CA2125572A1 - Degradable multilayered structures - Google Patents

Abstract

The invention provides a compostable thermoplastic polymer composition comprising a thermoplastic polymer, a transition metal salt selected from cobalt, manganese, copper, cerium, vanadium and iron, and a fatty acid or ester having 10 to 22 carbon atoms providing unsaturated species and free acid. The composition will oxidatively degrade to an embrittled state within at least 14 days at 60 ·C and a relative humidity of at least eighty percent. The invention also provides degradable multilayered polyolefin structures incorporating a transition metal in the form of a salt, degradable and compostable multilayered barrier films, degradable, radiation-resistant compositions and articles, and methods of forming and using such compositions, structures and articles.

Description

W O 93/11941 ~ 1 2 5 t) 7 2 PCT/US92/10718 DLGRADABLE MULTILAYERED STRUCTURES

5 Related A~lication~
This application i~ a cont~nuation-in-part of pending United State~ Pat-nt Application Serial No 07/806,769, filed December 12, l99l, the ontire contQnts of which are expressly incorporated by reforence h-rein ~
~ ,.
Field of tb Invention Thi- invention rolat-- to a novel polymeric blend having enhanced onvironmontal degradability propertie- comprising a non-b$odegradablo thermoplastic polymer This invention al-o relateo to multilayered structur-s of non-biodegradable thermoplastic polymer- that ar- environmontally degradable, to degradable -~
radiation-r-oi~tant compooition~ and art~clo~, and to method~ of forming and u-ing uch tructure-, compoeition- and articles ~ckoround of the Invention Th-r- ar- nu~ rou- pat nto d aling with onhancing the degradability of conventional non-biodegradable polymerc such a~
polyol-fin- by u-e of additiv y-tem- These additiv~ ysteme are quite fr-quently de-ignod to ~nhance the polymers d gradability in a cpecific typo of environment and over a pecific-l-ngth of tim- For oxample, U S Patent No 3,840,512 ~Brackman) xomplifi~- prodegradant y-tem- compri-$ng ferric toArat- with variou~ free fatty acidff, both saturated and unoaturat-d Mangan -- toarat- i- al-o xe~plified in a y~tem with tearic acid Brackman tatee that thermoplastic film~
(e g , polyolefin fil~-) ormed with these prodegradant y-tem~
will ~mbrittle wh n expo--d to artificially W-activated irradiation at timo- ranging from 2 to 35 day- It ie pecifically tated that th natur~ of the hydrocarbon group on th fatty acid do~ not have a larg~ influence on the rat- of W
degradation Brackman doeo not addre~e the i-sue of dogradability ~n other environments, such a- in a compo~t nvironment A pat~nt dealing with a oimilar prodegradant y~tom, U.S Pat-nt ~o 4,067,836 ~Pott- et al ), di-close~
adding a tran-ition m tal alt, an auto-oxidativ- u-ceptible additiv , and an anti-oxidant to polyethylene The only ox-mplifiod auto-oxidativ u-c~pt$ble additiv-s were polypropyl-n and polyethyl-ne oxid (WhiCh did not work a~
acc-ptably a- polypropyl~ne). The d~gradation of the oamplo- wao to-t~d by oxpo-ure to an artificial ~olar light opectral 2 1 ~ ~ ~ 7 ~

distribution The degradability characterietice of theee prodegradant additives were never demonetrated in otber sn~ironments uch aa a compost environment Generally, additive y~tem- a- de-cribed abo~e, d-~igned to ~ake a polymer degrade when ~xpo--d to nvironmental radiation, have proved of doubtful practical utility Only a relatively emall portion of thR wa~te tream i- evor expo~ed to ~unlight, even for ahort periode o tim In U S Patont No 3,921,333 fClendinning, et al ) it iB
