'US00921590082 2) United States Patent (10) Patent No: US 9,215,900 B2 Johnson et al (45) Date of Patent: Dec. 22, 2015 (64) LIGHTWEIGHT, DURABLE APPAREL AND (58) Feld of Classifiation Search LAMINATES FOR MAKING THE SAME CPC. AMID 31/085; AID 31/00, YIOT 156/10 sec 2/488; 442/89, 76, 77,79, 80, 181 (71) Applicant: W. L. Gore & Associates, Ine, Newark, ce application file for complete search history DE (Us) 7 7 66) References Cited (72) Inventors: Matthew A. Johnson, Bear, DE (US): Edward €. Gunzel, Oxioni, PA (US) US. PATENT DOCUMENTS (73) Assignee: W. L. Gore & Associates, Ine., Newark, 3,586,596 A 6/1971 Ainsworth et a Sostses A 41970 Gore DEW 4302806 8 LVI981 Donovan (*) Notice: Suijct to any disclaimer, the term of this S533 871985 Nem patent is extended or adjusted under 35 Soas7m2 A 51980. Deki eta USC. 158(b) by 517 days 4960998 8111990 Hesn (Contin (21) Appl. Nos 180488 : : (22) Pied Maw 14,2013 POREIGN PATENT DOCUMENTS 6s) Prior Publication Data N iss77 62006 US 201310232673.A1 Sop. 12,2013 (Continaed) OTHER PUBLICATIONS Related US. Application Data (60) Division of apptcaton No, 12/530,234, led on Aug, PCTUS20I00O1145, Intemational Seach Report, Jl 2, 20106 11, 2009, now Pat. No. 9.084447, which is a PRESS continuation-in-part of application No, 12/465,383, (Continued filed on May 13, 2009, now Pat. No. 9,006,117 Primary Examiner — Peter Choi Gh) me. vacates ona (74) Auornes, Agent, or From — Amy L. Miller ‘AdID 3102 (2008.01) 7 é 1w328 27712 (Go0601), oO) ABSTRACT AMD 1300 Govs.o1) ‘Laminates are described having dursble outer film surface ‘441 3/00 (2006.01) for use in making lightweight liguidproof articles, including (2) US.C1 anicles of apparel, such as outerwear garmeats.A method of cre AID 31/0055 (2013.01); ASTD 13700 raking the laminate and « lightweight outerwear garment (2013.01); AdLD 31402 2013.01): B32B 27/2 having anabresionresistantextrior fim surfaces described, (2013.01); A41D 3/00 (2013.01); 8328 23057026 2013.01), YI0T 136/10 2015.01) 27 Claims, 4 Drawing SheetsUS 9,215,900 B2 Page 2 66) References Cited FOREIGN PATENT DOCUMENTS. USS. PATENT DOCUMENTS oso is98 ip stages 92004, SuUSSS67 A 101992 Non P soesss £2008 ssw A 71905 Ww P gorrms 33009 SR1sd08 A 91998 Brancaet 2 siaivons 1982 SS85738 A 31909 Hanon » ssisos7 3 1983, OUIRKID A 22000 Kinget al » tio? 21986 6.541589 B1 42003 Baile w aoo10ni779 “T2001 SIG TS BI 42004 Houner w 2001313236 112001 ‘82004 Sato stat w donors = 'k2002 122007 Racin etal » aoossosios 33005 750451 BL 62009 w aooseise39 92005 7s72331 B2 82009 » aoorsizos7 52007 Troksoe B] 42010 ke soosoons21> $2006, aoosd0siiss at 32003, Wo QopeI2a054 112006 doosors0%93 AL 7/2003 doonowoaer9 AL 1/2007 aoororTasos AL 11/2007 aooooottmas AL '32008 20100120629 AL 32010 (OTHER PUBLICATIONS PCPUS2010001144 International Search Report A pases 26,2010,6,U.S. Patent Dec. 22, 2015 Sheet 1 of 4 US 9,215,900 B2U.S. Patent Dec. 22,2015 Sheet 2 of 4 US 9,215,900 B2 FIG. 2U.S. Patent Dec. 22, 2015 Sheet 3 of 4 US 9,215,900 B2 FIG. 3aU.S. Patent Dec. 22, 2015 Sheet 4 of 4 US 9,215,900 B2 tmm x80 FIG. 3bUS 9,215,900 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,12/539,234, fled Aug. 11, 2009, which i a continy- stiou-in-part of US. patent application Ser. No. 12/465,383, filed May 13, 2009, FIELD OF THE INVENTION Deseribod horein sa breathable lightweight durable la rate having an outer film surface, anda Fightweight durable ‘article of apparel made from the laminate having an exterior ‘km surface, BACKGROUND OF THE INVENTION Articles of apparel having film layers for providing water resistance o liguidproo tines while simultaneously provide ing breathability are known, Laminates and garments are ‘constructed to provide protection tothe film layer so 2 {0 resist tearing, damage by puncture or abrasion, and the like. Inner and outer fabric layers are most frequently added 10 both surfaces of the film to protect the film surface from damage. ‘Allematively, garments having film surface uncovered by protective inner or outer layer of fabric are often constructed for use in combination with another garment whose fabric surface wll provide protection to the lm layer aginst dam- aye. For example, an undergarment comprising film com- posite locking an ouler protective fabric layer is constructed to be used under a separate outer garment where itis Tess susceptible to sustaining direct damage