CA2075211A1 - Roll of molded, ballistic resistant cloth and method of making same - Google Patents

Abstract

The present invention provides methods for treating continuous lengths of resin-impregnated sheets (11) so that they can be supplied in roll form, i.e., like a bolt of cloth, for subsequent processing or use. The methods feature the step of winding the continuous length (11) and a separation layer (12) of a material into a roll (10) with the layer separating successive wraps of the continous length of sheets, followed by a curing step if the resin is a thermosetting resin or by the application of heat and/or pressure otherwise. The continuous lengths optionally may comprise at least one sheet of film, too. The separation layer (12) of material remains separable from the continuous length (11) after treatment. Composite articles made from certain of these continuous lengths are ballistic resistant.

Description

WO91~12136 PCT/US91/00463 ROLL OF MOLDED, BALLXSTIC RESISTAN~ CLOTH
~D ~ Q~_QF ~ErNG S~

This is a continuation-in-part of copending U.S. Serial No. 480,982 ~iled ~r~ry 16, l990.
~he present invQntion relates to mathods of treating continuous l~ngths o~ rQsin-i~pregnatad ~heets so that they can be suppliad in roll ~or~, i. Q-, like ~ bolt of cloth, ~or sub~equ~nt proces~ing or u3e. In particular, certain o~ thQ tr~at~d l~ng~h~ are use~ul in 1o ~lexible hard ar~or applications, whil~ certain other of the-tr~at~d leng~h8 ar~ u~eful in 80~t ar~or .~ applications. The pres~nt invenSion also relates to r~lls ~ trRated in ac~ordance with the methods.
;: 2. Prior Art Ballistic ras ant articles such as ~ulletproof ve~ts, h~ ts, hard and 80~t armor, structural m~mbers of helicopt~rs and oth~r ~il~tary equipment, vehicl2 pAnel~, bri~ca~es, r~incoats and . u~brel~as containing high 6trangth f~bers are Xnown.
Fibsrs co~vention~lly u~ed ln ~h~9 articl~s include ' aramid flbers 8uch a~ poly(p-ph~nyl~nQ terephthala~ide)~
gsaphite fibars, nylon ~bQr~, cera~ic ~ibers, glass fibers and the like. For ~Any ~pplic~tions, ~uch as vests or parts o~ vests, th~ ~ibQrs ~r~ u~ed ~n A woven or knitted fabr~c. For ~any of the other applications, the f~rs are ~nc~psulated or e~bedded in a ~atrix mat~rial.
Ballistio-resistant composite articles comprisad of networks o~ high ~olecular weight polyethylene or polypropylene fibers, and ~atrices composed of olefin polymers And copoly~ers, unsaturated polyester resins, epoxy re~ins, ~nd other resins curable below the ~elting point of the f~er are taught by USP
4 ~03 012 and USP 4 457 985, hereby incorporated by reference.
UsP 4 623 574, hereby incorporated by reference, di~closes the formation of prepreg sheets comprised of elastomer coa~ed hi~h ~trengt~ fibers which ~re , :. ' : - :
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WO9~/12136 P~T/VS91/00~^

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~ubstantially parallel and ~ ned alo~g a common fiber direction. The patent teaches that the prepreg sheets can be plied together, with successive sheets being rotated relative to the ~irst ~heet, to ~orm si~ple composlte materials. These composite ~aterials are of a given ~ize, . g., 12 x 12 inches (4~7 X 4.7 cm), and are individually ~olded prior to b~ing 6ent to the customer who then cuts and fabricate~ ~he mat~rial in~o a desired con~iguration.
There would ~a le88 wast~ o~ ~t~rial, and thu8 le~
1o ~xpense, if the co~posit~ ~aterlals could be ~urnishad to .
the custo~er in continuou~ roll for~, l.e., liXe a bolt of cloth, rather than in squares or rectangles. And the continuous length would be ~uch ~asier to handle if it was - ~olded - in e~fect, it would drape liX~ a fabric rather ~han being stiff nnd awXward to cut. Molding ty~ically take~ place with compre~sion or heat: the ti~e required ~or h~t moldin~, ~.g., between hsated rolls or plates, is e~sentially ~oo long to penmit th~ practial in line ~olding of the mater~al ~fter its for~ation.
The present invention, which ~a~ developed in an atte~pt ~o ~verc~me the deficiancie~ o~ the prior art, provides a molded co~posita ma~rlal in continuous roll for~ ~nd ~ethods o~ ~akinq ~ame.

This in~ention i8 a ~e~hod Or con slidatin~ a continuous ply of at leas~ two resin-impregnated sheets, comprising th8 ~teps of:- aO win~ing tha continuous ply and a separatio~ layer o~ a material into a roll with the layer separating successive wraps of the continuous ply;
30 and b. exposing the roll to a suffi~iant a~ount of heat and/or pressure ~o ~use the resin-i~pr~gna~ed ~heets to substantially adhere ~o one another, the ~terial being separable ~rom ~he ~ontinuous ply. The resulting ply can have utility in both ~he soft and hard armor fields.
Depending on thle resin D~trix used, a oonsolidated length of ~heets ~ay o:r ~ay not 6tic~ ~o 2nother ~uch l~ngth.

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~O91/12136 PCT/US91/00463 ~ ~ t~

- Those lengths that ds not stic~ to other l~n~th~ are good soft armor cnndidates w~ile thosa that do stick to other lengths and ~rs not modl~i~d Wi~l a film ~ur~ace or o~herwise traatad ~o not ~tick ar~ poor candidates for s soft armor: however, ~ plural$ty o~ ~hese latter lengths could b~ ~tack~d, h~atQd and pr~sed to ~orm a hard ~r~or lamina e.
~ he present invention is also a me~hod of con~olidating a continuous l~nqth co~pri~ing at l~ast one . 10 r~sin-impr~gnatad sh~et and ~t l~st one ~h~et of ~ilm, comprising ~he ~teps of: ~. winding the continuous lsngth and a s~paration lay~r of a material into a roll with ~he layer sQparating ~UCC~S~iY~ wraps of the continuous length of sheet ; and b. ~xpo~ing the roll to : 15 a su~icient amount o~ h~at ~nd pressurQ to cause the resin-~pr~gnated sheat ~nd the sheet o~ ~lm to substantially adher~ to on~ annther, thQ ~eparation layer of ~aterial being soparable fro~ the ~ontinuous length of shaets. T~e re~ult~ng con~olidated length o~ ~heets can 20 b2 used in ~oft ar~or appltcations~ e.g., ~ ~ vest insert. The fil~ ~urfaco on on~ or bo~h ~ide~ of the length ~an be cho8~n to ~llow ~lippRg~ r~lative to another l~ngth. For thi5 a~bodi~ent, ~e i~prQgn~ted ~heet is prefQrably a nQt~or~ sf woYen ~i~er.
In ~nother e~b~diment, the present invention is a ~ethod o~ treating a continuous length compri~ing at least one uncured ther~os~tting resin-i~pregnated ~heet, th2 length ~a~lng a thic~ness and the ~hermos~tting resin ha~ing an elongation such that the leng~h o~ ~heet is 30 fl~xible when t~e ther~o~tting re3in i~ cured, co~prising the steps o~: a. ~in ing ~he continuou~ length and a separation laye!r of a ~ateri~l in~o a roll with th~ layer sep~rating ~uccessive wraps of t~e continuous le~gth of ~heet, the ~atorial being separable ~rom th~ continuous 35 length of sheet after the ther~osetting resin is cured;
and ~. curing the t~ermo3etting r~in. ~th this ~ethod , , , - , ., : . , : : :.

WO91/12136 PCT/U~91/004 you can eli~inat~ the film surf2lce of the preYious embodiments for soft a~mor ~ppli.cations and aohieve about a t~enty percent weight reduction. The cured th~rmo8atting resin would pro~ide the required ~urface 5 slippage for 80rt ar~or appl~cat:ion~.
Th~ present invention al60 includ~ tha rolls of material pr~duced by the ~ethods, o~ ~hi~ i~vention.
~g D~CRIE3IQ~ OF I ~
Figure 1 depicts a ~olded roll ~O of the 10 pr~ent invention.
~' ~
~ By sheet i5 ~eant a shap~d article such as a :~ fil~, tape, or a network of fi~er or tape, biaxially ~ oriented or otherwise, ~ost preferably a network o~`
:: 15 fib~r.
By fiber i8 ~nt ~n el~ngate body, the length dimension of w~ich is ~u~h greater ~han the trans~erse di~nsions of width and th~ckna~s. Accordingly, the term : fiber includes ~onofilament, multifila~ent, ribbon, s rip, ~0 staple and other ~Qrm~ 0~ chopped or out fi~er and ~he like having r~gul~r or irregular cros~-sec~ions. Fiber and filament are used interchangeably h~reafter.
By n~t~ork $8 ~ant t~p~s or ~ibQrs arrang~d in con~igurations of various types. For ex~ple, ~he 25 plural$ty o~ fibers can be grouped together to ~orm a twisted or untwisted yarn. The ~ibers of yar~ ~ay be ~or~ed as a felt, knittei or woven (plain, basket, satin and crow feet weaves, etc.) into a network, fabricated into a non-w~ven fabric (random or ordered orientation), rranged in a parallel array, layered, or formed into a fabric by any o~ a variety of conventional techniques.
Similarly, the ~apes may ~e woven into a ne~work, fabricated into a nonwoven ~abric, arranged in a parallel ~rray, or formed into a fabric by ny of a variety of 35 con~entional techniques.
In ~he pre~erred embodiments o~ the invention, WO9l/1213~ P~T/V~91/004~3 J~