propo-od to mako the composition of Potts, et al , discussed above, degradable in a eoil type environment by adding a biodogradable polymer such a- poly(caprolactone) The invention describod ie allegedly ueoful for matorials such as traneplanting containers, mulch film and the like Again, only a emall portion lS of tho pla-tic in tho waBto etream is ever ueed in such environmont~ and a- ouch tho compoeitions deecribed are of limitod appl~cability ba-ed on thoir limited intended uee U S Patont No 4,038,228 (Taylor, et al ) describes placing a transition mstal ealt of an un-aturatod organic acid or eeter into a polymer film ~e g ,, poly thylono or polypropylene) to enhanco it- degradability in th absence of sunlight The transition metal ~alt- discueeed are identical to many of thoee oxemplified in the above Clondinning et al and Potts et al patonts; however, they are oxemplified at extremely high concentrations Tho oxomplified film degrades to an embrittled condition within throe day- at room temperature Such a film is of doubtful utility as it would likely degrade before uee and the oxemplified high concentration- of cobalt used would create an extrem~ly costly and toxic material ~0 A moro rocent patent, U S Patent No 4,931,488 (Chiguet), ~--describes a polymer (e g , polyethylene) composition which allegedly will degrado whon expoeed to heat, ultraviolet radiation, sunlight, or under compoeting conditions The prodegradant system broadly described consiete of a biodegradable substance uch as starch, an iron compound and a fatty acid or fatty acid oster, optionally w$th coppor etearate The x mplified film-, howevor, are limit-d to poly thylono blended with forric t-ar~te and oya oil, with a minor proportion of cuprLc tearat- in c-rta$n examplee Although it ie alleged that the-e comp~-$tion- aro te-ted undor composting conditione, the cond$t$on- ar~ not actually et forth and the reported film~ do not pp ar to dogrado for up to tw nty wooks, a e~tuation which would be unacceptable in most comm~rcial composting situations - W O 93/11941 7~ :l 2 5 5 7 ~ PCT/US92~10718 where peak temperatureo are reached for only approximately two ~
weeks. ~ ' A- can be ~een the art continue~ to ~eek to improve the degradability of conventional plastic films in various environment~ by u~e of additive prodegradant oyotemo These y-t m~ have been de~ign d to provide degradability propsrtieo in a wide vari-ty of nvironmental eondition- Sy-tems that have b~ n found to work in on --t of condition- do not neceosarily work und r a -par-te -t of eondition- which ean vary from a dry unlit expo-ur- to the wet, dark, and relatively infertile condition- of a compo-t-r S-veral pat-nt- hav- al-o dealt with the degradability of multilayered tructur-o form d from varioue polymers For example, U S Patent No 3,647,111 (Stager et al ) diwlooe~ a biodegradable eontainer formQd from a eore layer of an organic filler mat-rial, ueh a- peat, and a phenolie re~in impr-gnated with a metallic ~alt of a fatty acid This core layer io lam$nated with an outer protective coating, such a~ a water-solublQ paint, and an inner protective coating, such as a thin pla-tic lin r, a metal fla-h, or a very thin layer of wax All~gedly, th extr-~ely thin inner lay~r, which performo no ignificant tructural function, will break down under normal atmo~ph-r$c condition-U S Patent No 5,009,648 ~Aronoff et al ) di~closeo biodegradabl- film- eompri-ing starch blended with a polymerie material, uch a- ethyl-n vinyl aeetate, as well as ostomy pouches formod from ueh filmo Supposedly, theoe films and pouche~ will degrade whsn depooited in a landfill or compoot heap after tran-it through a municipal sawage eyotem and collection at a ewage treatm nt plant.
Furthormore, U.S Patent No 5,108,807 ~Tucker) disclooes degradabl- multilayer thermoplaotic article- compr~ed of a wat-r--oluble and/or biod gradabl- core layer ourrounded by two oppo-ing lay-r- of thermopla-tic polymere containing an effective amount of a prodegradant, uch that theoe layer- will degrade by photo, th rmal, or ehemieal mean- Such articleo are dlsclosed to b--u~-ful in th con-truetion of bag- formed from multilayered film-In a diff-r-nt a-p et, con-iderable reoeareh has been eonduct-d r garding th formation of radiation resi-tant polymerie eo~po-ltion- and truetur-s In thi- regard, attempt~
hav b n ~ad to o~ reom- d gradation problem- a-rociated with `~
ery-tallln polypropylone. For xa~ple, mesomorpbou~
polypropylene, a~ do~er~b~d ~n U S Patent No 4,~31,230, and ' . . .

