2) United States Patent oy oy ~ 0) ey @y 6s) (2) Gn (2) Johnson et al LIGHTWEIGHT, DURABLE APPAREL AND. LAMINATES FOR MAKING THE SAME Applicant: W. L. Gore & Associates In., Newark, DEW) Inventors: Matthew A. Johnson, Bear, DE (US) Edward C. Gunzel, Oxiord, PA (US) Assignee: WAL. Gore & Associates, Inc, Newark DEW Notice: Subject to any disclaimer, the teem ofthis patent is extended of adjusted under 35 USC. 1540) by 517 days. Appl. Now 13/826,046 Filed: Mar. 14,2013, Prior Publication Data US 2015001927531 Aug. 1, 2013 Related US. Application Data Division of application No. 12/465.383, filed on May 13, 2009, now Pat. No, 9,006,117. Int. Cl. AdID 3100 (2005.01) AMID 306 (2005.01) Ban 524 (2006.01), DosP 192 (2008.01) A4ID 2700 (2006.01) aad 31002 (2006.01) B32B 37112 (2006.01) (Continued) us.cl. CPC AID 3/04 (2013.01), A4TD 27/00 2013.01) ‘BDI S724 (2013.01; DUGP 1/90 (2013.01): AID 31/02 (201301), B32B 37/1284 (2013.01); 8328 38/145 2013.01), 8328 'US009215897B2 US 9,215,897 B2 Dec. 22, 2015 (10) Patent No. 4s) Date of Patent: 2037/2435 (2013.01), B32B 2305/18 2013.01); 18328 2307/73 (2013.01): B32B 2327/15, (2013.01), 8328 2377/00 2013.01}, B32B 2459/00 201301}; YI0T 2949826 201501) YLOT 442/3878 2015.04); YIOT 442/469 (201508) (58) Fleld of Classification Search, CPC... AMID 31/0035; AID 31/00, YIOT 156/10, usp 2/455; 442/59, 76,77, 79, 80, 181 ce application file for complete search history. 66) References Cited US. PATENT DOCUMENTS 3580595 A GIITL Ainsworth ta sosisee A 41076 Gore (Continued) FOREIGN PATENT DOCUMENTS eS 2006 (Continved) OTHER PUBLICATIONS PCTUS201N001145, ntrational Search Report, Jl, 20, 2010,6 pases (Continved) Peter Choi Amy L Primary Examiner (74) Attornes Agent, or Firm Miller on ABSTRACT Laminates ae described having a durable outer film surface foruse in making lightweight liquidproot articles of apparel sch as outerwear ganments.A method of making the lami nate and a lightweight outerwear garment having an abrasion resistant exterior film surface is described 12 Claims, 2 Drawing SheetsUS 9,215,897 B2 Page 2 GY Ineck 2o07100096% AL v/2007 8320 3800 (2006.01) aooninymasns AL 12007 Fe ian aT 00801) Gomorra AL 3200) Courney 2100129629 AL $2010 Teceeah 65) References Cited FORPIGN PATENT DOCUMENTS US. PATENT DOCUMENTS 5 Contes 4302896 A LW1B81_ Donovan a scene eons SaoSet A "iba Som 2 Soomne aan Gematol ean in salvos iow. Goasrte & Sto ita. fe 5 183 Shoe Sts * Bios Susser A t0tpe2 i” aontorir> —‘Taoot Sivan A "Sone 3 i Sooisisess 112001 Ssisaos A $558 i Sonseorie ‘X02 Saisie A tbo % oossoews Dams stints A 32000 : ” doosnetd 93008 Ssars Br 4008, ie doorsioas? S207 Share BL 42004 eet ome ae eoma%e m2 S00 Wo avoltaet 2008 00729 2 EA00T cme tal Tes6401 BL 62009 Favor ea OTHER PUBLICATIONS Frutson Be 400 nat 2003'005415$ AL 3'2003 Nomi et al. ‘PCTAUS2010/001144, Intemational Search Report, Aug. 26, 2010,6 doovo130303 AL 7/2003. Cavanaugh etal posesU.S. Patent Dec. 22, 2015 Sheet 1 of 2 US 9,215,897 B2U.S. Patent Dec. 22,2015 Sheet 2 of 2 US 9,215,897 B2 geUS 9,215,897 B2 1 LIGHTWEIGHT, DURABLE APPAREL AND. LAMINATES FOR MAKING THE SAME (CROSS REFERENCE TO RELATED "APPLICATIONS, ‘This application is a divisional of US. patent application Ser. No. 12/465,383 filed May 13, 2009, the entre contents of ‘which are expressly incorporated herein by reference in its tirety. FIELD OF THE INVENTION Described herein is breathable lightweight durable lami= nate having an outer film surface, and a lightweight durable aniele of apparel made from the laminate having an exterior film surface, BACKGROUND OF THE INVENTION Anicles of opparel having fl layers for providing water resistance o liqhidproofness, while simultaneously provide ing breathability are known. Laminates and garments are ‘constructed to provide protection tothe film layer $0 28 t0 resist tearing, damage by puneture or abrasion, and the like. Inner and outer fabric layers are most frequently added (© both surfices of the film to protet the film surface from damage. Altematively, garments having a film surface uncovered by saprotetive inner orouterlayer of fabric are often constructed Tor use in combination with another garment whose fabric surface wll provide protection tothe film layer against dam ‘age, For example, an undergarment comprising a lm com- posite lacking an cuter protective fabric layer i constructed to be used under a separate outer garment where itis less susceptible to sustaining direet damage. The addition