The addition of outer and inner fabric layers protect film layers from damage adds weight to a apparel, and results materials having higher wate pickup ‘on the outer surface. Moreover, wearing an outerwear par- ment to protect an undergarment having film layer forms & bulky ensemble. SUMMARY OF THE INVENTION Jightweight laminate having an outer film surface is described. The lightweight laminate is sufficienly durable ‘agunst abrasion for use in making articles of apparel and ‘ther ances, such as outerwear garments and shelters, hav ing an exterior film surface that remains liquidproot afer an abrasion challenge. The lightweight laminate has # porous polymer surface that ean be colorized, for example, by print fing, The laminate outer film surfage cu be coated with @ hydrophobic and oleophobie coating composition to provide ‘leophobcity and aid in the retention of waterprootness oF ‘A method of making a lightweight laminate having an abrasion resistant outer film surface is deseribed. The method ‘comprises the steps of selecting a textile layer; selecting a rugged porous fluoropolymer memibrane; coating and eol- ‘orizing the porous fuoropolymer membrane form a hydro= Phobie and oleophobie luoropalymer film having an outer film surface; ancl laminating the textile and he porous fuo- ropolymer film to form a laminate, optionally bere or ater the coating step or the colorizing step, to form a laminate having an outer film surface and an inner textile surface. In ‘one emboslimeat, a laminate is omned having moisture 0 o 2 vapor transmission rate that is preter than 1000 w/m?i24 hours, laminate mass per area less than 200 gin? and the laminate outer flim surface that s abrasion resistant, resulting ina durably liquidproof laminate ‘A method of meking an antile of apparel, such os ight- ‘weight outerwear garment, having an abrasion resistant dura by liquidnroof exter film surface is described. The method ‘comprises the steps of selecting a laminate having a woven, eit, or non-woven textile layer laminated to « porous Bao polymer membrane; coating and colorizing the porous {luoropolymer membrane with an oleophobic polymer com- position, ptionally before of after the laminating. step, thereby forming laminate having an outer fim surface and ‘an inner textile surface, assembling an outerwear garment ‘rom the laminate so tht the colorized outer film surface is the outerwear garment exterior film surlace and the textile inner surface ison a sie opposite the outer film surface DESCRIPTION OF THE DRAWINGS The operation of the present invention should become apparent fom the following description when considered in conjunction with the accompanying drawings, in whieh FIG, 1a is perspective view of one embodiment of gar- meat front surfiee FIG. 1 is perspective view of one embodiment of a gar- ment hack suriaee FIG. 2 is perspective view of one embodiment ofa lami FIG. 3a is a micrograph of a cross-sectional view of a sample ofthe hook material used inthe Hook Moditied Abra- son Tet FIG. 3) is a micrograph ofa top-down surface view of sample of thebiook material used in the Hook Modified Abra- son Test, DETAILED DESCRIPTION OF THE INVENTION Described, herein, is a breathable lightweight, durable Jaminate for use in making liquidproof articles of apparel faving ow water pick-up, sch as outerwear garments, The Jaminate is designed having a durably colorized outer film surface. A breathable lightweight, outerwear garment is described that comprises an exterior fl surface that es {wat to abrasion and is therefore durablyliguidproo ad bas ‘printable non-textile exterioe surface ‘One embodiment, exemplified in FIGS. ta and 1, illus- trates a perspective view of a gament (1) inthe form of a jacket having a gament exterior non-textile surface on the ‘zarmeat foat surface (20) andthe garment back surface (21) Te jacket (1) comprises an exterior non-textile surface (2) and an interior textile surface (3 that laces towards the body ‘ofa wearer, The jacket (1) comprises a font closure (4), sleeves (8) with wrist cuffs (6), and a waist band (9). The ‘garment is formed from a laminate, exemplified inthe cross Sectional illustration of FIG. 2, In one embodiment, the ar ‘meat comprises a laminate (10) that comprises an outer fl surface (11) and an inner textile surface (12). The laminate (10) comprises porous membrane (13) adjacent oa textile