~1æ 5~ 7 2 article~ manufactured from me~omorphous polypropylene, ~uch as deecribed in U S Patent No 4,950,549, provide resistanc4 to sterilizing irradiatlon~ In addition, polymer blend~ of me~omorphou~ polypropylene and a polymer compatible with ~uch polypropylene, a~ described in U S Patent No 5,140,073, have b en developed By eontrollinq the ~ethod of preparing mo~omorphou~ polypropylene, through the quenching of such polypropylen- aft-r hot-molt extru-ion, the material or article~
formed therefrom ub~tantially malntain their ~tructural integrlty after ~xposure to ionizing radiation at dosage~
~ufficient to degrade crystalline polypropylene Applicant~ hav~ found a eomposition which will rapidly degrade under eonditions of a typieal eommereial eomposting unit yet pro~lde an articl- ueh a- a film which is funetional undor normal u-- conditione A typieal eompo~ting unit g~nerally i~
expo~ed to poak t mperaturo~ of greater than 60C for period~ of approximately two week~ or 1--~ During that period, the organic matter in th~ compo-ter i~ g nerally exposed to an extr~mely high humidity, genorally elo-e to on hundr d p~reent The~ humidity eondition- ar- g~nerally favor bl- for biologieal attaek, howsver, they ar~ generally inhospitable to oxidative type degradation- where transition metal alt~ are typically employed In addition, Applieant- have also di-eovered various multilayer polyolefin trueturss that will degrade under a variety of eondition-, ineludinq the commsreial eomposting eondition~ de-eribed above Surpri-ingly, such d~gradation will oeeur when one or more of the polyolefin layers is laeking in a prod~gradant y-tem Al-o, uch d gradation ean surprisingly be aeeompli-hed with eompositions, articles, and structures formed from radiation re-i~tant, me-omorphou- polypropylene BRIEF SUMMARY OF THE INVENTION
The pr~-ent i~vontion provides a degradabl~ eomposition eomprising a ther~oplastie polymer, a tran-ition metal ~alt elected from ~altc of eobalt, mangan~se, copper, eerium, vanadium and iron, and a fatty aeid or ester having ten to twonty-two earbon atom- eompri-ed pr-dominantly of un-aturated ~p~eioe and eompri-ed at l-a-t partially of free acid The compo-ition lc d--igned o that it will oxidatively degrade to form an embrittled polymer within at least fourteen days at 60C
and at a relative humidity of at lea-t eighty pereent After thic p ak period, th tempsratur- of a typieal eompo-t unit clowly d elLn--, d ereaslng th rat~ of oxidative d~gradation, often quite dramatieally ~ WO 93/11941 2 1 2 5 ~ 7 ~ PCT/US92/107t8 The pr---nt inv-ntion al-o provides degradable multilayered polyolefin tructuro~ wh-re$n the fir-t lay-r contain~ a prod gradant y-t-m compri-ed of tran-ition metal ~alt~, and the -cond layer that do-- not cont~in th prodegradant y-t~m In addition, th pr--ent inv-ntion provides degradable and compo-tabl- multilayered barri-r fLlm-, a degradable, rad$ation r--i-tant co~po-itlon, art~cl-- formed from uch compo-itions, film- and tructure-, a~ w ll a- m thode for containing a p~ri-habl- matRrial with a degradablc packaging film, method- of forming a degradabl-, rad$ation-r -i-tant article, and m thode of u~ing a d gradabl- multilay r d barrier film All of the multilay r d mat-rial- of th pr---nt inv-ntion will oxidativ~ly d grado to ~mbrittl _ nt at a t~mpnr-tur~ of about 49C over a p riod of at l-a-t about fourt- n day- In addition, mo-t of th -- _ mat-rial- will al-o oxidati~-ly d grade to form an mbrittl d multil-y red tructure within at lea-t about fourteen day- at 60~C and at a r-lati~e humidity of at le~t eighty percent DEFSNISSONS
For th~ purpo-~- of thi- inv~ntion th~ definition of ~polym r~ includ - a homopolymer, a copolymer, or an oligomer, as w ll a- any mixtur-- or bl-nd- of one or more homopolymQrs, and/or on or mor- copolymer-, and/or on- or mor- oligom~r-Th t-rm ~copolym r~ r f~r- to a polymcric mat~rial produced by the polym rization of two or more di-similar monomcr-, ither with or without another functional group, uch a- maleic anhydride, graft d ther to, a~ well as to a homopolymer with a functional group graft~d th r~to Thus, the term ~copolymer"
includ -, without l~itation, random copolym~rs, block -~-copolym r-, -qu-ntial copolym~r-, and graft copolym~r-~Propylene-ba-~d mat-rial~ r-fer- to propylene monomer, or polypropyl-n~ polymcr --Th- t-rm ~moiety~ r f-r~ to any ubstance which can be combin~d with a propyl-n -ba--d mat-rial to form a copolymer, and ~nclud -, without l~ltation, a monomer, a polym r, or a ~ol-cul-~M -oph--- propyl-n -ba- d material~, ref-r~ to a propylene-ba--d mat-rial, in th ord r d, mo-opha~ form, which i- neither amorphou-, nor ~o ord r d ac to con~titute tbe i-otactic I
cry-tallin form ~- g , cry-tallin polypropyl~ne) a~ de-cribed by G Natta t al , ~8t N ctur and Propcrti-- of Icotactic Polypropyl-n ~, D l Nuovo C~nto, Suppl Al, Vol XV, Serie X, No l, 1960, pp 40-51, the di~clo-ure of which iB herein .