of outer and inner fabric layers required 10 protet film layers from damage adds weight to an article of ‘apparel, al results in materials having a higher water pickup ‘on the outer surface. Moreover, wearing an outerwear gar ment to protect an undergarment having fl layer forms @ bulky ensemble SUMMARY OF THE INVENTION A lightweight laminate having an outer film surface is dseribed. The lightweight laminate is sufficienly durable ‘aginst abrasion for use in making anicles of apparel suchas ‘outerear garments, having an exterior film surface that remains liquidproo! after an abrasion challenge. The light ‘weight laminate has @ porous polymer surface that ean be ‘colorized. for example, by printing. The laminate outer fa surface can be coated with an oleophobie coating composi tion to provide oleophobiciy ‘A method of making a lightweight laminate having an brasion resistant outer film surface is described. The method ‘comprises the steps of selecting a textile layer, selecting a rigged porous tluoropol brane; coating and col ‘orizng the porous flaoropolymier membrane to form an ole ‘ophobicnoropolymer fl having an outer fil surface: and Jaminating the textile and the porous Ruoropolyme film #0 orm laminate, optionally before or after the coating step oF the colorizing step to form a laminate having an outer fim surface and an inner textile surface. In one embodiment, @ laminates formed having a moisture vapor tansmission rate Js greater than 1000 pim/24 hours, laminate 2 Jess than 200 g/m", and the laminate outer lm surfoee that is abrasion resistant, resulting ina durably iquidproof laminate ‘A method of making an article of apparel, such 2a light ‘weight outerwear garment, having an abrasion resistant dura- by liquidproo exterior film surface is deserbed. The method comprises the steps of selecting laminate havinga woven or [eit texte layer laminate toa porots fompolymer meme ‘brane; coating and colrizing te porous fuoropolymer mem- brane ith an oleophobic polymer composition, optionally before or after the laminating step, thereby forming lami pale ving an outer film surface and an inner textile surface: assembling an outerwear garment from the laminate so that the colorized outer film surface is the outerwear garment film surface and the textile inner surface is ona side the cuter film surface, DESCRIPTION OF THE DRAWINGS ‘The operation of the present invention should become ppareat fom the following description when considered in ‘conjunction with the accompanying drawings, in which FIG, 1a is perspective view of one embodiment of 3 gar- met front surfiee TFIG. 1) is perspective view of one embodiment of gar- ment back surface FIG. 2 is perspective view of one embodiment ofa lami pate DETAILED DESCRIPTION OF THE INVENTION Described, herein, is a breathable lightweight, durable laminate for use in making liquidproof aricles of apparel stich as outerwear garments, The laminate s designed having 4 durably colorized outer film surface. A breathable light- ‘weight, outerwear garment is described that comprises an exterior film surface tat is resistant to abrasion and i there- fore durably liquidproof, and has a printable non-textile exte- or surlie. ‘One embodiment, exemplified in FIGS. La and 1, illas- tratea perspective view ofa garment (1) inthe form ofa jacket having a gimient exterior non-textile surface on the garment front surface (20) and the garment back surfice (21). The jacket (1) comprises an exterior non-textile surface (2) and an interior textile surfiee (3) that faces towards the body of ‘wearer. The jacket (1) comprises front closure (4, sleeves (6) with wrist cus (6), and a waist band (7), The garment is {ormed from a laminate, exemplified in the ross-setional illustration of FIG. 2 In one embodiment, the gaement com- prises a laminate (10) that comprises an outer film surface (11) and an inner textile surface (12). The laminate (10) comprises a porous membrane (13) adjacent to textile layer (14). The porous membrane (13) may be colorized with & coloraat (16) andr an cleophobic composition, forming the ‘outer film surface (11) ofthe laminate (10). The textile layer (14) adjacent the porous membrane (13) on a side opposite the onter film surface (11) and is attached to the porous membrane by attachments (15), which are exemplified in FIG. 2 as discontinuous attachments. Is desirable to make laminates having a film surface that ‘can be durably coated, for example with colorants