th~ shQet comprises untwisted monofilament yarns which are substantially p~rallel and unidir~ction~lly aligned to ~orm a uniaxi~l layer in which a ~atrix material Gubstantially coats the individual ~ ants. Although the present s inv~ntion include5 a ~inyl~ su~h layer lor ~heet), two or more of these layers are pre~erably used to forffl ~he continuous leng~h, with each layer ~otated ~ith resp~ct to ad~acent layers. An exa~ple i3 a fi~e l~yer lenyth with the second, third, fo~rth and ~i~th l~yer~ rotated ~45 , 10 ~~5-, 99- and 9- with r~3pact ~o ~h~ ~r~t lay~r~ ~no~her, - pr~arred ~x~ple in~lud~ t~o lay~rs ul~h 4 0-/90- layout.
The cross-6ections o~ ~ilament~ for u~e in this in~ention ~ay vary widely. They ~y be of circular or of ~lat or of o~long or of irragular or regular multi-lobal 15 cro~s-section having one or more regular or irregular lobes projec~ing from the linear or longitudi~al ~xis of ~e filament. It i~ particul~rly prsferred that ~he filaments ~e of 8ub8tantially cir~ular, flat or oblong cros~-~ection, ~oGt preferably ~he former.
Th~ equivalent di~m~ter sf ~he fil~ments and the thickn~ss of t~ layer ~ay vary wldely. In general, the s~aller the Qquivalant diameter ~nd the thinner the layer, the grQat~r th~ ballisti~ prot~ction provided; and conv~rsely, the greater the ~guival~nt diameter of t~e 25 filaoent and the greater th~ thickn~s~ of the layers, the lowær the balli~tic protect$on provided. The ratio of the ~h~ckn~ o~ the layer to ~he equivalent dia~eter o~ the filament ~nd ~he ~qui~alent dia~eter of the filaments are pre~erably a~ set ~orth in ~SP 4 916 O00, h2reby 30 incorporated by reference.
The type o~ fila~ents u~d may vary widely and can be met~llic ~il~ments, ~emiometallic filaments, inorganic filamentS a~d~or organic fila~ents. Filaments for use in ~he practice o~ this invantion are ~ho5e having 35 a tenacity equ~l to or greater than about 7 g~d, a tensile UlU8 egual to or gre~ter than about lS0 g/d and an energy-t~-br~ak ~qual to or gre~er tha~ a~out 8 . , . . ~ . :
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-, - :: . , , ,, , . : : :- ' 2~36 PCT/US91/0~46 -Joules/gram (J/g). Pref~rred ar~ filaments having a t~nacity ogual to or sr~ater than about 10 g/d, a tensile modulus equal to or great~r than about 200 g/d and an energy-to-bre~X egual to or greatsr than about 20 J/g.
S More prs~erred filame~ts are ~hose h~ving ~ tenacity equal to or greater thsn about 15 g~d, a ten~ile modulu~ equal to or greater than about 300 g/d snd an energy-to~reak equal to or graater than ~out ~0 J/g. Particularly pr2f~rred ~il~ments ar~ those hav$ng a t~nacity ~qual to 10 or greater ~han Dbout 16 g/d, a ten~ odulus ~qual to or great~r than sbout 400 g/d, and an ~nergy-to-break aqual to or greater ~han about 27 J~g. A~ong~t these particularly preferred ~mbodi~ent~, ~ost pre~erred are those ~mbodi~ents in which the tenacity of the fil~ents 15 is squal ~o or gr~ater ~han ~bout ~2 g/d, the tensile modulus is equ~l to or greater th~n about 900 g/d, and the energy-to-breaX is ~qual to or great r than about 27 J/g.
In the practice of thi8 invention, fila~ents of ohoice have a tenacity equal to or greater than a~out 35 g/d, the 20 tensile ~odulus i8 ~qual to or greater than about 1500 ~/d and the snergy-to-~reak i~ ~qual to or ~reater than about 50 J/g.
. ~llustrativ~ o~ u88~Ul organio ~ilaments are thosa composed of polyester~, polyole~ins, polyeth~ramides, 25 fluoropoly~ers, polye~h~rs, cellulo~es, phenolics, polyesterz~ide~, polyure~hanes, epoxies, aminoplastics, siliconesJ polysulfones, polyetherke~ones, polyetheretherk~tones, polyesterimides, polyphenyl~ne sulfides, polyether ac~yl ketones, poly(amideimides), and 30 polyi~ides. Illu~trative of other us2ful organic filaments are those composed o~ ara~ids (aromatic polyamides)~ such as poly(m-xylylsne ~dipa~ide), poly(p-xylylene sebacamide)~
poly(2,2,2-trimethyl-hexamethyl~ne terep~thalamide), poly(piperazine se~acamide), poly(metaphenYlene 35 isophthalamide) ~No~ex) and poly(p-phe~ylQne terQphthalamide) (Xevlar): ~liphatic ~nd ~ycloaliphatic ' ': .~. `"'' ` ' . ' vo 91/12136 ~T/US91/004S3 polyamide~, such as the copolyamide of 30S hexa~ethylene diammonium isophthalate ~nd 70% hexamethylena dia~monium adip~te, the copolyamide o~ up t:o 30% bis (-~midocy~lohexyl~ethylena, tes-ephthalic acid and 5 caprolactam, polyhexa~hyl~no ~dipamide ~nylon 66), poly(~utyrolact~) (nylon 4), poly(9-aminonoanoic acid) (nylon 9), poly(enan~holact~m) (nylon 7), poly(capryllact~) ~nylon 8), polycaprolaat~ (nylon 6), poly~p-phe~ylQn~ tsrQphthala~ida), polyh~xa~hylene 10 sebacamida (nylon 6,10), polyaminoundQcan~midQ (nylon 11), polydodec~nolactam (nylon 12), polyh~xam~thylene isophthalamide, polyhexame~hylene terephthal~mide, polycaproamid~, poly~noname~hylene a~lamide (nylon 9,9), poly(dec~m2thylan~ azela~ide~ (nylon 10,9~, 15 poly~decame~hylene ~abac~ida3 (nylon lO,lO), polytbi~-(4-aminocycloh~xyl~methane 1,lO-decanedicar~oxamid~ (Qiana) (trans), or co~bin~tions thersof; and aliphatic, cycloaliphatic and aro~atic polyester~ such as poly(l,4-cyclohexylidsne di~ethyl 20 2netereph~alate) Ci8 ~nd trans, poly(~thy'~ne-1,5-naphthalate), poly(~hylsn~-2,6 naphtbala~e), poly(1,4-cyclohexane di~hyl~n~ terephth~la~e) (~r~n8), poly(duca~hyl~ne ter~phthalate), poly~ethylen~
t~rephthalata), poly(~thyl~ne i~ophthalate), poly(ethylene 25 oxybenzoate), polytpar~-hydroxy benzoat~), poly(dim~thylpropiolactone), poly(dsc~thylene adipate), poly(et~ylene ~uccinate); poly(e~hylene azelate), poly(dec~ethylena sabacate), poly(~Z- di~etbylo propiolactone), and the like.
~lso illustrativ2 of use~ul organic filaments are ~hose of liquid crystalline poly~ers such as lyotropic liquid crystalline polymers whioh include polypeptides such as poly r-~enzyl L-glutamate and the like; aromatic polyamides such as poly(l,~-benza~ide), poly(chloro-1-4-35 phQnylene ~erep.hthalamide~, poly(lr4-phenylene ~umar~mid~), po.ly(~hloro-l,4-phenylen2 ~u~ar~mide), WO91/12136 PCT/US91/004~ -poly(4,4'-benzanilide trans, trans-muconamide), poly(l,4-pAenylene ~esaconamide), poly(1,4-phenylene) (trans-1,4-cyclohexyl~ne amide), poly(chloro-1,4-phe~ylene) (trans-1,4-cycloh~xylanQ amide), 5 poly(1,4-phenylen~ 1,4-dim~t~yl-tran~-1,4-cyclohexylene amide), poly(l,4-phenyl~ne 2.5-pyridine a~ide), poly(chloro-1,4-phenylene 2.5-pyrid~ne ~mide), poly(3,3'-dime~hyl-4,4'-biph~nyl~ne 2.5 pyridine amide), poly(l,4-phenylene 4,4'-stilben~ a~id2), 1o poly(chloro-1,4Ophenylen~ 4,4'-s~ilbQn~ ~fflide), poly(l,4-pbenyl~ne 4,4'-azob~nzena ~ide), polyl4,4.'.-azob~nzene 4,4'-azobanzene ~mlde), poly(l,4-phenylene 4,4'-azoxybenzene a~id8), poly(4,4'-azob~nzene 4,4'-azoxyben2Qne amide), poly(l,4-cyclohexylene 4,4'-15 azobenz~ne amide), poly(4,4'-azo~enzene tersphthal amide), poly(3,8-phenan~hridinone tereph~hal amide), poly~,4'-biphenylene terephthal amide), poly(4,4'-biphenylene 4,4'-biben20 amide~, poly(l,4-phenylen3 4,4'-b~benzo amide), poly(l,4 phenylen~ 4,4'-terephenylene a~ide), po~y(l,4-20 phenyl~ns 2,6-naphthal afflide), poly(l,5-napbthalene tersphthal a~ida), poly(3,3'od ~thyl-4,4-b~phenylene ter~phthal amide), poly(3,3' di~e~hoxy-4,4'-biphenylene terephthal amide), poly(3,3'-dimethoxy-4,4-~iphenyle~e 4,4'- bibenzo a~ide) and the like: polyoxa~ide~ such as 25 those deriv~d from 202'-di~,e~hyl-4,4'-di~ino biphenyl and chloro-1,4-phenylene diamine; polyhydrazid2s such as poly chloroterephthalic hydrazide, 2,5-pyridine dicarboxylic acid hydrszide) poly(terephthalic hydrazide~), poly(terephthalic-chloro~erephthalic hydrazide3 and the 30 like; poly(~ide-hydrazides~ such as poly(terephthaloyl 1,4 amino-~enzhydrazide) and those prepared from 4-amino-benzhydrazide, oxalic dihydrazide, terephthalic dihydrazide and para-aromat.ic diacid chloride~: polyesters ~uch as those of th~ co~,posi~ions include pc,ly(oxy-trans-l, 4-35 cyclohe,xyl~,neoxycarbonyl-tran~,-1,4-cyclohexylenecarbonyl-b-oxy-l~4-pheny~ neoxyteraphthaloyl) and poly(oxy-ciE,-1,4-, .. :. ..