W O 93/11941 PCT/US92/107t~
~12rj~7 '~ ' ' `

incorporated by reference A meeophaee propylene-ba~ed material i~ formed by quenching a propylene-baeed material from the melt stat-, a- defin d below, and includee, without limitation, m -omorphou- polypropyl-n-, me-opolymer blende, and/or S mceocopoly~re~ ae thoee terms are d-fined below ~Quenching~, r-f-re the procees of immediately and rapidly cooling propyl-n -baoed mat-rial from the melt tate such that meeophae- propylen -baoed material ie obtained A~ u--d hor-in, ~a non-chlorine containing organic polymer which i- ~ubctantially impermeable to oxygen gae n refere to polymeric materialo which are seentially free from chlorine, and which hav- oxyg-n tranomie-ion ratee of leee than about 150 cc/m2/day-atmooph-r- at 25C and 0* relative humidity ~Olefin polymer~ or ~polyolefine~, r-fer~ to polymere of the unoaturated hydrocarbono of th general formula CnN2n, including copolym~ro of olefins with oth r monomere euch as ~thyl~ne with vinyl acetate ~Me~omorphou~ polypropylene~ (~PP) refer~ to the polypropylen~ homopolymer in the meeophase form The term ~mssopolymer blend~ refere to a mLxture of meoomorphouo polypropylene with at lea~t one additional polymer (h-reinaft-r A ~eecond polymer~) The term ~mesocopolymer~ r-fer~ to a copolymer of a proi~yl-n--ba--d material and a di-cernable amount of at leaet one moiety that i- qu-nched from the melt ~tate to form a copolymer in the meeophaoe form ~Tran-$tion m tal alt~ m-ans any compound er compoeition containing a traneition metal ion and at leaet one other element Ao u~-d h rein, a tranoition metal includes slements 21 through 30, 39 through 48, 57 through 80 and 89 through 103 of the Periodic Tabl-, all of which have a partially filled outer shell of electron-The term! ~degradable~, ~oxidativ-ly degradable", or ~oxidative d gradation~ r-f-r to the breakdown of thermoplaetic polymsro, uch a- polyolefin polymsr-, to l-eeQr molecular weight componentr through oxidative chain eci-sion facilitated by a prod-gradant oy-tem, ae that t-rm i- defined below~ The oxidativ- degradation of a thermopla~tic polymer al-o l-ade to chanqeo in tho phyeical prop rtie- of the polymer, euch a- loee of tenoile otrength and ~mbrittle~ent, ao that term iB defined b410w Cen-rally, a multilay red etructure according to the pre-~nt inv-ntion i- con-id rod to be dogradable if it bscomee -~
embrittled in tho pro--nce of tho prodegrAdant sy-tQ~, when ~ W 0 93/11941 2 1 2 S 5 7 2 P ~ /US92/10718 maintain-d at a t-mperatur- of about 49c ov-r a period of approxi~ t-ly fourt- n day- or l---~ Co~po-t bl-~ r-f-r- to the oxidativ- degradation of th r~opla-tlc poly~or- in th w~rm and moi-t nvironment of a ~unicipal or co~m rcial compo-ting facility In g-n-ral to be con-$d r d compo-tabl-, a polymeric compoeition or multilayered tructur ccording to th pr---nt invention hould degrade to mbrlttl-~ nt a- d fin d b low, within at l-a-t about fourte~n d y- at 60C and ~t a r-lativ hu d dity of at l-a-t about 80 p rc-nt ~or th purpo-e- of te-t$ng th compo-itions and tructur - of th pr---nt inv ntion comm-rcial compoeting condltion- w r ~Dulat d by placing ingl- nd multilayer-d fil~ into ~-r of wat-r which wa- then buff-r d to a pH of 6 by a pho-phat- buff-r and h ~t d to variou- t~p-ratur-s A ~prod gradant y-t-m~ m-an- ny co~po-ition of ~t l-a-t one tran-ition ~etal alt that facilitat-- the oxidative d~gradation of a thermopla-tic polymer, uch a- a polyolefin polym~r The prodogradant y-tem may al-o optionally includ an auto-oxidative co~pon nt, ~- that t-r~ i- defined b low When u-ed to form a co~po-t-bl- th D pla-tic poly~er or t N ctur , th prod gradant y-t-m will lnclud uch n ~uto-oxidativ co~ponent An ~auto-oxidativ compon~nt~ ~ean~ any ub-tance, compound or compo-ition, whlch in co~bin-tion with th tran-ition metal -lt of th prod gr~dant y-t-m nhance- the oxida~ive d gradation of th n~opla~tlc poly~er, uch that th polym~r i8 brok n down at a fa t-r rat- than if lt wa- contact~d with the tr-n-ition ~ tal alt alon ~h n u--d to form a compostable poly~er and/or t N cture th! auto-oxldativ~ component includes a fatty ~cld or -ter having t~n to twenty-two carbon atoms co~pri-~d pr dominantly of un-aturat-~ op ci~- and co~pri--d at l-a-t p rti-lly of fr cid A u d h r-in, ~-~brlttlem nt~ m-an- th point at which ampl-- of th rmopl--tic polym r- maint~in d in heatod oven or a ~ulat d coqpo-ting nvironm-nt lth r crumbl- upon folding or cr aeing, or hav littl- or no t-ar tr-ngth r-maining The ~t~e to ~brlttl _ nt~ i- th tot-l lap ~d tim- from th~