and ole- ‘phobic coatings. Where themembrane layers alow surface energy film, sich as many fluoropolymer materials, mem- brane porosity ishelpful to aehieve durable mechanical bond- ‘ng of the coating compositions within the membrane strc- ture, However, many porous films ae known 10 abrade easily ‘making it dificult to achieve durable liquidproofnes¢ sing the porous fils in applications that will subject them toUS 9,215,897 B2 3 abrasion, Laminates deseribed herein have a film surface Tormed from membrancs having sullcient porosity to provide adurable coating bu that are resistant toabrasion maintaining Tiguidprootness “The outer porous film surface (11) ofthe laminate (10) ean bbe made, for example, from a porous membrane comprising polymeric materials such as fuoropolymers, polyolefins, polyurethanes, and polyesters. Suitable polymers may com prise resins that can be processed 10 form porous oF microporous membrane structures. For example, polyte- rafluoroethylene (PTFE) resins that canbe processed to fon freichel porous structures are suitable for use herein, For ‘example, PTFE resins can be stretched to form microporous ‘membrane structures characterized by nodes interconnected by fibrils when expanded according to the process taught in patents such as i U.S. Pat. Nos. 3,953,566, 5,814,405, of 7,306,729. In some embodiments, expanded PTFE fiuo- ropolymer films are made from PTFE resins according 0 US. Pat, No. 6,541,589, having comonomer units of poly- ‘Avorobuiyletiyleae (PFBE), For example, microporous ‘expanded PTEE (@PTFE) fluoropolymerscan comprise PTFE having from about 0.05% by weight to about 0.5% by weight ‘of comonomer units of PPE hased upon the total polymer weight none embodiment, the outer porous membrane (13) om prises ePTFE having a mierostructure characterized by nodes Interconnected by ibis, wherein the pores ofthe porous im are sulficiently tight 90 as 1 provide Iguidprooless and sufficiently open to provide properties such as moisture vapor transmission, and penetration by coatings of colorants and ‘leophabie composts. For example, in some embadi- ments, it is desirable forthe porous membranes fo have an average median lw pore size of less than of equal to about 400 nm to provide water resistance, and a mesian Hos pore size greater than about 50 am for colorization. This may be accomplished by compounding a PTFE resin which is sited to produce a node and fibril mierostrutire upon stretching. “Theresincan be blended with analiphatichydeocarbon lube ‘cant extrision aid such asa mineral spit. The compounded resin. may be formed into a eylindrial pellet and paste cexinaded by known procedures into a desired extrudable shape, preferably a tape or membrane, The article can be cclendered tothe desired thickness between rolls and then, thermally dred to remove the lubricant. The dred artile is ‘expanded by stretching in the mochine and/or tamsverse slirections, for example, according to the teachings of US, Pat, Nos. 3.983,566, 5.814.405, or 7.406,729, to produce an ‘expanded PTFE stricture characterized by a series of nodes which are interconnected by fibrils. The ePTFE article is then amorphouslyToeked by heating the article above the erystal- line melt point of PTFE, for example between about 343°- 375°C. ‘Where laminates are deseribed as durubly’liguidproot. itis ‘man that the laminate remains iquidproof after an abrasion challenge acconting to the Liguidproof After Abrasion test, method deseribed hercin. In some emibodiments, laminates that achieve durable liquidproofness comprise a textile lami nated to’ porous membrane that hs a hall burst load greater than 17 By oF greater than about 19 Thy when measured according the Ball Burst load est doseribedhorein. Insome ‘embodiments, laminates that achieve good durable lguid= proofhess comprise textile laminated to 9 porous membrane having certain properties when tested according tothe Tough- ness, Maximum Load, MTS, and Modulus test dseribod herein For example, in some embodiments, laminates having a textile laminated to © porous membrane with an avemge ‘maximum Toad (the average of the maximum load in the 0 o 4 longitudinal and transverse directions) greater than ION, oF treater than 12N, oF greater than 20N, are durably liguid- rool, Suitable porous membranes may have an average ‘modulus in the transverse and longitudinal direction of areater than about 40 MPa or greater than about 50 MPa, or ‘greater than about 60 MPa. In