Jayer (14). The porous membrane (13) may be colorized with ‘colorant (16) and/or coated with aa oleophobic compositic that s also fyrophobic, forming the outer film surface (1 ‘of the laminate (10), The textile layer (14 is adjacent to the porous membrane (13) ona side opposite the outer film sur- ace (1) and is attached to the porous membrane by attach- meals (15), which are exemplified in FIG. 228 discontiouous attachmentsUS 9,215,900 B2 3 Is desirable to make laminates having film surface tat ‘can be durably coated, for example with colorants and ole- ‘phobic coatings, Where the membrane layers low surface ‘energy film, sich as many fuoropolymier materials, mem= brane porosity ishelpful io achieve durable mechanical bond- ing of the coating compositions within the membrane stic- ture, However, many porous films ate known to arate easily aking it dificult to achieve durable liguidproofness whea using the porous films in applications that will subject them to abrasion. Laminates described herein have a film surface Jormed from membranes having sufficient porosity to provide ‘adursble coating bu thatare resistant abrasion maintaining Tiguidprootness “The outer porous flm surface (11) ofthe laminate (10) ean bbe made, for example, trom a porows membrane comprising polymeric materials sueh as Muoropolymers, polyolefins, polyurethanes, and polyesters. Suitable polymers may com Prise resins that can be processed (o form porous oF microporous membrane structures. For example, polytt- rafluoroethylene (PTFE) resins that ean be processed to fom stretched porous stractures are suitable for use herein. For ‘example, PTFE resins ca be stretched to for microporous ‘membrane strictures characterized by nodes interconnected by librils when expand seconding a the process taught ia patents such as in US. Pat. Nos. 3,953,566, 5,814,405, of > 706,729. In some embodiments, expanded PTFE fhuo- ropolymer films are made from PLFE resins according 0 US, Pat, No, 6.541.589, having comonomer unis of poly- ‘Taorobutylethylene (PFBE). For example, microporous ‘expanded PTFE (ePTFE) fluoropolymers can comprise PTFE. having from about 0.05% by weight to about O.5Y gating the stress strain curve fm the sanaple ocaleulte the ‘rea below the curve, and averaped for three measurements foreach ofthe Land T directions, This number represents the ‘energy required to break the sample, reported asthe sample 0 o 10 ‘oughness. Then, the average toughness was calculated by averaging the toughness L with the tougnest for T ‘The modulus of each sample is determined by taking the slope from the liner elastic portion of the stress-strain curve First, the modifus in the longitudinal (L) and transverse (T) irctions are calculated from the average of three measure- ‘meats. Then, the average modulus i elculated by averaging the module of L withthe module of i Repelleney Test In dese tests, ol rating was measured using the AATCC ‘Test Method 118-1983 when testing the outer most lm side ‘of laminate samples, Three drops of the esol are placed on the sample surface. A plss plate is placed directly on top of the cil drops. ARer 3 minutes, the glass plate is emoved and any excess oil blotted off the surface. The film side of the sample is visually inspected fora change in appearance indi- cating penetration or staining by the test ol. The oil rating corresponds to the highest number oil that docs not eause visible staining on the film sample sie being tested, ‘Moisture Vapor Transmission Rate Test (MVTR) "The moisture vapor transmission rate foreach sample was determined in aeeordance with ISO 15496 except that the ‘sample water vapor transmission (WYP) was converted into (MVR moisture vapor transmission rate (MVR) based on ‘the apparatus water vapor transmission (WVPapp) aod using the following conversion, MVR ete Pet) (LYE LNB Air Permeability "The si permeability for each laminate sample was deter- amined in aocondance with ASTM D737 using the standard pressure drop of 125 Pa, but with the following epparatas voditication, Analterate test head area having an area of 20, cm? as tse. The test apparatus used was an EX 3300-20 avaiable from Advaneed Testing Instruments of Sehwverzen- bach, Switzerland. The values, reported in cubie fest per smite, ate shawn in Table 3. ‘Water Pick-Up Test ‘An 8°" square samples weighed using acalibratedseale thatreads tothe nearest .1 