pl-c _ nt of th rampl-- of d gr-dabl- polymer- in th ov-n or imul-t-d co~po-ting environ~ nt to th point of mbrittl~ment of th ampl--A ~naturally biod gr~dablc polymer~ r~f-r~ to any polym~r th t i- u-c ptibl- to br -kdown to le--er molecular weight compon nt- through th etion of living organi m-, uch a-b-ct-ria, fungi, nd lqao W O 93/11941 ~ PCT/US9~/10718 ) 12 5 7 ~

~RI1Z:F DESCRIPTIO. N OF l~E~E DRAWINGS
The invention may be further illuetrated by reference to the accompany~ng Drawlnge wherein FIG. 1 1- th- wide-angl- x-ray diffraction pattern of the film of Ex~mpl- 152, howing meeomorphous polypropylene containing the prodegradant yetem of the preeent invention;
FIC 2 iB tb- wide-angl- x-ray diffraction pattern of the film of Compar-tiv Ex mple 154, ehowing cry-talline polypropylen~ containing th prod gradant ~ystem of th- preeent invention;
FIG 3 iB th wid -angl- x-ray diffraction pattern of the multilayered barrier film of Exampl- 153t and FIG 4 i~ th wide-angl- x-ray diffraction pattern of the multilay-red barri-r film of Comparative Example 155 - DETASLED D~SC~ ON OF
~BODIMENTS OF THE INVEN~ION
I ComDostable ComDosition and film-In a firet ~bodiment, th inv ntion i- gon rally directed to a compo-tabl- thermopla-tic polym r composition compri-ing a thormopla-t~c polymor containing a prodegradant syetem of an auto-oxidant of an un-aturat-d fatty acid or e-ter having ten to twenty-two carbon atomc, and certain transition metal salts The fatty cid or e-t-r i- pr--ent in the polymer composition at a concentration of about 0 1 to 10 weight percent so as to provide a conc-ntration of un-aturated species of greater than 0 1 weight perc-nt and a conc-ntration of free acld specie~
greater than 0 1 perc-nt by w ight based on the total compoeition Further includ d i- a traneition metal alt at a relatively low conc~ntration of 5 to 500 ppm of the metal itself wher- th tran-ition metal i- ~ ct d from the group co~prising cobalt, mangan e-, copp r, cerium, vanadium and iron, pr ferably cobalt, mangane-e, copper or cerium The compoeition is formulated ~uch that it will oxidatively degrade, pr~ferably to an mbrittled tat-, w~thin fourteen daye at a te~perature of about 60C and r lativ hu~idity of 80 porc-nt or more, pref-rably 100 perc-nt aft-r r a-onable shelf life Gen rally, it ie xp ct d that th- compo-ition will have to be helf-stable for a time ranging from on- w ek to 12 monthe AB th-d grad-tion occur- lowly, ven at room temperature, for longer h-lf-lif- product-, g n rally low r conc-ntrat$one of the tran-ition m tal or fatty acid (fr- acid and/or un-aturated epecie-) wLll be reguir d to provide a compo-table film at the WO 93/1t941 2 1 2 i ~ 7 ~ PCT~US92/10718 f ~ int-nded me~n shelf life Conv~roely, higher concentration- of the metal or fatty acid p~cie0 will be required for films with short-intended sholf live-Thermopla-tic polymer0 uitable for uoe with the pre~ent prodegradant y-tom include polyolefins such as polyethylene, polypropylene, polybutylene or poly~4-methyl-l-pontene) Other uitabl- poly~er~ include poly~vinyl acetates), polyester~, polyur-than ~, poly~vinyl alcohol-), polyamidee, poly~tyrenes or polyamin - Copolymer~ and blend- are also uitable Pr f-rably, th polymer employ d iB a aturat-d thermoplastic polym r uch a- poly thyl-n or polypropylene ~uitable for ~xtru~ion or coextru-ion ~ost pr-f-rr d aro polypropylenee or polypropylene blend-, uch a- blends of polypro wlone and poly thyl-n -ba--d polymer- and copolymers The tran-ition m-tal ~alt- ~nclude those di-cu-eed, for exampl-, in U S Pat~nt No 4,067,836, which alts can be onos having organic or incrganic ligand- Suitable inorganic ligand~