"'091/12136 PCT/US91/00463 2 ~

g cyclohexylaneo~ycarbonyl-trans-l,4-cyclohexylenecarbonyl-b-oxy-l,4-phanyl~neoxyterQph~haloyl) in methylene chloride-o-cresol poly(oxy tr~n3-l,4-cyclohexylen~ oxyc~rbonyl trans-l,4-~yclohexyl~necarbonyl-b-oxy-(2-~othyl-l,4 ph~nyl~ne30xy 5 -t~rephthaloyl) in l,l,2,2-tetrachloroe~ane-o-chlorophanol-phenol (60:25:1S vol~vol~vol), poly r oxy-tr~ns-l,4 cycloh~xylenaoxycarbonyl-trans-l,4-cyclo haxylenecarbonyl-b-oxy(2-methyl-l,3-phenylene)oxy-tsrephtha loyl] in o-chlorophenol and ~h~ liXe; polyazo~ethines ~uch 10 a~ tho;se pr~p~r~d from 4,4'-di~mino~nzanilide an~
terèphth~laldephide, methyl-l,4-phenylenedia~ine and teraphthalaldehyde and the like; polyi60cyanides 6uch as poly(-phenyl ethyl i~ocyanide), poly(~-o~tyl i~ocyanide) and the like; polyisocyanates such as poly(n-alkyl 15 isocy~nates) as ~or example poly(n-~utyl isocya~ate), poly(n-hexyl isocyanate) and the liXe: lyo ropic crystalline polymers with heterocyclic units 6uch as polytl,4-phenylene-2,6-bænzobisthi~zole) (PBT), poly(l,4-p~enylene-2,6-benzobi~oxazole) (PB0), poly(l,4-phenylene-20 l,3,4-oxadi~zole), poly~l,4-phenylene-2,6-benzobi~imidazole~, polyt2,516)-ben2~idazole] (A~-PBI), polyt2,6-t1,4-ph~nylene-4-ph~nylquinoline~ polytl,l'-(4,4'-biphænylen~ is(4-ph~nylguinoline)] and the like;
polyorganopho~phazines such a~ polyphosphazine, 25 p3lybisphenoxyphospA~zin~, poly~bis~,2,2' tr~luorosthylen~ phosphazin~] and the like; metal polymer~ GUCh as tho8e derived by condensation of trans-bis(tri-n-butylpho~phine)platinum dichloride with a bisacetylene or trans-bis(tri-n-butylphosphine)bis(l,4-30 butadinynyl)platinu~ and similar co~binations in thepresence of cuprous iodine and an ~ide; cellulose and cellulose derivatives such as e~ter~ of c211ulose as for example triacetate cellulose, acetate cellulose, acetate-butyrat~ cellulo~e, nitrate cellu}ose, and sulfa~e 35 cellulo6e, ether& of cellulo~e as for example, ethyl ether cellulose, hydroxymethyl ether cellulose, hydroxypropyl WO9~/12136 PCTJUS91/004f-e~her cellulose, carboxy~Q~hyl e~her cellulose, ethyl hydroxyethyl Q~her cellulo~a, c:y~noethylathyl ether cellulosa, Qther-ester~ of cellulose as for example acatoxyethyl ether c~llulo~a and bcnzoylo~ypropyl ether 5 cell~lose, and urethane cQllulose ~ for ~xample phenyl urethan~ cellulo3e; ther~ot~opi.c liquid cry~talline poly~ars such a3 cellulo~e~ ~ndl ~heir deri~atiYes as for exa~pla hy~roxypropyl callulose, ~thyl cQllulose propionoxypropyl c~llu106~; then~otropi~ copolyQsters as 10 for ~xa~pl~ copolyn~r~ of ~-hydroxy-2~naph~o~c acid and~
p-hydroxy ~nzoic acid, copoly~ers o~ 6-hydroxy-- 2-naph~hoic ncid, ter~phthalic ac~d ~nd dihydroxyb~nzophenone, copolymers o~ phenylterephthalic acid ~nd hydroguinone, copolymers of chlorohydroquinone, 15 terephthalic acid and p-~c~toxy cinnamic ACid, c~polymers of chlorohydroquinone, terRphthal~c acid and ethylene dioxy-4,4'-dibenzoic acid, copoly~r~ of hydroquinone, ~ethylhydroquinone, p-hydroxy~enzoic acld ~nd isoph~halic acid, copoly~ers of (l-phenylethyl)hydroqslnone, 20 tarephthaiic acid and hydroguinone, ~nd copoly~ers of poly~thylene t~reph~halate) and p-hy~roxybenzoic acid:
and thermotropic poly~ides and ther~otropic copoly(~ide-~sters).
Also illustrativ~ of u8e~ul organic filaments are th08~ co~posed of ~x~ended ~hai~ polymers formed by poly~erization o~ a~-un~tura~ed ~onomars o~ ~he formula:
RlR2 C--CH2 wherein:
- Rl and R2 are the s~e or different and are 30 hydrogen, hydroxy, halogen, ~lkylcarbonyl, carboxy, ~lXoxycarbonyl, heterocycle or alkyl or aryl either unsubstituted or substituted with one or ~ore substituents selected fro~ the ~roup consisting of alXo~y, cyano, hydroxy, al~yl and aryl. Illustrative of uch polymers 3s of ~,B-unsaturated ~ono~er~ ~re poly~ers including polystyrene, Flolyethylene, polypsopylene, .: . . .: , .,.. ,. . . ~
,, . - - .

"'Ogl/12136 PCT/US91/0~463 poly(l-octadecene), polyi~obutylene, poly(l-pentene), polyf2-m~thyl~tyr~ne), poly(4-~ethylstyrene), poly(l-hexene), poly(4-m~thoxystyrena), poly(5-~ethyl-1-heYene), poly(4~ hylpent~ne), poly~l-butene), polyYinyl 5 ~hlorid~, polybutylene, polyacrylon~trile, poly(~ethyl p~ntene-l), poly(vtnyl ~lcohol), polytYinylac2tate), poly(~inyl butyral), poly(~inyl chloride3, poly(~inylidene chloride), Yinyl cholorld~ovinyl acetate chloride ~opolym~r, poly(~inylldena fluorid~), poly(~e~hyl 10 acrylate), polytm~thyl m~thacrylate), poly(m~t~acrylonltrile), poly(acryl~ide), poly(vinyl fluoride), poly(vinyl fonmal), poly(3-methyl-1-butene), poly(40~t~yl-l-butene), poly(4-~ethyl-1-pentene), poly(l-haxane), poly(5-~ethyl-1-hexene), 15 poly(l-o~tadece~e)~ poly~vinyl cyclop~ntan~), poly~vinylcyclohQYane), poly~a-vinylnaphth~lene), poly(vinyl ~ethyl ~her), poly(vlnyl~thyl~ther), poly(vinyl propylethsr), poly(vinyl carbazole), poly(vinyl pyrrolidone), poly(2-~hloro~tyr~ne), poly(4-chlorostyrene), 20 poly(vinyl ~or~ate), polytvinyl butyl ether), poly(vinyl octyl ~ther), poly(vinyl ~¢~yl ketone), poly(methyli~opropenyl k~tons), poly(4-phenylstyrene) and ~he like.
Illustrative of useful organie fil~s for uso in 25 the pre~nt invention ~re ~hose co~po~ed of the poly~ers d~cribed a6 use~ul for filaments, nbo~e.
Illustrative o~ use~ul inorganic fila~ents for us~ in the pre~ent imrentiorl are gla~s ~ibers ~uch as fibers for~ed :rrOm quartz, magnesia aLu~uninosilicate, 30 non-alkalin~ a:Luminoborosilicate, ~oda borosilicate, soda silicate, ~oda lime-~luminosilicate, lead silicate, non-alkaline l~ad boroalumina, non-alkaline barium boroalumina, non-alkaline ~inc boroalu~ina, non-alkaline iron ~luminosilicate, cadmi~ borate, alumina fibers whioh include ~sa~fil" ~iber in eta, delta, and theta phase ~o~, a~bestos" boron, silicone ca~bide, gr~phite ~nd , :"... . , -- ~ , :

WO91tl2136 PCr/US91/0046 carbon such as those deri~ed from the carbonization of polyethylene, polyvinylalcohol, l~aran, polya~ide (Nomex) type, nylon, polybenzimidazole, polyoxadiazole, polyphenylene, PPR, petroleum and coal pitches s (isotropic), mesophase pitch, ce:Llulose and polyacrylonitrile, ceramic fibers, ~stal fibers as ~or axample steel, aluminum metal al:Loys, and the like.
In ~he pre~rred embodi~ents of the inventio~, th~ conti~uous lsngth o~ ~h~at i~ r~bric~t~d Srom an ~o impr~gnat~d filament nQtwor~, wh$ch ~ay includ~ a high molQcular ~eight poiy~hyl~ne filam~nt, a ~igh molecular weisht polypropylene filament, ~n nr~id ~ilamont, a high molecular ~eiqht polyYinyl alcohol ~ila~ent, a high molocular weight poly~crylonitrile filament or mix~ures 15 theraof. ~SP 4 457 985, hereby inco~porsted by referencP, ~enerally discusses ~uch hiyh ~olecular weight poly~thylene and polypropylene filaments. In tha case of polyethylene, suitable filamants ære tho8e of molecular waight o~ ~t least 150,000, preSer~bly ~t least ona ~illion and ~or~ prQ~rably batw~en two million and f ve million. Such ~Yt~nded chain po~yethylon~ (ECPE) *ila~hnts ~ay ~ gro~n in ~olution a8 d~cribed in USP
4 137.394 or USP ~ 3~6 138, or may be a.filament spun from a 501ution to form ~ gel structure, as described in German 0~. 3 00~ 599 and GB 20512667, and e~pecially descri~ed in U.S. 4 551 296. As used herein, the term poly~thylene ~hall ~ean a prsdominantly linear polye~hylene m~tarial that may contain minor amounts of ~hain branching or co~onomers not exceedin~ S modi~ying units per lO0 main 30 chain carbon atoms, and th~t may al~o cont~in ad~ixed ~erewith not morQ than about 50 weight percent o~ one or more polymexic additives such as lkene-l-poly~ers,1 in particular low density polyethylene, polypropylene or polybutylene, copolymers containing mono-ole~ins as 35 primary monomers~ oxidized polyolefins, graft polyolefin copoly~er~ an~ ~polyoxymethylenes, or low molecul~r weight ... ..... ..
-.. ~ I
. ~ , - .. ~