mg. available from Metter Toledo ‘of Columbus, Ohio, product item number AG 104. Thesample is then placed ina hydrostatic tester ofthe sort described ia ASTM D751 “Standard Test Methods for Coated Fabric section 4] dhrough 49 "Hydrostatic Resistance Procedure B with a 4.25" diameter cic challenge area. The sample is placed 80 that the laminate surface that Was designed as the ‘outer facing surface is challenged by the water, at 0.7 psi for 'S minutes, Take care to ensue that no residual water adheres ‘ris absorbed by the back side of the sample during place- ‘meat or removal, as this willalter threading Aer exposure, the sample is removed from the tester and weighed again on the aforementioned scale. All weight gan is assumed 10 be from water absorbed inthe challenge area of 4.25" diameter circle because of the high clamp pressure used to hold the Sample in ples. The water pickup is based on this area using the following calculation fo convert to grams per square meter ‘Weer pital sane ein sole eit 42s 4 nhsP om Liguidproof Test (Suter) Liquidproof testing was conducted as follows, Laminates ‘were tested for liguigproofness hy using amodified Suter test apparatus with water serving asa representative test liquid. ‘Water is forced against a sample area of about inch diam eer sealed by two rubber gaskets ina clamped arrangement.US 9,215,900 B2 un Samples are tested by orienting the sample so thatthe outer film surface ofthe samples the surface ausinst which water is foreed, The water pressure on the sample is increased (0 bout 1 psi by a pump connected to a water reserit, as indicated by an appropriate gauge and regulated by an in-line valve. The test sample is at an angle, andthe water is rie culated to assure water contact ant not ar against the sam- p's lower surface. The surface opposite the outer im sre {accor the sample observe fra period ofS minutes forthe sppearance of any water which would be forced through the sample, Liguid water seen on the surface is interpreted as & Teak. A passing Ciguidproot) grade is given for where no Tiguid waters visible onthe sample surface within 3 minutes A samples “Tiquidproot” as use herein, iit passes this test. Samples having any visible liquid water leakage, et in the form of weeping pinhole leak, te re no iquidproof and fail the test. Hydrostatic Resistance—Initial The initial hydrostatie esistane ofeach sample was deter- ined inacconlance wth ASTM D751 “Standard Test Meth- ‘ods for Coated Fabrics” The pressure was increased until the sample ruptured. The hydrostatic resistance reported was the hydrostatic pressure valve at which the sample ruptared. This ‘value was reported in pounds pr squae inch (si). ook Modified Abrasion “Abrasion Was tested as per ASTM D4966, “Standard Test Method for Abrasion Resistance of Textile Fabrics (Martin- ‘dale Abrasion Tester Method)” using Martindale Abrasion test apparatus with the following modifications. A. 6.25" «iameter circle specimen was placed over the standard piece ‘of fet om the testing table face up so the film surfice of the sample is subject o abrasion challenge The specimen in the spscimen holder was eplacedby aS" diameter circle ofthe hook side of hook and lop faster with the hooks facing sdowaso that they challenge the sample. This materials aylon hook obiainable at part number 1508000075 from Norman Shatz Co, of 3570 Fast Steet Road, Bensalem, Pa 19020 as “Two inch wide Black Hook and Loop”. FIGS, 8a and 36 are scanning electron micrographs of an example of the hook materi tht is suitable for use in tis test “Abrasion movements were conducted at regular intervals ‘with color change andlor hydrostatic resistance meastre= ments made at the end ofeach movement interval. Italy the movement interval is 400 movements until 2400 move- ‘ments are reached. fier this, the movement interval jumped to 800 movements until 9600 movements are reached, Aer this, the movement interval jumped 10 1600 movements foe the remainder ofthe est. Sample testing forall simples was stopped at 16000 movements, ‘Color Change after Hook Mexified Abrasion ‘Aller each abrasion movement interval the sample is removed from the above described Martindale test able and its performance is evaluated. An L*a"b* reading of the midate ofthe sample was ten using an X-Rite 11 Basie spocttphofometer (X-Rite Workd Headquarters in Grand Rapids, Mich. or