includ- chloride~, nitrates, sulfate-, and tho liko Preferred ar- organic ligand- such a- oct no-te-, acetate-, tearates, ol-at--, n-phth nat--, linol-at--, tallate- and th lik~
Although a wid range of tran-ition metal~ have been di-closed in the art a- ~uitabl- for variou- prod gradant systems, for a compo-tablo poly~eric film it ha- b~en found that the trans$tion metal mu-t be -lect-d from the group comprising cobalt, mangan ~e, copp r, c-riwm, vanadium and iron in a concentration rang- of from 5 to 500 ppm and pr-f-rably cobalt, manganese, copp r and o-rium for mo-t polymer- Pr-ferably, the transition m tal $~ u-~d in a concentration of from 5 to 200 ppm which i~
highly desirable a8 uch m-tals are generally undesirable in larq- cone-ntration- High tran-ition metal concentration~ in compo-t material can lead to toxicological and environmental conc-rn- duc to groundwat-r l-aching of these metals into the urrounding environment Further, higher transition metal concentration- can y$eld un-table films with th invention 3S prodegrad-nt y-tem Oxidativ degradat$on in a typical compo-t-r occur- under ub-tan~ially aturat-d tmo-ph ric humidity condition- The pla-tic on it- ext-rnal fac- will normally -~ a humid~ty of approx~at-ly l00 p rc-nt Th -- ar- xtremely ev-r- conditions for oxidat$ve d qradation and it has been found that the prod gradant y-t _ de-cribed in th art are not u$table for ad guat- d gradation of pla-tico under these condit$ons It $- found th-t ad quat- degradat$on under typical compo-ting eond$t$on~ requir-- alts of the above mentioned WO g3/11941 PCr/USg2/10718 :.
212~'J7~ ' tran-ition m-tal- in combination with acid moi-tiee euch ae tho~e found in un-aturat-d fatty acid- It ha- al-o be-n found that un-aturation in th fatty acid, or an admixed fatty acid -t-r or natural oil, i- r quir-d to produc- ad quat- d~gr-dat~on with th~
S prop~r tran-ition ~t-l compound Pr f-rably, thi~ un-aturated fatty acid i- pr --nt in the polymer -o~po~ition at conc-ntration- of at l-a-t 0 1 w ight percent of the composition, pr f-rably at l-a-t 0 25 w ight p rc-nt, and mo-t pref-rably at l-a-t 0 5 w ight p rc-nt Al-o uitabl- are bl-nds of fatty acid- and fatty acid -t-r- or oil- a- long a- the amount of free acid and un-aturat d peci-- are gen-rally equivalent to the abov d--cr~b d rang - for a pur- fa^ty acid containing compo-ition G~n rally, it ha been found that un-aturat~d fatty acid~
h ving 10 to 22 carbon tom- function well in providing the d gradation rat- r gulr d for a compo-tabl- material Un-aturation uch a- found in bnormal oil- i- found to be pr-f~rred Such un-aturation include- two or more double bond~
~n th fatty acid or -t-r chain- Gen rally, un-aturation where two of th doubl- bond- ar -parat-d by two ingle bond-, r--ulting ~n a doubly all-lic earbon atom, ha- be~n found to be highly d -irabl-, although con~ugat d double bond~ ar also pr-f-rr d Sampl-- of ~at-rial- whlch contain doubly allelic c rbon atom includ- lin ~ d oil, linoleic acid and linol-nic acid An xampl- of a co~mon con~ugated fatty acid i-l o~t-aric acid found in high conc-ntration, in tho st-r form, in natural tung oil 0th r n~tural oil- containing fairly high amount- of un-atur~tion includ~ fi-h oil- ~uch as ardine, cod liver, m nhad n, and h rring oil Fatty acid- deriv~d from the~e naturally occurring oil- cont~ining high percentag - of un-aturation aro al-o uit bl- a- auto-oxidative acc-l-rating compon nt-Al-o uitabl- ar- fatty acid derivative~, ~ub-titut d fatty acidc or d riv-tiv ~ or corr--ponding r duction product~ uch as amine- or alcohol~ and the lik , although ub-titution- should not be d~ac-nt to all-lic or con~ugated doubl- bonds or other ourc-! of un~aturation a- they t-nd to r duc- th ff-ctivene--of uch fatty acid- nd d rivativ - G n rally, oth r acid- have b n found to b un-uitabl-, including dicarboxylic fatty acid-How-ver, additiv amount- of ro-in acid- uch a- Forall~ AX have b n found to b u~-ful in co~Q inctanc--Pr-f-rably, th co~po-ition furth~r include- an anti-oxidant Anti-oxld-nt- h-lp tabili~- tho polymer during extru~ion op ration- during th- formation of a film or other article a~