. .. . ::

91~12~36 PCT/US91/00463 ~-~ s additives such ~ antioxidants, lubricants, ultraviolet s~rQening agonts, colorants and the like which are ~
co~monly incorporatQd by ref~rQnce. Depending upon the formation technique, ~h~ ~r~w ratio and te~peratures, and 5 o~her conditions, a variQty of properties can be imparted to ~hese filaments. The ten city o~ the fila~ent s~ould be at l~a~t about 8 ~/d, preferably at least ~bout 15 g/d, more preferably at least about 25 g/d ~nd most prQ~erably ~t l~a t about 35 g/d. Similarly, ~he tsnsile ~odulu~ of 10 the ~$la~snts, a~ ~Qasur~d by ~n Instron t~nsil~ testing ~a~ne,-is-~t l~st about 160 g/d, pr~ferably at least about 500 y~d, more prs~Qr~bly- 8t l~ast ahout lO00 g/d and ~ost prefera~ly at lea t ~bou~ l~00 g/d. The energy-to-braak o~ the fil~meDts i8 at least ~bout 8 J/g, preferably at l~a~t about 25 J/g, ~ore pr~erably at least about 40 J/g and most pr~erably at l~ast about 50 J/g.
The~a hig~ast ~alue~ for t~na~ty, tensile ~odulus and enargy-to-br2ak ~re g~narally ob~a~nable only by e~ploying solution grown or gel fila~n~ p~ocesses~
2Q Similarly, highly oriented polypropylene o~
~olecular w~isht at least 200,000, pre~rably at least one ~illion ~nd ~orQ prerersbly at l~ast two million, ~ay be us~d. Su d h~h ~olecular weight p~lypr~pylene may be formed i~to re~sonably well oriented filaments by 25~Q~hnigues dQ~cr~bed i~ th~ various rs~erence~ r~f~rred to ~o~e, and ~specially by the tec~niqu~ of USP~ 4 663 lol and 4 784 820 and US Patent ~pplication Serial No. 069 68~, filQd July 6, l9B7 ~s~e publi~hsd application wo 89 00213). SincQ polypropylene is a nuch l~ss crystalline 30 ma~erial t~n polyethylene and co~tains pend~nt methyl groups, t~n~city value~ aehiQ~abl~ wi~h polypropylene are generally substzlntially lower th~n the corre ponding values for poly~hylene. Accordingly, a suitable tenacity is at l~ast about R g/d, prefe~bly nt least about 12 g/d, 35 and ~ora prefer~ly at l~ast abou~ 15 g/d. The tensile ~odulu8 for poly~ropylene is at least ~bout 160 g/d, . ~ . .. . . .
. . : : ~ :..: - . ,. . :. . .

. . . . :; ~

WO91/~2136 PCT/US91/00~6 prefera~ly at least ~bout 250 g~d, and more pr~ferably at lea6t about 300 g/d. ~he ~ne~gy-to-break o~ the polypropyl~ne is at l~ast about 8 J/g, pr~erably at least about 40 J/g, and most prefera~ly at least about 60 J/g.
Hi~h ~012cular weight polyvinyl alcohol filam~nts having high t~n6~le ~odulus are d~scribed in USP
4 440 711, ~areby ~ncorporat~d ~y referanc~. Pre~erred polyvinyl alcohol fil~ents will havQ ~ tenaci~y o~ at l~ast ~hout 7 g/d, ~ ~odulus o~ ~t l~t ~bout 150 g/d and 1o an anerqy-to-brsak of at l~ast ~bout B J/g, ~nd -~particularly pr~f~rrQd PV-O~ ~ila~2nt8 will have a tenac~ty-of at l~a~t about 15 g/d, a modulus of at least about 300 g/d and an energy-to-brs~k of at least about 25 J/g. ~ost preferrad PV-O~ ~ilamants w$11 have a tenacity of at loast about 20 ~Jd, ~ modulus o~ at least ~bout 500 gJd and an energy-to-br~k o~ at least ~bout 30 J/g.
Suitable PV-OH ~ilam~nt having a wsight average molecular ~eight of at least about 200,000 can be produced, for exampla, by the process ~isclosed in USP 4 599 267.
In ~h~.case of poly~rylonltrile (PAN3, PAN
~la~nt ~or use i~ th~ pre~nt inven~ion ar~ of ~ol~cular Yeiqht o~ at l~ask about 400,000. PArt~CU1~r1Y useful PAN
fila~nt ~hould hav~ a t~nacity of at le.st about 7 g/d and an Qne~gy-to-bre~k o~ ~t l~st about 8 J/g. PAN
25 ~ila~ent having a ~olecular weight of at least abo~t 400,000, a tenaci~y Or at l~as~ ~bout ~5 to about 20 g/d and an energy-to-break o~ at least about 25 to about 30 JJg ~ ~o~t u8~Ul in producing balli~tic resistant articles. Such ~ilaments ~re disclosed, ~or example, in 30 US 4 5~5 027.
In tlhe case of ~ramid fil~ents, ~uitable aramid filaments ~ormlad principally from aromatic polyamide are described in USP 3 671 542, which is hereby inco~porated by re~erence. Th~2 aramid fila~ent will have a tenacity o~ at 35 least about 15 g/d, a modulus of at least ~bout 400 g~d and an energy-to-break of ~ l~a~t ~bo~t 8 3/g. Preferred : . . : :. - . ~
- - . ~
: :: . -- - . . .

~vo 91/12136 PCT/US91/00463 ~ ,?~

_ 15 _ aramid filament will have a tenacity of at l~a~;t about 20 g~d, a tensilQ modulus of at l~ast a~ollt 500 g/d and an sn~rgy-~o-~r~aX at 1~aE;t ~bout 20 J/g, and particularly pr~f~rred ara~id fila~D~nts will have a te~acity of a~ least 5 about 20 g/d, a ~odulus o~ ~t lea5t about 1000 ~d and an ~nergy-to-~reak of at l~t ~bout 2 0 J/g . Mo~;t pre~Ferred aramid ~ilaments wlll hav~ ~ tdnacity of ~t lQa~t about 2 2 g/d, a fflodulu~ of at least ~ou1: 900 s~/d and an ~ne~rgy-to-2:~reak oi~ st l~a3t à~out 27 ;~g . ~or ~xa~ple, poly (p 10 phanyl~n~ t~r~ph~ala~id~) ~il~a6~nts produc~d co~srcially ~-~~ ~ ~ -by l~upont Corpor tion und~r the trad~ n~ae of }~evlarC~29, 49, 129 and 149 and having ~odRrately h~gX Jnoduli and tena~ity values are particularly u~eful in ~OrIlliRg b~ tic re3i~tant ~o~posi~es- A180 useful in the 5 pSaCtiGe of thi~ invention i~ polytmetAph~nylene isophthalamide) filaments produced c:b2~ercially by Gupont mder ~e trade nu~e No~Dex.
In t:he case o~ liquid crystal copolyesters, suitable ~il~ent~; are disclGsed, for ex2lmple, in U.S.
20 P~tant~; 3 975 487, ~ 118 372, and 4 l~l 470, h~reby incorpora~sd by r~r~a~c~. TQna::itiQs of ~out 15 to 30 g,td, moro pro~Qrably about 20 ~o 25 ~/d, ~odulu~ o~ out 500 t:9 150t) g/d, preferably a~out lO00 'co 1200 g/d, and an ~nergy-to-br2~k of at la~8t ~IbOUt`. 10 J/g ~Ire pa~icularly 25 desire~a~ls.
The matrix ~aterial e~ployed in the practiee o~
8 invention comprises one or ~ore the:r~osattiny resins, or one or ~ora thermoplastic r~sins, or a blend of ~u~h re$ins. ~he elongation o~ ~ho ~esin/resin syste~ must be 30graat~r than t~at of ~h~ re$nforcing ~ila~ent and preferably ranges ~ro~ about 3 to a~out 500 percent (ASTM
D-638). ~esin!; ~ay be blended in order to achieve higher elongation values, e.g., an ~poxy resin (E~VN 828, Shell Che~ical) with an elongation of ~bout 0.5~ ~y b~ blended 3swi~h another epoxy resin (EPON 736, Sh~ hemioal) having an elongation of abou~ 40t to achieve an epoxy r~ in . : : ~ : , , ............................. , . ~

- ~ , ;: ' ;
., W091/12136 PCT/US91/~04~-,? ' ~

~y~te~ having ~n Qlong~tlon o~ ~bout 14S. Suitable reinforc$ng filament~ for this system would include, by way of example ~ gla~5 ~ ar~id, p~lyethylene, polypropylene, polyvinyl alcohol, poly~crylon~trile or ~ix~ures ~hereof.
~ s us2d hsrein ~th2rmopla~tic re~ns" are refiin~ which can ba heat~d ~nd soft~n~d, cool~d and hard~n~d li~itle88 ti~ea wi~hout und~rgoing a basic altsration, and ~th~rmo8ettlng re~$ns~ ~r~ resin6 which do 10 not tolerate-th~rmal~cycling and wh~ch ca~not be r~softened and rsworked aftar ~olding, extrudimg or cas~ing-and which at ain new, $rrQversible prop~rties when once set at a t~peratur~ which is ~r~tic~l to e~ch re~in.
~h~r~os~tting r~sins U~QfUl in the practice of 15 thi~ invention ~ay vary widely. Illustrativ~ o~ u~eful t~er~o~etting resi~ are alkyds 8U~h as those d~rived from est~rification of polyba6ic ac$d~, ~s for exampl~, ph~halic anhydride, fumaric ~cid, ~aleic anhydrid~, isophthali~
acid, terephthalic acid, tri~ssic acid, h~i~ellitic acid, 20 succin~c anyhydride, ~atty acid~ deFived fro~ ~ineral or v~getable oils and ~he liXe, ~n~ polyhydric alcQhol~ as for Qxa~ple glyc~rol, ethyl~n~ glycol, propyl~ne glycol, p~nacol, 1,4-hutanodiol, l~3-prop~nediol~ sorbitol, pan~a~rythritol, l,2-cyelo~ex~ned~ol and the like. Other 25 us~ul th~r~08etting resins are ~crylics such as cro~linkable polyAcrylic6, polyacrylates, ~poxydiacryl~t~s, urethane diacrylate~ and ~he like.
Still other ~a~ful ther~o8~tting resins are ~mino resins deriv~d from r~action b~twe~n ~or~aldehyde and Yarious 30 amino compounds 8UCh as m~lanine, urea, aniline, ethylene urea, 5ulfona~ide, dicy~nodinm~d~ and the like. Other u~eful tb~rmosetting r~sins include ur~thanes derived from r~action o~ polyisocy~n~t~s or diisocyanates such as 2,6-tolylsne diisocyanate, 2,4-tolylene diisocyanate, 35 4,~'-diphenyl-~ethane diisooyanate, 4,4' dicyclohe~yl ~th~ne diisocy,~nate and the like, and polyol~ ~uoh as .