www.xrite.com). The difference between this “ater abrasion” reading and the initial reading taken in the same spo but prior any abrasion movement is cal Tate. To determine the color change a eah abrasion move- ment interval, the root mean square ofthis difference valu is calculated using the equation below. Color cbangetiovenent Letina ‘rating rena rating 7 ‘This wot mean square ofthe colorchange valve is reported in wits of delta E (aE), 0 o 12 Liquidproof (Suter)—afer Hook Modified Abraso ‘The Fiquidprooiness of each sample ater any given abr sion movement interval was determined using the “Liquid proof Test (Suter” described above. A sample is no longer Tiquidproof when any visible water leakage, such as Weeping, pin hoe leak ee, is observed, No further abrasion oF liquide roo testing conducted on the sample Hydrostatic Resistance after Hook Modified Abrasion “The hydrostatic resistance after abrasion was determined in accordance with ASTM D751 “Standard Test Methods for Coated Fabrics” with the following exception. Each test specimen was abraded in accordance with the previously rmentioncd Hook Modified Abrasion Method, however, sumples were abraded fo 1,000 movements using the hook side ofthe hook fastener as the abradant, Each specimen was thon tested for hyelostatic resistance in accordance with ASTMD 751 oriented so thatthe outer film suriee facing the ‘water, These values are reported in pounds per sare incl (si, EXAMPLES ‘Two layer laminates were formed having an outer film surface and an inner textile surface dseribed according tothe following examples, ‘Membrane 1 (MI) A moisture vapor permeable, microporous polytetrafluo- roethylene (PTFE) membrane was produced that ws pro- duced from a PTPE resin made according othe teachings of US. Pat, No, 6,541,589, The PTFE resin comprised about 0.5 .W1% polyuorobutyledylene (PFBE) based onthe total esin ‘weight, and was processed into an expanded PTFE (ePTFE) ‘membrane according to the teachings of U.S. Pat.No. 3,953, ‘566, Properties for this membrane are detailed in Table I Membrane 2 (M2) A moisture vapor permeable, microporous PTFE. mem- ‘brane Was produced from PTFE resin and processed into aa expanded polytetmfluomethylene (ePTFE) membrane according tothe teachings of US. Pat. No. 5.814.405. Prop- tis for this membrane are detailed in Table 1 ‘Membrane 3 (M3) A moisture vapor permeable, microporous PTFE mem- trae was prosiced from PTFE resin and processed into an expanded polytetafluorethylene (ePTFE) membrane ‘according tothe teachings of US. Pat No. 3,953,566. Prop- ens fr this membrane are detailed in Table I ‘Membrane (M8) A moisture vapor permeable, microporous membrane was produced {rom PTFE resin and processed into an expanded polytetraftuoroethylene (ePTFE) microporous membrane according to the teachings of US. Pat. No. 3,953,566. The properties for this membrane are detailed in Table ‘Membrane $ (MS) A microporous membrane prodtced from PTFE resin pro cessed into an expanded microporous polyterafloomethy- ene (€PTFE) membrane acconling tothe teachings of US. at No. 3.983.566. The properties of this membrane are setsled in TableUS 9,215,900 B2 14 ‘Mean ow pore 20 13 Bat as 10) . - - Beem) sno sae een sa var i eee (LPaverage) (Mpa) - Toate) Pl “Avwoven polyester textile wasprovided that was comprised ‘fam and weighing about 80 gin availabe Irs Milken ‘& Company (Sparanburs, SC: syle umber 141128) ‘Tete 2 (12) Avovennylon6,6tetle was provided that wascomprised ‘ofyamsand weighing bout 50 gn* availble from Méiken ‘& Company (Spartanburg, SC: syle umber 131307.) ‘exile (3) “Aknit textile was provid that was comprised of polyester jin the form ofa Mat warp kit having a Weight of eppox: nately 38 wn, fom Glen Rave, Inc. (Glen Raven, N. pat number 41012) Colorization Method 1 (Be) “Aller amination, the ePTFE membrane surface ofthe 160 layer laminate was printed using a blue colored, solvent: based, pigment-contining inkcapableof weting the ePTFE “The laminate was printed using an Fpson solvent capable, jnksjet printer to form a colorized ute lm surice Coloization Method 2 (Re) “Aller amination, the ePTFE membrane srtace of the two layer laminate was printed sing oe colored, solvent-based, Piamecat-contsining ink capable of weting the ePTFE. The Jaminte was printed using an Epson solvent capable ink et printer to form a colorized outer film seco. ‘Oteophobie Coating 