- WOg3/llg41 2 1 2 5 ~ 7 2 PCT/US92/10718 w ll a- help provid a uitabl- helf lifo for tb~ degradable articles Any uitable anti-oxidante ueed with th- conv~ntional baee polym r ar- acc-ptabl- including uch typical anti-oxidante uch a~ t~rically hind-r d ph~nol-, aryl amin -, thiourea-, S thiocarbamat--, thio th r--t~rs, phoephit~s, or the like Illu-trative anti-oxidant- can be found, for example, in U S
Pat-nt No 4,067,836 Pr f-rably th anti-oxidant i- present in a concentration of approximat-ly 0 l welght percent or more ba-ed on th total polym r coapo-ition Th coapo-tabl- poly er coapo-ition aleo pref-rably includoe a naturally biod gradabl- poly~er ucb a- poly(caprolactone), poly~lactic acid), poly(hydroxybutyrat--valerat-t, poly(ethylene adlpate)~ poly~vlnyl alcohol)~ modifiod tarch/ol ofin copolymer-, poly(propyl-n oxid )~ nd poly~-thyl-n oxide) Other uitabl- biod grad bl- polya r- are g~nerally w ll known and ar~ d -cribod in, for xampl-, U S Pat-nt No 3,921,333 The-- biodegradabl- polym r- a--iet in further biodegradation of th- compo-ition following the tran-ition aotal alt catalyzed oxidativ- d gradation, which r-duc-- th ba-- th rmopla-tic re-in to a low-r ol-cul r w ight ub-tanc- Although theee biod gradablo polym r- lon can b- broken down fairly rapidly in any coapo-t type nvironm-nt, tbeir phy-ical propertie- are g nerally $nf-rior to tho-- of conventional thormopla-tic film-Further, their co-t- are often quite prohibitive for uee in typical comm~rcial application- However, bl-nded with conv ntional th rmopl--tic aat-rial-, uch a- polyol-fin-, theee biod gradabl~ polym r- hould a--i-t in the biological breakdown of the article- following the catalytic embrittl _ nt period G n-rally, the natur-lly biod gradabl- polymor can bo includ~d in aaount- froa 5 to 50 w ight porcent of the compoc$tion, pr f-rably th -- b$od gradabl- polymor- aré u-ed at fro~ 5 to 25 w-ight p rc~nt 0th r conv ntional additiv - c-n be add~d to th polymor compo-ition including fill-re, dy--, pigment-, anti-blocking ag nt- or th~ e The inv nt$on coapo-ition find- particularly advantageou- u-e for produc~ng fila- or flb r- due to th~ coapo-ition'- bility to b- extrud d without ign~ficantly affecting p rformanc- With uch xt N ded flla- or f~b~r-, th fatty acid peci-- pr-forably ar- pr-dominantly C12 to C22 -pecie- These fatty acid peciee ar g-n rally aor tol-rant of typical xtru-ion condition-How-v-r, th co po-ltion can b- u- d in other xtruded articlee or non- xtrud d artLcl~-2125;37 2 Typioal u-e- for the compo-ition as extruded film- or fiber~
includ- di-po~able item- wh~ch would in u~e be at ambient condition- or b low, or xpo- d to levated temperatur-- for a r-lativ ly hort p riod of tlm Thi- would include traoh bags, di-po-abl- diap r component- (e g , diaper back-heet~, polymer film compon nt-, xtrudod nonwov n fiber web-, and the like), fr oz-r bag-, di-po-abl- medical bag- or components, d~spooable garm nt-, hygi-n- articl~ nt-rnal packaging film-, tc II ~earadabl- com~o-$slLons and Articl-s MultilaYered ~Structur-- M thod~Lof Formation and U~e In a -cond mbodi~nt, the inv ntion i- dir-cted to degradabl- co~po-ition-, article-, and structure~, including compo-t bl- ~at-rial-, compri-ing polyolefin polyo~r- containing B prod gr-d nt y-t-m of tran-ition m-tal alts The tran-ition m tal alt of th~ prod gr-dant y~tem can b- any of tho-- defined h r in Pr ferably, th tran-ition m tal alt compri--~ the ~ame Alt- di-clo- d in S-ction I abov , uch ao the organic ligand alt- of cobalt, m ngan --, copp r, c-rium, vanadium, and ~ron To f-cllitat- th d -ir d d-gradation, ths-e tran-ition m-tal-ar mploy d in on or mor- polyol-f~n lay-r- at conc-ntrations of from about S part- per ~illion ~ppm) to about 2000 ppm, more