. . . ..
, :: ~:. - . .:. .
., .; ~ .. . . :
: . .:- . .. , .: : , '~91/1~136 ~C~/US91/0~463 glycerin, ~tAylena glycol, dieth1ylane glycol, tr~ethylolpropane, 1,2,6-hexaneltriol, sorbitol, pentaerythritol and ~he llke.
~x~mplary of stlll other thermo~ttiny r~sins 5 u8~Ul in th8 practic~ of ~i3 in~ntion ar~ unsaturated polyestQrs dGrivQd ~ro~ reaction o~ dibasic acids ~uch as mal~ic ~nhydride, ~umaric aeid, ~dlpio aoid, azelaic acid and ~he l$ke, ~nd dihydric alcohols ~uch a~ e~hylene glyeol ~nd propyl~ne gly~ol, 1,3-butyl~n~ glycol, 102,3-butylen~ glycol,-di~t~ylsns glycol, dipropylene qlycols and the like; and ~iliconQs ~uch as d~e~hyldichloro ilana and ~h~ llkeO
Y~t ano~her cla~s o~ u~aful ~hermose~ing resins are epoxies ~as~d on ~aturat~d or unsaturated ~aliphatic, cycloaliphatic, aro~atic and het~rocy~lic epoxides. Use~ul ~poxide~ includq glycidyl ethers derived fro~ epichlorohydrin adducts and polyols, p~rticul~rly polyhydr$c phenols. ~nother u~a~ul epoxide i~ the diglycidyl ether o~ bisphunol ~. Addition~l ~xamples of 20u8eful polyepoxide~ ar~ r~orcinol diglycidyl ether, 3,4-~poxy-6-~thylcyclohaxyl~e~hyl-9,1~-epoxy~tearate, 1,2,-bi~(2,3-~poxy-2-~thylpropo~y)~th~On~, diglycidyl ether-of ~,2-(p-hydroxyph~nyl) propane, butadiene dioxide, dicyclopentadisne dloxide, penta~ry~hritol tetrakis~3,4-25epoxycyclohsxanecar~oxylate~, vinylcyclohexene dioxide,divinylbenzen~ dioxide, 1,5-pant~diol bis(3,4-~poxycyclohexanla carboxylat~ thylene glycol bis(3,4-Qpoxyc~clohexan~e car~oxylate), 2,2-diethyl-1,3-propanediol bis(3,4-epoxycycloh~xanecarboxylate~, 1,6-hex~nediol 30bis(3,4-~poxycyclohexOn~carboxylOte), 2-butene-1,40diol bis~3,~-epoxy-6~-methylcyclohexanecarboxylate), 1,1,1-trimethylolpropane tris (3,4-epoxycyclohexanecarboxylate), 1,2,3-propanetr:iol tris~3,~-epoxyeyclohexanecarboxylateS, dipropylene glycol bis~2-ethylhexyl-4,5-epoxycyclohexane-3sl,2-dic~rboxyl~ta), diethyl~ne gly~ol bis(3,~-~po~y-6-m~thyl~ycloh2xarlecar~oxylate)~ triethylene glycol bis(3,4--. : , :.

-: ~ - . .. . .
. :- . . .... ...

~O9l/1~136 PCT/US91/0046^-apoxycycloh~xanecarboxylate), 3,4-epoxycyclohexyl~ethyl 3,4-~poxycyrlohexanecarboxylate, 3,4-epoxyol-~e~hylcyclohexylnethyl 3,4-epoxy-1-nethylcyclohaxanocarboxylate, ~i(3,4-S ~poxycyclohexyl~ethyl) pi~lat2, bis(3,4~epoxy-6-~thylen~eyoloh~xylme~hyl) ~alnat~, bi~(3,4 epoxy-s-~thylcyclohexyl~ethyl) ~uccinate, ~i8 (3,4 epoxycyclohexyl~ethyl) ox late, bis(3,4-epoxy-6-~Qt~ylcyclohsxylm2~hyl) ~Q~acatQ, ~i~t3,4-~poxy-6-1o ~hylcycloh2xylms~hyl~ ~dipate, bi~(3,4- ~ ~~~.
Qpoxycyclohexyl~ethyl) ~r~phthalate, 2,2'-sulfonyldiethanol bis(3,~-epoxycyclohexansGar~oxylate), N,N'~hyl~ne ~is(4t5-epoxycycloh~xane-1,2-dicarboxl~i~a), di(3,4-15 epoxycyclobexyl~ethyl~ 1,3-tolylen~dicarb~mate, 3,4-epoxy-6-~ethylcyclobaxan~c~boxaldehyde acetal, 3,9 bis(3,4-epoxycyclo~exyl) spirobi-(~ethadioxane), and ~he liXe.
Useful ~har~o~tting r~sins also lnclude 20 phs~olic re~ins produced ~y kh~ ~actio~ of ph~nols and ald~hyde~. U8~ h~nols ~n~lud~ ph~nol, o-cre~ol, ~-cresol, p-cr~ol, p-t~rtbutylph~nol, p-tertoct~lphenol, p-nonylphenol, 2,3-xyl~n~l, 2,4-xylenol, 2,5-xylenol, 2,6 xylanol, 3,1-xylenol, 3,4-xylenol, rQsorcinol, 2~ ~3phenol-A and the like. Useful ~ldahydes include fo~maldehyde, acetaldehyde, propionaldehyde, n-~utyrald~hyde, isobutyraldehyde, glyoxal, ~ur~ural and the lika.
O~her u~e~ul ther~osetting r~sins are aro~atic 3Q vinyle~ter~ sudh ~8 th~ condensation product of epoxi~e r~sin~ and un~ urated acids usually diluted in a ~ompound ` having doubla l~ond unsaturation such ~ vinylaromatic ~ono~r as ~or example ~tyrene and vinyltoluene, and diallyl phthal~lte. Illustrativ~ of useful vinylesters are 35 diglycidyl ad$pate, diglyc$dyl i~ophthal~te, di(2,3-epoxybutyl) ~dlpa~2, di(2,30epoxybu~yl) oxalate, di(2,3-".' . '. ,, ,1 , . ' .
.: , . . .
.. . . . .
- , , .. ~ :, . ' ;
- ~ :: , . ~ . . , . ,:: .-.. - ,:
. : : .. ~.- ,, O91/12136 P~T/US91/00463 epoxyhexyl) succinate, dil3,4 ~poxybutyl) maleate, di(2,3-epoxyoctyl) pim~lata, di(2,3-epo~utyl) ph~halate, di(2,3-epoxyoctyl) tetrahydroph~h~late, di(4,5-~poxydode~yl) malea~e, di(2,3-~poxy~utyl) terephthalate, di(2,3-epoxypentyl) thiodiprop~onate, di.(5,6-epo~ytetradecyl) diphenyldicarboxylat~, di(3,4-~poxyheptyl) sulphonyl~i~utyrate, tri(2,3-epoxybutyl) 1,2,4 butanetricarboxyla~, d~(5,6-epoxypent d~cyl) ~aleate, di(2,3-~oxy~utyl) az~l~ta, di(3,4-opoxy~utyl) citrate, di(5,6-8poxyoctyl) ~ycl~h~xane-1,3-dicarboxylate, di(4,5- - -epoxyoctadecyl) ~lonate, biRphenol-A ~u~aric acid polyes~er and ~he like.
Pra~errsd ~harmo~tting resins for use ~n the t prac~ice o~ this invention are ~inylester~, unsaturated polyesters, epoxies and phenolics. P~rticularly preferred thermosetting rssin~ are vinylest~r~, apoxie~ and phenolics, wi~h ~inyle~ters being the ther~o5etting xesin of choica.
Tbe~oplastic re~ins for use in ~he practice of thi~ invention ~y also vary ~$dely. Illu~trative of use~ul th~r~oplasti~ r~in~ are poly~ctone~ ~uch as poly~piv~lol~ctone), poly(~-e~prola~ton~ and ~he lik~;
polyure~hanes deriv~d ~ro~ r~action o~' dii~ocyanates such a3 l,~-naphthal~ne dli~ocyanate, p-ph~nylene diisocyan,te, ~-phenylen~ ~ii80Cyanat2, ~, ~ toluene diisocy~nate, 4,4 dtphenyl~ethana diiso~yanate, 3,3'-dLmethyl-4,4'diphenyl~ethane dii~ocy~nate, 3,3'dimethyl-4,4'biphenyl diisocyanate, 4,4' diph~nyli~opropylidine diisocyanate, 3,3'-dimethyl-4,4'diphenyl d$isocyanate, 3,3'-dimethyl-4,4'-diphenylmal~ane diisocyanate, 3,3'-dimethoxy- ~
~,4'-~iphenyl d:Lisocyanate, dianisidine d$isocyanate, tolidine diisoq~anate, hexamethylene diisocyanate, 4,4'-diisocyananodiphenyl~ethane and the like and linear long-chain diols ~uch as poly(tetramethylene adipate), poly(~thylene ~clipate), poly(l,4-butylene adipate), poly(l,5-p~ntyl~!ne adipz~e), poly(l,3 bu~ylene a~ipate), ., : - . -:
;. .: . . .. .