1 (C1) The colorized, ePTFE outer film surface othe laminate wat coated with 2-propanol (Sigmo-Alsieh Chemical Cor potion, St Louis, Mo.) so tha the fil was completly wet. ‘After wetting, it was immedi (in les ttn about 30 seconds coated withafluropolymersolution, formulated by mixing about 6.0 g of Buowearbon (AGSO25, Asahi Glas, Japan) in about 14.0 go deonize water The colorized fa surface was hand coated withthe mixture using a roller to a coating weight of approximately 3 g/n” The coated film was cured at 180°C. for? sates, ‘Oleophobic Coating 2 (C2) ‘The colorized, ePTFE outer film surface ofthe laminate was enderedoleophobic by coating ithabout 2.5% soliton ‘of Teflon AF (DuPoat Fluoropolyaers, Wilmington, Dl) inFluoriner& FC-40 3M Comporation, Minneapolis Minn.) solvent. The colorized film surface was hind coated using roller coating weight of approximately gim and dried 180° C.forabout 2 0 o Laminates were formed comprising an outwardly facing colorized outer film surface anda textile. ‘Laminate samples for Examples 1-14 were constmicted using the specific porous membrane and textile detailed in ‘Table 2, The porous film and textile were laminated together by gravure printing a do pattern of moisture curable polyure- thane adhesive oato the membrane suface, The adesive was prepared acconling to the teachings of USS. Pat. No. 4,532, 316, covering approximately 35% ofthe membrane surface The adhesive-printed side of the ePTFE membrane was pressed o-one side of the woven textile ina nip roll and then passed over a heated rll t form a two layer laminate, The moisture eure adhesive was allowed to cure for 48 hours. ‘The laminates were colorized according to the specific colorization and oleophobie coating methods in accordance to Table 2 TABLE 2 rs atau amie Example Nimfer__Menbvte Tele Coloration Costing 7 Mo mm Ble a é Fi Boe 5 n Ble 2 > a Ble wo Ble h Ble B n Ble i n Blue te R be OG Laminates were formed that were lightweight, moistre vapor permeable, ar permenble, having an oil rating ofS or greater and low water pickup, when tested according. to the ‘methods deseribed herein. The reslts are reported in Table. "To compare the low water pickup of laminates having an ‘outer film surface to materials that are liquigroot bt having a textile outer surlaee, « comparative material sample wasUS 9,215,900 B2 15, ‘obtained, Comparative Sample | was a commercially avail. able material comprising «nylon textile (tightly woven) hav ing a microporous polyurethane on one side and a durable ‘water repellant (DWR) coating om the other side. Compans- tivesample I was tested for water pickup on the DWR side of $ the sample, and had a water pickup of about 11 gsm, signifi ‘cantly higher than water pickup of Examples I-11 reported in ‘Table. TABLE amine Charteris. ae i a 6 noes eg) ° ms “The laminates were tested to determine the number of abrasion movements before loss of liguidprootiness and for hydrostatic resistance before and afer abrasion, as described inthe test methods herein. "The results are reported in Tabled. a Sa Po 6B UB o “The laminate of Example | was tested forthe durability of the sesthotc appearance by testing according to the method for Color Change After Abrasion described, herein. After ss abrasion on the outer film surface the laminate had a color ‘change of about 8 dE. 16 Example 15 An outwear jacket having an exterior film surface was ‘constricted using simple game pattem having no pockets ‘ hood, ancl full length oat zipper (4), as exemption in FIGS. la and 1b, ‘A laminate was constructed comprising an ePTFE onter film surface similar to that of Example 3 except laminated to knittextile layer, ratherthan the woven textile of Example by discontinuous adhesive attachments, An cleaphabic eo ing was applied tothe outer film surface. The garment sleeves Were terminated with elastic eulls having adjustable hook and Joop tabs. The bottom citcunferenial hem was provided with an clastic draw cord inorder to aecommadaten range of Waist The jacket was constructed sewing the patterned laminate pivees together by orienting the outer film surface to the exterior side of the jacket usinga single nee seam machine hhaving 265 ball point noodle. The sewing machine included a knife edge whieh trimmed off aay excess laminate 0 that the seam could later be sealed sing a narrow seam tape. The jckot seams were sealed with