding width is 0.25mm after the braiding of fiber, and fold height is 0.0356mm, braiding after braiding Aspect ratio is 7.0 afterwards, and density is 1.20 grams/cc after braiding.The ratio between folding width after width and braiding before braiding For 1.8:1.

Embodiment 5

Ribbon has been made according to the mode same with embodiment 1a.Then the ribbon is cut open, to produce 4.57mm Cross section thick wide, 0.236mm, and unit weight is 7937dtex.Then the ribbon of the incision is with 6.00:1 drawing The plate than the extensibility with 70%/second by the heating for being set to 390 DEG C is stretched to be expanded.Afterwards with 2.50:1 draw ratio The plate for passing through the heating for being set to 390 DEG C with the rate of extension of 74%/second carries out another expansion.Further with 1.30:1 Plate of the rate of extension of draw ratio and 26%/second by the heating for being set to 390 DEG C is expanded.Afterwards in 1.4 seconds with 1.00:1 draw ratio passes through the plate for the heating for being set to 390 DEG C, produces amorphous state locking (amorphously locked) Intumescent PTFE fibers.

The ePTFE fibers of amorphous state locking (amorphously locked) measure 452dtex unit weight, With rectangular cross section and have the following properties that:Width=2.2mm, height=0.0406mm, density=0.51 gram/cube li Rice, fracture strength 11.48N, toughness 2.55cN/dtex, and fibrillation length=60 micron.Figure 36 is shown at 1000 times The scanning electron micrograph of the lower fiber surface shot of amplification.Figure 37 is shown in 1000 times of fibers shot under amplifying The scanning electron micrograph at side view visual angle.

Weaving pattern is plain weave, and thread count is 50 × 50 yarns/inch (19.7 × 19.7 yarns/centimetre).Braiding Preceding fiber width is 4.3 with distributing to the ratio between space of single fiber in the Weaving pattern calculated:1.The braided fabric has Following property:Thickness=0.24mm, MVTR=14798 grams/m/24 hours, water absorption rate=15gsm, hand lever (hand)= 281g, oily level=<1, WEP=1.86KPa, the cfm of air permeability=2.1.Figure 38 shows what is shot under 150 times of amplifications The scanning electron micrograph of braided fabric.Figure 39 shows the scanning at the side view visual angle of 150 times of fabrics shot under amplifying Electron micrograph.The length and width in the gap between fiber respectively may be about 0.04mm and 0.01mm.Figure 40 and 41 is shown In the scanning electron micrograph of the top surface of 120 times of fabrics shot under amplifying, it respectively depict horizontal direction Gap width is measured and the gap width of vertical direction is measured.The weight of fabric is 211 grams/m.

Fiber (452dtex) is taken out from braided fabric and complying with after its braiding carries out dimensional measurement under state, with Show the compliance of fiber.Folding width is 0.40mm after the braiding of fiber, and fold height is 0.1524mm, braiding after braiding Aspect ratio is 2.6 afterwards, and density is 0.74 gram/cc after braiding.The ratio between folding width after width and braiding before braiding For 5.5:1.

Embodiment 6

In addition to the thread count of plain weave pattern is 40 × 40 yarns/inch (15.7 × 15.7 yarns/centimetre), with The mode that embodiment 5 is described similarly constructs braided fabric.The braided fabric has the following properties that:Thickness=0.25mm, MVTR=27846 grams/m/24 hours, water absorption rate=7gsm, feel (hand)=71g, oily level=<1, WEP= 1.69KPa, air permeability=3.87cfm.Figure 42 shows sweeping for the top surface of the fabric shot under 150 times of amplifications Retouch electron micrograph.Figure 43 shows that the scanning electron microscopy at the side view visual angle of 150 times of fabrics shot under amplifying shines Piece.Figure 44 and 45 respectively illustrates the scanning electron micrograph at the side view visual angle of the fabric shot under 300 times and 400 times. Figure 45 clearly shows that fiber is complied with braiding interval, and the fiber itself is folded.

The length and width in the gap between fiber respectively may be about 0.08mm and 0.02mm.The weight of fabric be 157 grams/ Square metre.

Fiber (452dtex) is taken out from braided fabric and complying with after its braiding carries out dimensional measurement under state, with Show the compliance of fiber.Folding width is 0.50mm after the braiding of fiber, and fold height is 0.1219mm, braiding after braiding Aspect ratio is 4.1 afterwards, and density is 0.74 gram/cc after braiding.The ratio between folding width after width and braiding before braiding For 4.4:1.

Comparative example 1

W.L. Ge Er and colleague's share (model V111776, W. L. Gore & Associates, Inc., Mali are obtained Lanzhou Ai Kedun (W.L.Gore&Associates, Inc., Elkton, MD)) system ePTFE fibers.EPTFE fibers are measured 111dtex unit weight, with rectangular cross section and has the following properties that:Width=0.5mm, height= 0.0114mm, density=1.94 gram/cc, fracture strength=3.96N, toughness=3.58cN/dtex, and fibrillation Length=uncertain (end points that fibrillation is defined without visible node).Figure 32 shows and shot under 1000 times of amplifications Fiber top surface scanning electron micrograph.Figure 33 shows the side view in 1000 times of fibers shot under amplifying The scanning electron micrograph at visual angle.

Successfully to weave the fiber, twisted with the condition of 315 turns/rice (turns/meter).Then this is twisted Fibrage enter in fabric, the use of 2/2 twill pattern and thread count is 100 × 100 yarns/inch.