some embodiments, durably Jiquidproo laminates comprise porous membranes having an verge matrix tensile strength inthe longitudinal and trans- verse direction of greater than 90 MPs, or greater than 9S (MPa. or greater than 100 MPa, or greater than 150 MPa, ‘The porous node and fib! stature of an expanded fuo- ropolymer membrane enables coating materials unr print materials to adhere to this porous substrate, Low surface energy foropolymer films, such as ePTFE, isknown to repel face treatments, thereby providing a challenge for durable coatings, such as those comprising colo- ras. However, in one embodiment, a coating composition comprise 8 binder and colorant to colorze a film surface used as the outer film surface of the laminate. ‘The coating ‘composition coats or encapsulates the nodes andor fbrls of the expanded Ruoropolymerstractare forming a durable ae thetic appearance. "Membrancs stable for use as the outer film surface have 8 surface that when printed provides a durable aesthetic. Aesthetic durability can be achieved in some embodiments ‘with colorant coating compositions that comprise pigment hhaving particle size sufficiently smal to ft within the pores of the porous substrate. Pigment partieles having mean tiamter of less than about 250 nm are wsefl for forming {durable color. Coating compositions may further comprise a binder capable of wetting the porois substate and binding the pigment to the pore walls Minltiple colors can be applied using multiple pigments, or varying the concentrations of one of more pigmenl, or by both techniques. none embodiment, laminate comprises aa ‘outer film surface and is colorized on more than 90% ofthe ‘outer film surface by printing or other application tochnigue, ‘while retaining porosity and moisture vapor transmission, In ‘one embodiment, the surface ofthe film can be colorized with colorant to form a solid color oe pattern (design). Coating ‘compositions comprising colorants can he applied to prewide variety of colors and designs, such as solid, eamtouflage and Frnt pattems. Coating compositions may comprise one oF ‘more colorants suitable for use in printing camouflage pat- tems such as woodland and desert pattems. Ia one embodi- ‘ment, a coating composition suitable for use in printing a ‘wonallands camouflage pattern on toa surface of pros fl ‘comprises black, brown, green, and light green colorant, Inan altemate embodiment a coating composition comprises ‘brown, Khaki, and tan colorant suitable for printing 2 desert ‘amoullge pater. Other embodiments comprise composi- ‘ions comprising colorants having shade variations within these wo examples, “The coating composition can be applisd to the porous ‘membrane, forming the porous outer film, by several meth- ‘ods. Application methods for colorizing include but are not Timited to transfer coating, seven printing, pravure printing, ink-jet printing, and knife cating. Additional topical treat- ts can be applied to the porous membrane, provided suf- ficient porosity throughout the laminate is maintained 10 remain moistre vapor tansmissve, Adkliional treatments ‘may be provided that impart functionality, such as but not Timited to oleophobicity. Examples of oleophobie ecatings ‘include for example, fluoropolymers such as faorowerylates ‘and other materials such as those tanght in U.S. patent app cation Ser. No. 11/440,870. When provided with an oleopho- bie coating, laminates are formed having an outer film surfaceUS 9,215,897 B2 5 with anol ating greater than about 2 when tested according to the Oil Repeliency Test described herein, ln other embodi- ‘ments, laminates may be formed whereia the outer film sur- face has an oil rating greater than or equal to about 4, oF treater or equal to about 5, oF greater or equal to about 6. ‘Optionally, the outer porous film may comprise a discontins- ‘ous coating, for example, inthe form of paticulates or diss ‘rete clements to provide even further abrasion resistance. A ‘coating of discrete materials may be sprayed or coated on the ‘outer film surface, and may compris. for example, polyure thane, epoxy, silicone, fluoropolymers amd the like, for Jmproving abrasion resistce of the laminate ‘An aesthetically durable colorized film surface can be formed having a color change of less than 20 Dela-E (4F) ‘when abrasion tested onthe colorized outer film surface ofthe laminate acordng fo the Color Change After Abrasion test described herein. Laminates ean also