a hot-melt seam tape baving a ‘lficently low melt-viscosty such that the adhesive can penetrate through the kit fabric, contacting the eP TEE mem- brane to make a watertight soam, using a standard hot-melt seam sealing machine. The seam seal tape was applied to the {nit texte sd of the jacket laminate. “The back lap along the inside edge ofthe from zipper was reinforsed with sheet adhesive, thereby preventing it from being caught inthe ziper. The resulting garment wasa men’s size XL having a total garment weight of approximately 9.1 Example 16 Tis laminate sample was constructed in the same manner as Examples 1-14 using the components sted in Table 2 with the following exception. Before lamination, the membrane, (Ma, was coated with a paially imbibed monolith polyune” thane layer according to U.S. Pat, No. 4,969,998. The poly- urethane coated Md was laminated such that the uncoated ePIFE. side was oriented away fom the textile, T2. All remaining processes are as detailed in the description of Examples 1-14, Example 17 A commercially available two layer laminate consisting of microporous polypropylene film bonded toa polypropylene point bonded nonwoven was used as a reference. This is available under the twade name DriDucks!™ from Frog ‘Togas (I31 Sundowa De NW, Arb, Al 35016) under part ‘number DS120:-04, This product was tested with the :meroporous polypropylene film as the external surface. This Jaminate was tested for liqidprooiness after abrasion, the results for which are reported in Table 4 ‘While particular embodiments of the present invention ‘have been illustrated and described herein, the present inven- ‘ion should not be limited! to such illustrations and deserip- ‘ions. If should be apparent that changes and modifiations ‘may be incomporated and embodied as part of the present invention within the scope of the following claims. “The invention claimed is: 1A method of making an outerwear garment having an abrasion resistant exterior film surface, said method compeis-US 9,215,900 B2 17 selecting awoven orkait textile anda porons polyteteaio= ethylene (PTFE) membrane; Jaminating the textile and the porous PTFE membrane t0 forms lominatchavinganovter film surlace andaniance textile surface: and assembling an omtenwcar garment from the laminate so that the outer film surface isthe outerwear garment exterior film surface and the inner textile surface is on a side ‘opposite the outersear garment exterior film surface; ‘wherein the laminate has @ moisture vapor transmisio rate greater than 4000 win?/24 hours, ‘wherein said laminate is Figuidproof after more than 6000 abrasion movements on the outer film surface when tested according to the Liguidproof (Suter) After Hook and Abnision Test ‘wherein said porous PTFE membrane has an average maxi ‘mum load in the transverse and longitudinal direction sxreater than 10 N, wherein said porous PTH ‘modulus in the transverse and longitudinal direction greater than 40 MPa, wherein ssid porous PTFE membrane his an average ‘matrix tensile strength in the longteadinal ad transverse direction greater than 90 MPa, ad ‘wherein said porous PTFE membrane has a ball burst load ‘greater than 17 Ib force 2. The method of claim 1 wherein the method comprises assembling the outerwear garment ffom 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 porous PIFE membrane comprising expanded PIFE (ePTFE), 4. The method of claim I wherein the method comprises selecting a microporous PTFE membrane comprising per- ‘Tuorobutylene (PFBE) comonomer. '5, The method of claim I wherein said porous PTFE mem= brane has a mass per area less than 80 gn 6, The mebod of claim I wherein the method comprises scleting a porous PTFE membrane having a thickness less than 35 am, 7, The method of claim 1 wherein the textile comprises 8 kat. '8, The method of claim 1 wherein the textile comprises 9 9, The method of claim 1 wherein the method comprises ‘colorizng the laminate outer film surface by printing witha Ink jt priner. 10, The method of claim 1 wherein the laminate outer fil surface has an oil rating of greater than 4. 11, The method of claim 1 wherein the method comprises seleting laminate that has @ mass per area less than 400 pi. 12, The method of claim 1 whersin the method comprises scleting a porous PTFE membrane having a thickness less than 120 um. 13, The method of claim 1, wherein the method further ‘comprises coating the porous PTE membrane with an ole ‘ophobie coating. 