The braided fabric has the following properties that:Thickness=0.12mm, MVTR=36756 grams/m/24 hours, water suction Rate=4gsm, feel (hand)=102g, WEP=0.39kPa, air permeability=367cfm, and oily level=<1.Figure 34 Show the scanning electron micrograph in the top surface of 150 times of fabrics shot under amplifying.Figure 35 is shown at 150 times The scanning electron micrograph at the side view visual angle of the lower fabric shot of amplification.The length and width difference in the gap between fiber About 0.09mm and 0.12mm.The weight of fabric is 94 grams/m.

Comparative example 2

Commercially available non-micropore ePTFE fibers (model V112961, W.L. Ge Er has been obtained from W.L. Ge Er and colleague's share And colleague limited company, Maryland State Ai Kedun (W.L.Gore&Associates, Inc., Elkton, MD)).ePTFE Fiber measures 457dtex unit weight, with rectangular cross section and has the following properties that:Width=0.6mm, height =0.0419mm, density=1.82 gram/cc, fracture strength=18.33N, toughness=4.03cN/dtex, and fibril Tie up length=uncertain (end points that fibrillation is defined without visible node).Figure 46 shows and clapped under 1000 times of amplifications The scanning electron micrograph of the top surface for the fiber taken the photograph.Figure 47 is shown in the side of 1000 times of fibers shot under amplifying Depending on the scanning electron micrograph at visual angle.

Successfully to weave the ePTFE fibers, twisted with the condition of 118 turns/rice.Then the fiber of the twisting is compiled It is woven into fabric, the use of plain weave pattern and thread count is 50 × 50 yarns/inch.

The braided fabric has the following properties that:Thickness=0.21mm, MVTR=11659 grams/m/24 hours, water suction Rate=10gsm, feel (hand)=380g, WEP=0.49kPa, air permeability=70cfm, and oily level=<1.Figure 48 Show the scanning electron micrograph in the top surface of 150 times of fabrics shot under amplifying.Figure 49 is shown at 150 times The scanning electron micrograph at the side view visual angle of the lower fabric shot of amplification.The length and width difference in the gap between fiber About 0.11mm and 0.08mm.The weight of fabric is 201 grams/m.

Comparative example 3

Commercially available ePTFE fibers (model V112961, W.L. Ge Er and colleague has been obtained from W.L. Ge Er and colleague's share Limited company, Maryland State Ai Kedun (W.L.Gore&Associates, Inc., Elkton, MD)).EPTFE fibers are surveyed 457dtex unit weight, with rectangular cross section and have the following properties that:Width=0.6mm, height= 0.0419mm, density=1.82 gram/cc, fracture strength=18.33N, toughness=4.03cN/dtex, and fibrillation Length=uncertain (end points that fibrillation is defined without visible node).Figure 46 shows and shot under 1000 times of amplifications Fiber top surface scanning electron micrograph.Figure 47 shows the side view in 1000 times of fibers shot under amplifying Figure.

Successfully to weave the ePTFE fibers, twisted with the condition of 138 turns/rice.Then the fiber of the twisting is compiled It is woven into fabric, the use of plain weave pattern and thread count is 64 × 64 yarns/inch.

The braided fabric has the following properties that:Thickness=0.24mm, MVTR=7840 grams/m/24 hours, water suction Rate=9gsm, feel (hand)=698g, WEP=1.12kPa, air permeability=26cfm, and oily level=<1.Figure 50 shows The scanning electron micrograph in the top surface of 150 times of fabrics shot under amplifying is gone out.Figure 51 shows and put at 150 times The side view of the big lower fabric shot.The length and width in the gap between fiber respectively may be about 0.07mm and 0.02mm.Fabric Weight be 261 grams/m.

Hereinbefore synoptically and present invention is described for embodiment.To this area It is obvious to the skilled person that in the situation of the spirit or scope of the present invention limited without departing from appended claims Under, various modifications and changes can be carried out to the present invention.

Claims (8)

1. a kind of single fiber silk fiber, it includes expanded polytetrafluoroethyl,ne, the density of the single fiber silk fiber less than or equal to about 1.0 grams/cc, thickness is below about 100 microns, and width is below about 4.0mm, and aspect ratio is greater than about 15, and with essentially The cross-sectional configuration of rectangle.
2. single fiber silk fiber as claimed in claim 1, it is characterised in that the toughness of the single fiber silk fiber is greater than about 1.6cN/ dtex。
3. single fiber silk fiber as claimed in claim 1, it is characterised in that the fracture strength of the single fiber silk fiber is at least about 1.5N。
4. single fiber silk fiber as claimed in claim 1, it is characterised in that there is fluorinated acrylic ester on the single fiber silk fiber Coating.
5. single fiber silk fiber as claimed in claim 1, it is characterised in that the single fiber silk fiber is compliance, so that In knitting structure, the single fiber silk fiber is folded on itself.
6. single fiber silk fiber as claimed in claim 1, it is characterised in that the single fiber silk fiber, which has to limit, runs through the fibre The node and fibrillation of the path of dimension.
7. single fiber silk fiber as claimed in claim 1, it is characterised in that the length of the fibrillation is about 5 microns-about 120 Micron.
8. single fiber silk fiber as claimed in claim 1, it is characterised in that the unit weight of the single fiber silk fiber is less than About 500dtex.
CN201710339191.8A 2013-09-17 2014-08-18 Compliance microporous fibre and the braided fabric containing the fiber CN107227536A (en)

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US20170044696A1 (en) 2017-02-16

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