be formed having an, aesthetically durable film surface having adE less than 15, or 284 fess than 10, "The lamtnate further comprises textile (14) bonded tothe pros outer fii (13) ofthe laminate (10) ona side opposite the outer film surface (1). The textile (14) can he selected 10 provide dimensional stability tthe porcus oer film (13) when formed asa laminate Suitable Hightweight textiles may ‘comprise materials such as cotton, rayon, aylon and polyes= ter, and blends thereot ‘Coatings can also be provided to the textile (4) layer to Jmpart a Variety of properties tothe laminate. For example, a ‘colorant can be applied! othe textileto colorize the layer ina solid or patterned color having one or more than one color, ‘The textile and the membrane making up the outer film sir face can be colorized by the same or diferent technique, and by the same or different color or patter, as the ote il The porous membrane (13) layer forming the outer film surface (11) aud the textile (14) are bonded together in & ‘manner that maintains a desirably high level of moisture ‘vapor transmission. In some embodiments, for example, 10 ‘maximize air pemneability and moisture vapor transmission rates, discontinoows adhesive attachment are used oi the layers, Inother embodiments, the porous membrane (13) and the textile (14) can be laminated with a continuous adhesive though itis desirable thatthe contiauous adhesive layer is moisture vapor pennicabe, and the laminate has a moisture vapor transmission rate greater than about 2000 g/m/24 hours, Adhesive compositions include thermoset adhesives, such as polytrethane, and silicone, Thermoplastic adhesives include thermoplastic polyurethane. The porous membrane layer and the textile are attached by adhesive attachment through lamination processes, such as gravure lamination, spray adhesive bonding, and fusion bonding with a thermo- plastic serim to form the lightweight laminate. ‘Durably liguidproof laminates are abrasion resistant and ‘do nt leak after abrasion testing om the outer fils surface of the laminate for greater than or equal to about 1400 abrasion movements when tested according othe Ligquidproof (Suter) ‘After Hook and Loop Abrasion tet described herein nother ‘embosdiments laminates are formed that remain liguidpeoot aller 3000 abrasion movements on the outer film surface, oF remain liquidproof afer more than 4000 abrasion movements ‘onthe outer film surface, or remain liguidproo! for more than, 6000 abrasion movements on the outer fil surface, ‘Moisture vapor transmission, or breathability, i important to provide cooling 1 a wearer ofthe outerweat apparel made from laminates deseribed herein. Laminates deseribed herein, ‘are therefore breathable, having a moisture vapor transmis sion rate (MV'TR) greater than 1000 g/m/24 hours, or greater than 2000 gin"/24 hours, oF preater than $000 wim*/24 hours, 0 o 6 cor arater thas 10000 a/n*/24 hous, oF arate thn 15000 in"?24 hous, or greater than 20000 yla28 hours, when tested according to the method deseribe. Lighteihtan ats deserbot herein canbe formed having’ mass per area Jess than about 400 gigtm, or mass por area Test than abot 380 gl or amass per ara less than about 200 ress ‘han bout 150,u/n ores than about 145 wins Tess than boat 125 gino les than about 100 ‘Laminates described herein having an outer film surface dave low wate pickup when compared. for example, to lige ‘proof Taminses having an outer texile sure. Ta some bodiment the lasiotes described herein hve a water Piekp ess than or equal to about 10 gn whoa estedaccord dog to the Woter Pickup test desribed herein. In other embodiments laminate ate formed having a wate piekupof Jess than of equa © abou 8 gia, oF Less than oF ual 0 hut 6 wn, orless than or equal to about 4 gin orlessthan regalo boat 3 wi Armethod is deseribod for making lightweight laminates ‘ving an abrsion resistant outer fim surface The meibod comprises the saps of solocing a oni layer seleting 8 pores foropolyiner membrane having, for example, an Iemge maximum load inthe transverse and longi] dGrction of greater than 10; coating and eoorizing the porous Avoropalymer membrane with an oleophobie polymer com- positon anda colorant to obtain ports Morepolyae having an olenphobie colorized outer film surge with an cil ‘ang greater than andninating the textile and the porous fTuoropolymer film to form a lminat, optionally before or ier the coating te or the ctorizing sie o forma laminate