14, The method of claim 1 further comprising coating discrete materials on the outer film surface for improving abrasion resistance ofthe laminate, 18. The method of claim 14, where the coating of diserete materials comprises a material selected from polyurethane, ‘epoxy, silicone o Hnoropolymers membrane bas an average x 0 o 18 16, A method of making an outerwear garment tin abrasion resistant exterior fil surface, sid method compe ing: ‘selecting a textile composite comprising an abrasion rsis- ‘ant laminate having a colorized, outer film surface, ‘wherein the laminate comprises 6). porous polyttrauoroethylene (PTFE) film mem- baie having an average maximum load inthe transverse ang longitudinal direction greater than 10N, and Gijtextleattached tothe porous PTFE membrane on aside ‘opposite the colorized outer film surface forming gant poe comprising he teil compos assembling an outerwear garment fom seid garment pioces comprising the textile composite by orienting the ‘garment pieces so thatthe colorized outer film surface is theouterear gament exterior film surface and henner textile surfce ison a side opposite the outer film sut- face: ‘wherein the laminate has & moisture vapor transmission rate greater than 4000 g/m*/24 hours ‘wherein sod laminate is liquid after more than 6000 ‘abrasion movements on the outer film surface when tested according tothe Liquidpeoot (Suter) After Hook ‘and Abrasion Tes, ‘wherein said porous PTFE membrane has an average ‘modulus in the tansverse and longitudinal direction _reater than 40 MPa, wherein stid porous PTFE membrane has an average ‘matrix tensile strength inthe longtadinal and transverse direction greater than 90 MPa, and ‘wherein said poroos PTFE membrane has a ball burst load ‘eater than 17 Ib fore. 17.4 method of making an outerwear article of apparel having an abrasion resistant low wate pickup exterior film surface, said method comprising: selecting a textile layer and a porous polytetrafluoroethyl- ‘ene (PTFE) membrane; Jaminatng the textile and the porous membrane to form a laminate having an outer film surface andan inner textile surface: assembling the article of apparel from the laminate so tht the cuter film surface isthe exterior film sufiee ofthe article of upparel und the inner textile surfaceisona side ‘opposite the exterior film surface; wherein the laminate has 9 water pickup of less than or ‘qual to 10 g/m, wherein the laminate has @ moisture vapor transmission rate greater than 4000 w/m*/24 hours, ‘wherein sid laminate is liquidproof afte more than 6000 abrasion movements on the outer film surface when tested acconding to the Liquidproof (Suter) After Hook ‘and Abrasion Tes, wherein sid porous PTFE membranc hasan averagemani- mum load in the transverse and longitedinal dirsction greater than 10 N, ‘wherein said porous PTFE membrane has an average ‘modulds in the transverse and longitudinal direction ‘geater than 40 MPa, ‘wherein ssid porous PTFE membrane has an average matrix tensile strength inthe longitudinal and transverse direction greater than 90 MPa, and ‘wherein said porous PTFE membrane as aba burst load ‘greater than 17 Tb force. 18, The method of claim 17, further comprising coating an ‘leophobie polymer on the porous PIFE membrane.US 9,215,900 B2 19 19, The method of claim 17, wherein the porous PTEE semibrae comprises microporous expanded PITE. 20, The method of elim 17 further comprising colorizing the porous PTFE membrane with a eolorant to obtain a col- ‘rized outer film surface 21. The method of claim 17 wherein said porous PTFE rmenbeane has amass per area between 19 gn ad 60g 22, The method ofelaim 17 wherein ssid outer lm surface js colorized and has @ Deta-E Jess than 15. 23, The method of claim 1, wherein the porous PTFE. membrane comprises microporous expanded PTFE. 24, The method of elim 1 Turher comprising colorizing the porous PTFE membrane with a colorant to obtain a col- ‘rized outer film surface 25. The method of claim 1 wherein ssid porous PTFE. ‘membrane has amass per ares between 19 yin ane 60 pin 26. The method of claim 1 wherein said outer film surface is colorized and has « Delta less than 15 27. The method of claim 1 wherein said Jaminate has 2 ater pickup less than or equal to about 10 ga" when tested soconding tothe Water Pickup Test. 20