.~.. : . ~ ' :

WO 91/1213~ P~r/VS91/0046 ?~ ~

poly (ethylene ~uccinate), poly ~2 , 3-butylene succinate), PO1YQther diol~ and th~ like, polycarbonates such as poly~mRthane bis (4-phenyl~ carbonat~, poly[1, l-~thsr ~)i5 ~4-phenyl) carbonate~, polytdliphenyl~nethane S b$~t4-phenyl) car~onate], poly~l,l-cyclo~x~ne bis(4Oph~nyl)carbonate~ and the like: p~ly ~ul~ones, polyet:h~r ~the:r ketoneæ, polyamidç~s ~uch ~8 poly ( 4 -a~ino butyric ~cid), poly (hexam~thylerie~ adipa3~ide), poly(6-~minoh~xanoic acid), poly(~a-xylyl~n~ adipaDlide), 1 0 poly (p xylylane s~s:a~idQ ), - poly ( 2 , 2 , 2-t~thyl ~ ~
he~thyl~ne terep~thalaD~id2), poly (~taphenylene iso~th~ nide) (Nomex), poly~p-ph~nyl~ne terephthala~nide) ~Xavlar~, and 'che like, polyesters such ~s poly(ethylene a2~1ate), poly~thylene-l,S-naphthalate, poly(1,4-cycloAsY~n~ d ~ethylen~ tarephthalate), poly(e~hylene oxy~enz3ate3 (A-~ell), poly~para-hydroxy benzoate) (Ekonol), poly(l,4-eycls~exyllden~ d~thylen~
tereph~h~late~ (Rodel) (as), poly~l,4-cycl~hexylidene di~thylene terephthalate) (Rodel) (t~ans), polyek~ylene ~ oph~h~iate, polybutylen~ t~r~phthalate and the like;
poly(aryl~ne oxid~s) ~uch ~ poly(2,C-dimQ~hyl 1,~-phenyl~na oYide), poly(2,6-diphenyl-1,4-phenylene oxide) ~nd th~ ; poly(sryl~nQ ~ul~id~s) suc~ ~s poly~phQ~ylanR sulfide) and ~he lik~; polyetheri~ides;
~her~opls~tic el~sto~ers such a~ polyusethane elasto~ers, ~luoroela~tomers, ~utadiene/acsylonitrile elastomer~, s~licone el~s~o~ers, polybu~adiene, polyi~obutylene, ~thylene-propylene copolyoers, ethylen~-propylene-diene terpoly~er~, polychloroprene, polys~l~ide ela~o~ers, ~lock c~polymQrs, ~ade up o~ nt~ of glas~y or cry~t~ ne ~locks ~uch as polystyrene, poly~Yinyl-tolu~ene)l poly(t-butyl styrene), polyester and the like and the elasto~eric bloc~s such as polybutadiene, polyisoprene, ethylene-propylene copoly~ers, ~thyl~ne-~utylene copoly~srs, polyether e~ter and the like as ~or e~a~ple 1~e copoly~ers in poly~tyrene-poly~utadiene-, ~

- - ,,: .

91/12136 ~ PCI`/VS91/00463 poly~tyrene block cs)polymer manufactured by Shell Chemical CoD~pany und~r th~ tr~de name o~ Kratorl; vinyl poly~ers and ~eir copoly~Der~ ~uch as polyvinyl ~est~te, polyvinyl alcohol, poly~rinyl chloride, polyvinyl ~utyrAl, poly~rinyl-5 idene chlorid~, ethyl~ne-vinyl acetate copoly~ers, and the liXa: polyacrylics, polya~rylate and ~air copolymer~; ~uch as poly~thyl acrylate, poly(n-butyl acrylatQ), poly~e~hyl laathacryla~e, polysthyl 3aethacrylata, poly(nobutyl D~Q~ac~ tQ), poly(n p~opyl ~ ryl~ts), poly~cryla~ide, -10 polyac~ylon~tril~, poly~cryllc alc$d, ~yl~ rylic acld oopoly~ers, ~ethyl m~th~c~yl~t2-styrQn~ copoly~ers, ethylen~-st~yl acrylat~ ~opoly~ars, ~thac~yl~te ~ut~diene-styrsn~ copolym~r~ and ~h~ lik~; polyol~ins such as low dens~ty poly2thylene, polypropylene, c~lorinat~d low 15 d~n~ity poly~thylen2, poly(4-me~hylol-pent~ne) ~n~ ~h~
liX~: io~o~r~; an~ poly~pi~lorohydrins.
In ~h8 pref~r~d ~odi~en~ of the in~Qntion, ~h2 ~her~oplas~o ~aterial ~ ~el~c~ed Sro~ the group consisting of polyur~han~s, poly~inyls, polyacrylics, 20 polyola~ins, and polyisopr~n~-polye~hyl2ne-butylen~-poly6tyr~na or poly~tyrene-polyi~oprene-polystyrQne ~lock copoly~er ~h~r~oplastic ~la~to~ers, ~ost prefer~bly ~he latt~r.
~h~ proportion o~ ~atrix to ~ ent in ~he 25 co~po~it~ ~rt~ i8 not cr$tical and ~y ~ary widely, In general, ~he n trix ~ater~l ~ay form fro~ ~bout l~ to a~o~t 9O~ by volu~e, pr~ferably about lO to BO%, and ~ost pre~erably ~bout lO to 30t.
The con~in~ou3 length~pli~ of ~hests can ~e 30 ~abricated using a number of proc~d~r~s. In the pre~erred a~bodi~ent, ~he fila~ent$ ar~ precoatsd with the dQsired m~trix ~at~rial prior to being ~rranged in a n~twork. The coating ~ay be ~ppliad to the f~la~nts in a variety o~
way~ and any ~thod known to ~hose o~ skill in the srt ~or 35 coating ~ilaments may be u~ed. ~he networks produoed t~ra~ro~ are for~ed into ~imple co~po5i~es," whioh alone . - " ,:: , : .

:
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WO91~1~136 P~T/U~91/0046~ `

~, Y ~
~ 2~ .
or wit~ the optional ~ilm layer ~ay be the precursor to preparing complex composite arti.cl~s. By Ksimple composit2~ i8 ~aant a composite ~de up of one or ~ore laysrs, oach of ~he ~sy~r~ containing ~il~ment~ as 5 describ~d a~ove with a ~trix ~at~rial which n~ay include minor proportions of othar ~atarial3 ~uch ~ ~illers, lubricants or the like.
Yarn bundl~s of ~rom about 30 to ~bout 2000 individual ~ila~snts o~ le8s than ~bout 12 denier, and 1o more preferably o~ hbout 100 ~ndividual ~ilam~ts of less than about 7 denier, are suppli~d ~ro~ a cr~el, and ars led through guides ~nd a spre~der b~r into a collimatin~
co~b just prior t~ coat~ng. Th~ colli~ating comb ~ligns the ~il~men~s coplanarly ~nd in ~ ~ub~tanti~lly p~rallel, and unidirectional fashion. The f$la~ents ~re then sandwic~ed b tween release papers, one of which is coated ~ith a wet matrix rssin. This ~yste~ i5 ~h~n passed under a series of pres~ure rolls to completQ the impregnation of the ilaments. ~he top relea~e paper is pulled off and 2~ sollsd up on 8 ~takeup r~al ~hil~ ~h~ impr~gnated network o~
fila~ent~ pr~cs~d~ through ~ ~at~d tunnel oven to re~ove solvont and ~hen b~ taken up.
In th~ ~08t pref~rr~d e~bodiment o~ ~his inv2ntion, two ~uch i~pregnated nQtworks are then con~inuously cross plied, pre~erably by cu~ting one of the net~orks into lengths that can ~e pl~c~d ~uccessively across ~he ~idth of the other nat~ork in a 0-/90-orienta~ion. This for~ a continuous ply. This continuous ply, optionally wi~h ~il~ as discus~ed below, i~ then ~ound wit~ a separation layer of material into a r~ll for treat~ent.
In another e~bodi~ent, one or ~ore uncured thar~osettin~ resin-i~pregnated networks of filaments are s~oilarly formed into ~ continuous length for winding with a separation layer of ~terial into a roll ~or curing of the resin. In this a~bodiment, th~ oontinuous length ~ust ... ,, : .

:, . .

~ 'O 91tl2136 PCI/US91/00463 -- 23 _ b~ of a ehickness and thoe res:Ln must havQ an elongation such t~at the ~ontinuous lengl:~ is flexible when the resin is c:ured.
Tn yat anothor ~odi~ent, one or ~ore resi~-5 impregs~at~d nQtworX~ o~ nt~ ar~ simil~rly fo~aed intoa continuous leng~ to which ~It laa~t one sheet of îilm, as dlscu3s~d b~low, is addQd ~or winding with ~ ~eparation layer o~ Dlaterial into a roll ~or tr~atment.
~il~ may optionally be u~ed as onQ or 311ore 10 layers of the c:orl~inuous length, praf~rably a~ an ou~er layer. The film, or fil~, are add~d ~ter application of t~e ~atrix ma~erial and for~ation o~ a co~i~inuous length sr ply~ as the case ~nay be. The ~ thickness minimally i8 about 0.1 ~il and may b~ ~s larg~ as de~ired so lo~g as the length of ~h2~t8 18 ~till ~u~iciently ~lexible to pe~t roll for~ation. The pr~xr~d ~il~ thicknsss rangas from about 0.1 to l.O ~il, ~ith about 0.3s to o.50 ~il being pr~ferr~d.
Film~ can be u~ed on the 6urrace o~ ~e len$th 2~ ~or ply) for a v~ri~y of r~a~ons, ~Og., to vary frictional propartias, to incra~Q ~ Q ~at~rd~n~a, to increase ch~ic~l rasist~nce, to ~n~r~e r~si~tance to radiation d~gra~tion, and~or to provont dif~u~ion of ~atsrial into tba 33trix. ~h~ ~ay or ~ y not adhere to the 25 continuous l~ngth or ply dupending on ~h~ choice of film, rssin and ilao~nt. Heat and/or pr~s~urQ ~y cause the de~ired adherence, or it ~ay ~8 necassa~y to u~e an adhe~iv~ which i3 he~t or pr~sure ~en~itive between the fllm and the length or ply to c use th~ da~ir~d 30 adherence. Illu5trative adho~ives inolude polystyrene polyi$oprene-polystyren~ ~lo~k copsly~er thermoplastic ~lasto~ers, ther~oplastic and thermos~tting polyure~hanes~
thar~opl~s~ic and ~heDo~et~ing polysul~ides, and typical hot ~elt adh~s~ive5 ~uch as polyvinyl chloride and ~he 35 like. Blend~ of ~dhesivR~ c~n also ~e used.
F~l~s which ~ay be u3ed in the pre~nt invention include thenaoplast~c polyole~inic fil~s, ther~opl~stic . . ................. : . :, .: ~::
,: - , - -, , .