faving an outer film surface and an nner textile surface. In coe embemient, he lamsinate asa moist vapor tans ‘Soo rte greater thas 1000 g/n24 hours, moss pears lexs {han 50 gn andthe aninateouter fil surfaces abrasion ‘essa, eminng igudproo! fer abrasion when ara on the outer fm surface ‘Armethod is also deserted for making lightweight aieles of apparel suchas, an outerwear zument having an abrasion resistant extecor film mirface. The method comprises the steps of: selecting. textile ayer and a porous Huoropolymer ‘membrane: asting and coloring the porous Buoeopolymer ‘membrane with an oleophobic polymer composition and a Coloraat a bisin an cleophobic colori ater in surface ‘witha orang pester han; laminating he ene ache porous Muorvpolymer. optionally before or aller the colina Step othe colorizing step, and forming laminate having an ‘utr fin surface sid an inner textite sures that s opposite to outer fl surface, wherein the laminate has a moistre ‘apor transmission ate greater tn 1000 g'n"/24 hours nd the laminate is abrasion resistant and durablyligidproot ler abrasion testing om the outer film surlace. The meio further comprises the steps of esembling an outerwear ga sna rom the laminate 0 thatthe colorized ute fim sree inthe outerwear garment exterior im surface Constrets made with the above described lasinstes include apparel such as oterwear gaments, jackets, pon: cos, raincoats, has, hoods, loves, puns, eral andthe ike Test Methods Mas Per Area “he mas per are of samples is measured acoating othe ASTM D 3776 (Standard Test Methods for Mass Per Unit Ao (Weight) of Fabre) test method (Option C) using 9 Metter Tolodo Scale, Model 1060, The scale i recalibrated pelocta weighing specimens, Weights are recorded i ounces {bthe caret half nce. This valve was converted to prams per square meters reported hereinUS 9,215,897 B2 7 Deasity for Membranes ‘Tomeasure the density of the membrane material examples ‘ofthe preseat invention and the comparative examples, prop= ‘erty data measured onthe samples were collected. As noted above, the 165 mmx S mm samples were measured to deter- mine their mass (using a Metler-Toledo analytical balance mode AB1O04) and ther thickness (using a Kafer 100030 ‘snap gauge). Using this data, density canbe ealeulated with the following formu where: prdensity (ee) mass (B) wwewidlh (1.5 em) Htength (16. em) ‘thickness (em) “Thickness for Membranes "To measure the thickness of the membrane material ‘examples of the present invention, a snap gauge (Kafer 1000/30) was used. Measurements were taken in st least ourareas ofeach sample, The average value ofthese multiple measurements is reported as the thickness value for each mmembeane. Gurley Air Plow “The sit permeability ofeach sample was determined based ‘om the time required to pass 50 ce of air trough the sample ‘acconting to FED-STD-1914 Method $452 withthe fllow- ing exception. This text methods was followed except that specimens were sealed prior to testing fo ensure a pood seal and no leakage around edges daring the test. Median Flow Pore Size Test ‘The average pore diameter of the porous membrane was reported as Median Flow Pore size (MEP). To determine MPP. a sample membrane having a 25 mm diameter was ‘obtained and wetted with perflouropolyether. The wetted sample membrane was placed in a Coulter Pommeter ‘wherein the average pore diameter of the final product was determined. Ball Burst Strength “The test method and related sample mounting apparatus ‘were developed by W.L Gore & Associates ne, foruse with ‘aChuillon Test Stand, The test measures the burt strength of materials such as fabries (woven, Knit, nonwoven, et.) porous or nonporous plastic films, membranes, sheet, Jaminates thereof, and other materials in planar form, ‘A specimen was mounted taut, but unstretched, between ‘0 annular clamping plates with an opening of 7.62 em diameter metal rod having a polished stel 2.54 em dia ‘eter ballshaped tip applied! a load against the eener of the specimen inthe Z-Jiecton (normal to the X-Y planar dire tions) The rod was connocted a its other end ton appropri- ‘ate Chatillon force gauge mounted in a Chatillon Materials, Test Stand, Model No. TCD-200. The load was applied atthe rateof 25.4 eav/minute until uiure ofthe specimen occurred. The failure (caring, burs, ete.) may occur anywhere within the clamped area, Results were reported as the average of throe measurements of the maximim applied free before failure, “Testing was done at ambient interior temperature and humidity conditions, renerally ta temperature of 21°C. t0 24°C. and relative humidity of 38% to 58%, Pall burst data ‘can be expressed as the ball burst siren 0 o 8 bass per area ofthe sample: mass per ara ofthe sample ean be determined from the product of deusity and thickness of the sample, Toughness, Maximum Load, MIS, and Modulis ‘Test Method ‘Sample preparation was accomplished hy wing a die punch t0 cut 165 mm long by 15 mm wide rectangular samples out of the ePTFE membrane web. The membrane web was placed on the cutting table such that it was fee from ‘wrinkles in the area where the sample was toe cut, The 165 smn] S mm die was then placed on the membrane (generally in the center 200 mm of the web) sueh that ts Tong axis is parallel to the direction that will be tested. The directions ‘quoted in this publication willbe measured inthe longitudinal ircetion (parallel to thedircctionof travel during processing) and the transverse direction (perpendicular tothe direction of ‘ravel during processing). One the ie is aligned, pressure is applied to cto eut through the membrane web, Upon removal ofthis pressure, the rectangular sample for testing should be inspocted to ensure itis free from edge defeets which may impact the tensile testing. ‘Atleast 3 samples inthe longitudinal () and in the trans verse (1) directions should be cut to characterize the mem- brane web. Once samples have been prepared, they were measured to determine their mass (using a Mettler-Toledo analytical balance model ABIO4) and their thickness (sing a Kafer FZ1000130 snap gauge). Each sample was subse- quently tested to determine is tensile properties using. an Inston $500 tensile tester running Merlin Series IX software (ersion 7.51). The samples were inserted into the tensile tester and held using Instron Catalog 2702-015 (rubber casted face plate) and 2702-016 (serrated face plate) grip ts such that each end of the sample is held between one Fabber coued and one seated fee plate. The presure applied to the grip plates was approximately 50 psi. The ‘ange length between the grips was set at 50 mm and the crosshead speed (pulling speed) was set toa speed of SOS ‘muvmin, A'0.1 KN load cell was used to cary out these ‘measurements and data was collected at arate of 50 points ‘see, The laboratory temperature should be between 68°F. and 72°F. to ensure comparable results. Finally, if the sample happened to break at the grip intetiee, the data was dis- carded, At Teast 3 samples in the Fongitdina and transverse dee tions should be successfully pulled (no slipping out of or ‘breaking at the grips) in order to characterize the membrane ‘web, The data analysis and calculations were performed with the Mein software orany other data analysis package. First, ‘the maximum load able to be supported by the sample during the tensile test for [and T directions was loeted, The ma ‘mum load for L and T was then normalized to the sample ‘physical properties (thickness and density) via the following ‘eqhation to calculate the matrix tensile strength for Lad T directions. wher: ‘MTS-Matri tensile strength (MTS) in Mpa aas-marinti load measured during test (Newtons) fos-theoretical density for PTFE (2.2 gramsiec) imple length (em)US 9,215,897 B2 9 Then, the average maximum load was calculated by aver. aging the maximum load for L withthe maximum load for T The average matrix tensile strength was calculated by aver- aging the matrix tensile for L withthe matrix tensile strength rl, "The toughness for each sample was determined by into trating the stress sean curve from the sampleto calculate the area below the curve, and averaged for three measurements foreach ofthe Land T directions, This number represents the ‘eneray required to break the simple, reported asthe sample toughness. Then, the average toughness was caleulated by averaging the toughness I with the toughness for . The modulus of each sample is determined by taking the slope from the linear clase portion of the sres-struin curv. First, the modulus inthe longitudinal (L) and transverse (1) brane havingan oleophobicouter membrane surfoceand oil ating greater than 2: coloring the porous PTFE membrane with a colorant to ‘oblain a colorized outer membrane surface: laminating the textile and the porous PTFE membrane to forma laminate, step orthe color ‘outer membrane surface and an inner textile surlace:and assembling anowterwear