:; :. ' . '': ;: . ' ' ' ' : :;

WO91/1~13~ PCT/US~1/004~ -r~ J. ~

alastomsric ~il~s, cro~slinked th~rmoplactic ~ilms, cros~linX~d Qlastomoric fil~s, poly~ster ~ilm~, polya~ide films, fluorocarbon films, ure~ane films, polyvinylidene chloride fil~s, polyYi~yl chlor.~ds f~ and multilayer 5 film~. Homopolymers or ~opolymer~ o~ these ~ilms can be us~d, and ths f$1ms may be unor:ianted, uniaxially oriented or ~iax~lly ori~nt~d. The ~ s ~ay tnclud~ pig~ents or plasticizers.
Use~ul th~r~opla~tic polyol~finic ~ s include 10 tho~ o~ low density polyethyl~ne, hig~ dQnsity - polyQthyl~n~, line~r low density poly~hylene, poly~utyl~ne, and copolymers o~ s~hylene and propylene which r8 crystalline.
Polyest~r ~ll~s wAich ~ay be u~ed include those 15 of poly~thylen~ ter~p~thalat~ ~nd polybutylene t~rephthalate.
The sQparation layer o~ Dateri l which is wrappsd in~o a r5ll wi~h tha continuous ply functions as an int2rl~af, and AS such, ~ust be separable W7 th a 20 ~inL~um of o~fort ~rom th~ continuous length of sheet/ply a~ter hoat~pr~uxe tr~at~nt. Th~ choice of ~atsrial for ~he int~rleaf ~ay vary dep~ding on what other functaons are desir~d of the ~ateri~l. The int~rleaf ~aterial can b~ us~d to ~upply ~be nece~sary pressure, if its tensile 25 s~reng~h i~ ~u~ciently high, i tightly wrapped with the con~inuou~ length o~ ~haet~ply when forming ~he roll of ~at~rial; acc~ptabl2 ~ater~als for thi~ application, by vay of ex~mplQ, ~r~ w~xed ~e.g., 8ilicone) pap~r such as Xraft pnper, nylon (e.g., nylon 6) ~ , or polyest2r 30 (Q-g-, Mylar) fil~. Pressure can alfio be applied by an in~erl~af ~aterial ~ade from a plastic film wrap which ~hrink~ when t~e roll is exposed to heat; aooeptable materials for ~his application, ~y way of exa3ple, are polya~ter, polye~hylenQ, polyvinyl chloride and 35 ethylvinylacet:ate.
~ he t~mpsratures and/or pressures to whieh the continuous lengths of ~heet/plies o the present invention . .
, ~ , . . ... ... . .

- ~ 91/12136 PC~r/US91/00463 _ 25 _ ar~ exposed to cure t~e t~er~osetting r~in or to cause -~dh~rence of the networks to ~ach oth~r ~nd optionally, to at l~a~t one shoet of fil~, ~ary depending upon the particular 3yst~m used. For ~x~ple, ~or ~xtended ch~in polyathylene filaments, ta~perat.ur~ ~angQ ~rom about 20~C.
; to about 150-C., pre~rably fros~ about 80-C. to about 145-C., ~ore pr~ferab~y from ~bout lOO-C. to about 135-C, d~pending on the type of m~trix ~t~rial ~el~cted. The pre~sures ~ay range fro~ about lO psi (69 kPa) to about 19,000 p i t69,000 XPa).. Pr~0~ur~ fro~ ~bout lO0 psi t690 kPa) to about lO,000 p~i (69,000 kPa), when coupled with temp~rature~ in ~h~ range o~ about 150-C. to a~out 155-C for a ti~e of betwQen 1 to 5 mi~., may cause tha f il m, i f any, to bacoma tran~lu ent or tran~parent.
For polypropylene filaments, th~ upper li~itatio~ of the t~mperature range would be about 10 to about 2~C. higher than for ECPE filament. ~or ara~ld ~ila~ent~, especially Kevlar filaments, the teDperatur~ range wou~d be abou~ 149 t~ 2~5-C. (about 300 ~o 400~
Pr~sur~ ~zy be appl~d to the roll in a Yariety o~ ways. Shrink wrappin~ wi~h plastic film wrap a~ t~B int~rlcaf and tightly wr~pping with an interleaf having sufficient ten~le ~tr~ngth are m~ntioned above.
AutoclaYing i~ ano~her ~ay D~ applying pressure, in thi5 25 case 8LmUlt~neol~s wi~h ~hB application of he~t. The exterior o~ ~h~ roll ~ay ~8 wrapped wi~h a h~at shrinXable ~terial or the ~n~ire roll can bs placed in ~ hea~
~rinkable bag ~nd then be exposed to temperatures which will shrink wrap ~he material~bag, and ~hus ~pply pressure to the roll.
Mamy o~ the rolls ~or~n~d witih continuous lengt~hs o~ ~heet~plies utilizing Qlastomeric resin systems, t~he2~nos~tting resin systeuns, or resin ~ystems wherein a t~he n~oplastic resin i8 co~ibined wit~h an elastomeric or t~Qr~nosetting resin can be trQat~d wit~h pressure alone t~
achieve the benefits of tihi5 invantion. Similarly, ~any of :, :. -, , : , . . - - - :
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- ., .,- ~ . . . . ..
- . . :. . ,.. - . - : :~ , W~ltl213~ PCT/US91/0046 the rolls formed with continuou~ lengt~s of 6heet/plies utilizing thermoplastic r~sin systams can be treated with heat alone to achieve the b~nefits of this invent~on. It is pr~ferred, however, to use both heat ~nd pressure in treating the roll.
T~ nu~b~r of sih~ts~layers forming the continuou~ l~ngth i~ unli~lited a~ long a~ the l~ng~h i5 sufficiently flexibla t~ pQ~it roll Por~atlon ~ollowed by ~olding~curing and unrolling, without advQrse a~fect on 1o utility. The ~lexibility of ~he trQatad l~ngths of the preferred ~bodiments-o~ the pr~ent invention can be d~onstrated by clamping ~ ~0 c~ sguare ~a~pl~ of the article horizontally along one 8$de adge ~nd measuring the a~ount of drapa of ~he ~rticle (the a~ount of drap~ being ~e~sursd by the di~tan~ ~at~en the level of ~he clamped ~ide edge and ~he oppo~ite adge). It i8 ~o~t preferred that the amount of drape b~ at l~st about lO cm, preferably at lQast abo~t 15 c~.
A ~olded roll lO of the present invention is 2 o ~hown in PI GURE 1 r wher~in th~ conti~uou~ length/ply is desi~natod by the nume~al 11, and wherein t~e interleaf is designated by th2 num~ral 12.
Studi~s o~ ~lllstic co~po~ites ~requently employ a 22 cali~r, non~defor~ng stael fr~g~en~ of specifiad ~eight, hardne4s and dimensions [Mil-Spec.
MIL-P-46593~tOR~)). The protectivQ pswer of a ~tructure i8 nor~ally ~xpr~sed by clting the i~pacting ~elocity at which 50% of the projectile~ are stopped, and i~
deRignated the V50 valu~.
Usually, a composite ar~or h~s the geometrical shape of a shell or plate. ~he speci~ic ~eight of the s~ells and plates can be expr~s~ed in ter~s of the areal density tADT). This ~real density corresponds ~ ~he weight pe'r.unit area of ~e struc~ure. In ~he case Or fil~ent reinforced co~posit~s, the ballistic resistance of ~hich depends ~ostly on the fila~2nt, ano~her useful -. - , ... .. . . .
- . .. .
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. . .~

-- ~ 91~12136 P~r/~S91/00463 J, ~ ,~ .

we~ght ch~r~ctari~tic is the f$1~ment areal densi~y of composites. This term corresponds to th~ weight oX the ~ila~ent reinforce~ent per unlt ~rsa o~ th~ compo~ite (AD).
The following exa~ple~s are pre~Qnted to provide a ~ore completa und~rsta~ding o~ ~he invention.

A 0~/90- continuous cros~ ply abou~ 54 inche~
~bout 137 c~ wide is ~or~ed a~ pr~viou~ly de~cribsd with t~o rn~in-i~prRgnat~d n~gworXs. Th~ no~work~ comprise un$diractional hi~h ~trQn5th ~xt~nd~d ch~in poly~ylene fila~ents ifflprQ~n~ted wi~h raton D1107 ~hermopla~tic ~lasto~ar ~strix ta poly~tyr~ne polyisoprQne-poly~tyren~-~lock copoly~er h~Ying 14 wel~ht percant styrene and a product of Sh~ll Ch~mical). Thi~ ent, com~ercially 15 -available frou Alli~d-Sign~l Corporation a8 SPE ~ 1000, has a reported tanacity o~ 3~ g/d, a r~port~d ~odulus of 2000 g/d and a reported elongation o~ ~bout 2.7 ~. Denier is 650 and an $ndiv~dual ~la~ent d~niar is 5.4, or 120 fil~ments per yar~ end. Fila3n~nt 8i2~ is about 27 micron~. Th~ fflatrix ~atorial fo~a about 20% by volume ~nd t~e fila~nt about B0~ by ~olu~e d~ ~h~ continuous ply.
The con~inuous cross ply/l~n~th is w~und ~ith a layer.of Xra~t paper in~o roll with tXe Kra~t paper saparat~n~ su~cessiv~ wraps o~ the ply. Thi~ roll is placad in an oven at about 71-C. t~bout 160-~.), ~nder no pr~s;ure, ~or ~our hours. The roll i8 ~hen allo~ded to cool to roo~ te~perature (sbout 25-C.).
It is expectsd t~at the ballistic perfor~ance o~ ~he material will be good and that the ~aterial will 3Q drape liXe a fabric ~nd handle ~asily.
~.~
A continuous cross ply is ~or~ed ~s in Example 1. ~n 0.5 mil linaar low density polyethylene film (such as i8 produced by P~aven Industries) is la~nin~ted to both ~id~3 of the ply, and the sesulting length is ~ound with a layer of Xra~ 'paper into a roll with ~he Rraft paper :, .,:, : . , ~
~''. , ," ~. .. , :