garment rom the laminate so that theoleophobic, colorized outer membrane surface is the ‘outerwear gamient exterior surface and the inner textile striae ison aside opposite the exterior surfoe ‘wherein said laminate is Higuidproof after more than 6000 abrasion movements on the outer membrane surfice ‘when tested aeconding to the Liguidproof (Suter) Ater Hook and Abrasion Test, ‘whorein said porous PTFE membrane has an averagemaxi- ‘mum load in the trnsverse and longitudinal direction aurcater than 10 N, wherein said porous PTFE membrane bas ‘modulus in the transverse and longinidi seater than 40 MPa, wherein said porous PTFE membrane has an average ‘matrix tensile strength in the longttadinal and transverse direction greater than 90 MPa, and. wherein suid ponous PTFE membrane has ball bust load ‘reat than 17 Ib Fore. 2. The method of laim I wherein the method comprises assembling the outerwear garment from the laminate so that the laminate textile inner textile surface is a garment interior textile surface 3. The method of claim 1 wherein the method comprises scloting a micmporous PTFE membrane comprising Per ‘uorobutylene (PFBE) comonomer. ‘4. The method of claim I wherein the method comprises selecting a porous PTFE membeane having a mass per area Jess than 80 gi 'S. The method of claim 1 wherein the method comprises selecting a porous PTFE membrane having a thickness less than 35 um, 6, The method of claim 1 whercin the textile comprises «| kat 0 o 16 7. The method of claim 1 wherein the textile comprises 3 '8. The method of claim 1 wherein the method comprises colorizng the laminate outer membrane surface by printing swith an ink et printer. '9. The method of claim 1 wherein the laminate onter miem= brane surface has anol rating of greater than 4 10, The method of claim 1 wherein the method comprises selecting laminate with a weight les than 400 g/m= 11. A method of making an outerwear garment having aa abrasion resistant exterior film surface, sid method eompris- ing: ‘selecting textile composite comprising laminate having, fan oleophobic colorized outer_-membrane surface, ‘wherein the laminate comprises: Ga porous PTFE membrane having an average maxim Joad inthe transverse and longitudinal direction greater than 10N, and (i) textile attached to the porous PTEE membrane on 3 side opposite the oleophobie colorized outer membrane surface: forming giment pices comprising the textile composite: assembling an oulerweer garment ffom seid garment Pieces by orienting the parment pieces so thatthe ole- ‘phobic colorized outer membrane surface isthe outer ‘Wear garment exterior surface and the inner textile sut= face i ona sie opposite the exterior surface; ‘wherein sid laminate sliguidproot aftr more than 6000 fchmision movements of the otter membrane surface When tested according tothe Liquidproof (Suter) After Hook and Abrasion Test, wherein stid porous PTFE membrane has an average ‘modulus in the tansverse and longitudinal direction ‘eater than 40 MPa, ‘wherein said porous PTFE membrane has an average ‘matrix tensile strength inthe longitadinal and transverse dlrection greater than 90 MPa, and ‘wherein said porous PTFE membrane has ball burst load ‘greater than 17 Ib fore. 12, A method of making a lightweight laminate having an abrasion resistant outer lm surface, sad method comprising: selecting a textile; Selecting a porons polytetrafiaonsethylene (PTFR) mem- ‘braachiving an average maximum loadin the ansverse and longitudinal direction greater than 10N, ‘coating and colorizing the porous PTFE membrane with an ‘leophobie polymer composition and a colorant to ‘obiaina porous PTFE membrane having an oleophobic colorized outer membrane surfice anol rating greater than 2 and laminating th textile, and the porous PTFE membrane to form a laminate, optionally before or after the coating step or the colorizing step to forma laminate having an ‘outer membrane surface and an inner textile surface: ‘wherein said laminate is Tiguidproof after more than 6000 ‘chrasion movements of the outer membrane surface ‘when tested according to the Liguidproo! (Suter) After Hook and Abrasion Test, wherein said porous PTFE membrane has an average ‘modulds in the teansverse and longitudinal direct sareater than 40 MPa, ‘wherein said porous PTFE membrane has an average nat inthe longtodinal and transverse direction greater than 90 MPa, and ‘wherein said porous PTFE membrane as a bal burst load ‘ereater than 17 Tp force.