.- ,. . ,: .: . . -: : : , , .: ., -.: :, .,,::, , . .. .: .
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WO 91/~2136 PC~/US91/0046 ~

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_ 28 --3eparating succQesive wraps of the ply. ThiE; roll i5 placsd in an o~tan, undQr no pr~ssurR, ~o thllt the center o~ the roll raaches a t~para~tur~ o~ about llD-C. ~about ~30-F.), ~ asur~d ~ ocouple, for about one 5 hour. ~ha roll i8 t:hen allo~d to cool to room t~mperature S~out 25-C. ) .
It i~ exp~ d th~t ~th~ balli~tic p~rfom~ance of the ~aterial will b~ good and th~t the 2~tsri~1 will dr~p~ li3ca a ~abric an~ ha~dls ~a~ily.
~
l~le 2 i8 r3p~t~d ~~~p~ t~at the roll is utoolav~d at a to3~ ratur~ o3~ about 121-C. (259CF- ) for an hour at a prossurs Or approx$~ ly 120 lb~ 2.
It $~ Qd t~at ~ balli~tic perfo~nce 15 Of t~ at~rial will bQ good and ~at th~ ~t@rial will drap~ likQ a ~a~ric amd handl~ ~ily.
E~
Ex~ple 2 1~ r~p~at0d oXG8pt 1:hat t~e ~ilm wh~ch is l~inated to both 6tdQ~ o~ 'che ply i~ an 0.35 mil 20 film a~aiiablR ~ro~ Rav~n Indu;E~ a ~lend o~ Dowl~x 2045-~, a li~oar low ~lty psly-~thyle~Q, ~nd Attane 4001, an ~thylen~-oct~no copoly~er.
It 18 ~ d that th~ b~ tlo per~on~lance of thQ ~ial ~rill b~ good and t~at the ~naterlal wlll drape~ fa~ric ~nd h~ndl~ ~a~ily.
E~
~ca~aplQ 4 i~ r~peat~d Gxcept that th¢ roll ~s aui:o~laY~d at 3~ t~ap~ratur~ o~ ~bout 121~C. (250-F. ) for an hour at a pres3ure of ~Ipprosci~tely 120 13~s~in2. .;r It i~ exp~cted ~at th~ balli~tic perfs~2lnce of #~e~ ~terial will bs good and that the ~terial will drape lika ~ nd ~andla ea~ily.

A 0 /90 contiruou~ cros5 ply i8 ~or~ed as in 3 5 ~xample 1 ~xc~pt that ~ matrix u~d i~ zl ther~ofi2ttiny r~in, De~ra)u~ne 3084 ~an aqueou~ di~per~ion o~

: . , .

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'Ogl/12136 PCT/US91/00463 _ ~9 _ vinyl~ster/~tyrene ~onomer (50/50 wt/wt) ~anu~nctured and sold by Dow Chemical, elongation about 10 to 12~], and it ~8 put on with coating roll~rs to achi~ve ~bout 20% ~y volu~e ~atrix and about 80~ ~y volume ~ ent in the 5 continuou6 ply.
T~ continuou~ cro~s ply/longth i~ wound wit~ a l~yer of Rra~t paper into a roll ~ith ~h~ ~rart paper ~epar~ting ~UCC~S8iV~ wrap~ of ~he ply. Thi~ roll i~
plac~d in an o~n ~t ~bout 105-C. (220-F.)~ hout 1o p~ssure, until ~h~ r~si~ cura~, about 20 ~lnut~sO ~he roll i5 ~hen ~llowed to cool to roo~ to~perature (abou~
. .
~5~C.) prior to testing.
It is exp~ct~d that th~ ball~$tic perfox~ance of the mat~r$~1 ~ill b~ go~d and ~hat ~Ae material will 15 ~r~pe like a fabric and haRdl~ Qa~lly.
~ .
A 0-/90- continuou. C~05~ ply iS form~d as in Exn~pl~ 1 except that th~ ~atr~x us~d i~ a bl~nd of ~
thermO8ettlng resin Der~k~n~ 8084 tlO~ by ~ight) and a 20 thermopl~tic r~in - Di~p~rcolI ~585 (~0~ by weight), an aqueou~ disp~rsisn of ~ t~ opla~tic polyur~than~, ~nu~acturad ~nd ~old ~y ~obay Corp. Th~ ~atrix ix put on ~ith ~oatlng roller~ tu achi~v~ ~bout 20% ~atrix and nbout 80% fila~2nt ~n th~ cross ply, ~h~ continuous cross.ply/len~ i6 ~ound with a lay~r of k~aft papQr into a roll ~it~ ~h~ Xra~t paper 83p~r~ting ~u~cessiv~ wrap~ o~ th~ ply. Thi~ roll is placad $n an oYen at about 105~C~ (220-F.), wi~hout pr~sur~, until the r~sin curas, hbout 20 ~inutes. The 30 roll is th~n ~llowed to cool to ro~m t~perature (about 2S'C.) prior to testing.
It: i~ 2xpect~d that the ballistic p~rformance of the ~at~ri.al will b~ good and th t the ~aterial will drapa like a fabric and handl~ ~a~ily.
a~a~oe$E_~
A 0-/90- continuous ply i~ ror~ed and wound into a roll ~,5 in Ex~mple 1. A cl~ar, he~t ~hrinkable .

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: ' ' ' '';' ' ' '` `'`" , ' ~VO 91/12136 P~rtUS91/004~ ``

-- 3~ --polyoster tape 5 . l c~ (2 inch~s~ in width arld commeroially ~vail~ls a Dunston~ ~ly~ Shrink Tape ~ro~ D~ans~or~ Corp.
of Charlott~, Nor~ ~arollna, i8 ~ound around th~ roll ln a slightly ov~rlapping ~piral to coD~pl~l:ely wrap the 5 roll. m8 wrapp~d roll i8 plac~d in an ov~n at a~out 7l-C. ~about 160F.) gor ~07ar hour~a Th~ taps ~b,rislks wit~ ~ heat to apply pr~ssurs ts ~h~ roll. The roll is t21en allo~sd to cool to rooD- t~;~pera~ (abuut 25 prior to tssting.
I~ e~d that t~ lstic por~o~ance of ~e ~aterial will ~o good and ~at ths Dlaterial wi drape li3ce a ~abric and handl~ ~a~ily.
~a~.2 ~h~ proo~ o~ ~pl~ 8 $8 re~p~at~d ~xrept l 5 that thQ ~apped roll i8 placod ~n ~n oven ~o ~t the cen~r o~ the roll reach~ a ~ rature of ~bou~ llO-C.
~a~out 230~F. ), a~ ~a~ d ~i~ ~ocoupla, for ~out on~ hour. Th~ tapo ~hrir3tcs ~ith thQ h~t to a~ply preQsure ~o ~he roll. Th~ roll i~ allo~s3d to cool to 20 roosll te~p~raturo (a~out 25-C.).
It i~ d tbat th~ tic psrformanc:e o~ t~e ~atcrial will b~ goocl and t~at the ~at2rial will drape lik~ ~ ~abric ~nd handl~ oasily. -. ~;. `.... ` ': :
.::
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. ,

Claims (15)

WE CLAIM

1. A method of consolidating a continuous ply of at least two fiber reinforced resin-impregnated sheets, comprising the steps of:
a. winding said continuous ply and a separation layer of a material into a roll with said layer separating successive wraps of said continuous ply; and b. exposing said roll to a sufficient amount of heat and pressure to cause the resin-impregnated sheets to substantially adhere to one another without the presence of an adhesive between said resin-impregnated sheets, said material being separable from said continuous ply.

2. A method of consolidating a continuous ply of at least two fiber reinforced thermosetting resin-impregnated sheets, comprising the steps of:
a. winding said continuous ply and a separation layer of a material into a roll with said layer separating successive wraps of said continuous ply; and b. exposing said roll to a sufficient amount of heat and pressure to cause the resin-impregnated sheets to substantially cure and adhere to one another without the presence of an adhesive between said resin-impregnated sheets, said material being separable from said continuous ply.

3. The method of claim 1 wherein said roll is exposed to a temperature ranging from 20°C to 150°C.

4. The method of claim 3 wherein said roll is exposed to a pressure of from 69kPa (10 psi) to 69,000 kPa (10,000 psi).

5. The method of claim 1 wherein the separation layer of material is a plastic film selected from the group consisting of polyester, polyethylene, polyvinyl chloride and ethylvinylacetate, whereby the pressure is applied when the plastic film shrinks from exposure to the heat.

6. The method of claim 1 further comprising the step of wrapping the roll with a plastic wrap selected from the group consisting of polyester, polyethylene, polyvinyl chloride and ethylvinylacetate prior to the curing step, whereby the pressure is applied then the plastic wrap shrinks from exposure to the heat.

7. The method of claim 1 wherein the separation layer of material is selected from the group consisting of a waxed paper, nylon film and polyester film, and wherein the pressure is applied by the layer of material during the winding of the roll.

8. The method of claim 1 wherein at least two of said sheets each comprises a network of filaments in which said filaments are arranged substantially parallel to one another along a common filament direction, said filament alignment directions of said two networks being rotated approximately 90°
with respect to one another.

9. The method of claim 8 wherein the filaments have a tenacity equal to or greater than about 22 g/d, a tensile modulus equal to or greater than about 900 g/d and an energy-to-break equal to or greater than 27 J/g.

10. The method of claim 9 wherein the filaments are polyethylene filaments.

11. The method of claim 9 wherein the filaments are poly(p-phenylene terephthalamide) filaments.

12. The method of claim 1 further comprising the step of placing at lest one sheet of film adjacent to at least one said of said continuous ply for winding into said roll for consolidation therewith.

13. The method of claim 2 wherein the thermosetting resin is selected from the group consisting of vinylesters, phenolics, epoxies, acrylics, urethanes, unsaturated polyesters and alkyds.

14. A consolidated roll made according to claim 1.

15. A consolidated roll made according to claim 2.