pr ferably at conc-ntr-t$on~ ranging from about 25 ppm to about 500 pp~ Wh n the tran-ition etals are utilized at - conc-ntration- of greater than 500 pp~, an anti-oxidant may be r quir d to maintain an acc-pt bl- h lf-lif- for th r~-ulting product How v r, a- not d abov , th concentration- of theee m-tal alt- hould pr-f-rably b~ minimiz-d to avoid toxicological and nvironm-ntal concern-, and to help ensuro acceptable helf tability for th d gradabl~ compo-ition-, structure- and articl-- of th pre--nt invention Th prod gradant y-t-m may optionally include an auto-oxidativ- co~pon nt, a- d -cr~b d in S ction I above AB in the compo-tabl- co~po-ition- and fil~- of Section I of this application, th uto-oxidativ compon nt compri-e- acid moi-ties uch - tho-- found in un-aturat-d fatty acid- or -ters Pr f-rably uch fatty acid- or -t-r- will hav from lO to 22 carbon atoo-~h n for~ing compo-t bl- multilay red ~t Ncture, including multilay r d barri-r and packaging film- according to the pr-sent inv ntion, the prod gr-dant y-t-m will compri-- the combination of tr n-ltion ~ tal -lt- and auto-oxidative compon~nts, lncluding th pr f-rr~d amount~ nd component- di-clo-ed in S~ction I of thi- application Thu-, un-aturated fatty acid~

W O 93/11941 2 1 ~ 5 5 7 2 PCT/US92/10718 having from lO to 22 carbon atoms, ~uch a- ol~ic acid, linoleic acid, and l$nol-nic acid, a- well a- natural oil- and fatty acid d-rivatives, uch ae lin-eed oil, tun~ oil, sardine oil, cod livor oil, and h rring oil, compri-e d eirablo auto-oxidative compon-nt- of th- prodegradant yst-m of th~ pr--ent inv~ntion A- not d bov-, th -- un-aturated fatty acide or d~rivativ~s ar~
pr-f-rably pr---nt in one or more polyol-fin lay-r- at conc-ntration- of at l-a-t O l w ight percent to about lO w~ight p rc-nt of th eo~po-ition of that layer, prof~rably from about 0 25 w ight p re-nt to about 3 weight percent, and most pr f-rably from about 0 5 weight pereent to about 2 weight percent The polyol-fin polymer- employ d in the compo~itions, tN etur - and art~el-- of th- pr---nt invention ean ineludo any polyol-fin- whieh wh n eo~bin d with the prod qradant y-tem of th pr --nt inv ntion will oxid~ti~ly d grad~, and/or compo-t in a uitabl~ en~ironm-nt, a- tho-- t-rms aro d~fino~ herein Nonlimiting examplo- of uitable polyolefin polym~rs include polypropyl-n , polybutyl-n , polyothylon-, low den~ity poly thyl-n (LDPE), lin ar low d!n-ity polyothylen (LLDPE), high d n-ity poly thylen (HDPE), ethyleno vinyl aeetate eopolymer ~VA), and thyl-n acrylic aeid copolymer (EAA) Pr-f-rred polyol-f~n polymor- for u-e in th~ dogradable eo~po-ition-, tructur - and rticlo- of the pro-ont inv~ntion includ polypropyl-n , poly thyl-n , and polybutylene, with polypropyl-n and poly-thyl-n b~ing particularly pref-rr-d In a pr f-rr d a-p et, th polyolefin polymer of the d gradabl- compo-ition-, tructur-s, and article~ of the present inv ntion eompri~-- opha-- propyl-n~-based material, uch a~
m comorphou- polypropylon , ~e-opolym~r blends, and/or m oeopoly~er- Se-, eop nding and eo-fil-d U S Patent Applieation-, Attorn y Doek t No- 47990USAlB (Rolando t al )~
47791USA8~ l~ilfong t al )~ 47008USA3A (wilfong et l ), 47008USAl8 ~Wilfong t l ), and U S Patent No 5,140,073, the di-elo-ur-- of whieh ar- h r-in ineorporated by r-fer-ne- Ev~n aft-r b ing xpo- d to a do-- of r-diation of from about 1 kGy ~0 lO-~rad) to about 200 kCy (20 0 Mrad), th -- me~opha~Q
propyl-n~-b-- d ~at-rial- d gr-do at ub~tanti~lly lower rato~
than eo par~bl- ery-t-llin propylene-ba-ed mat-rial-Un~xp et~dly, d gradabl- eompo-ition~, ~tructuros, and article~
form d from m -oph -- propyl n -ba- d mat~rial- oxidativ-ly d grad at eoqparabl~ rat-- to cry-tallin propylon~-ba-~d ~t-rial- wh n eombin d with th prodegradant ~y~t~m of the pr --nt invention .

W O 93/11941 ~ PCT/US92/10?18 ~12557 2 For oxample, the polyolefin polymer u~ed in the degradable material- of the preeent invention may comprie~ meeomorphous polypropylene homopolymer, or polymer bl~nde of mesomorphou~
polypropylen~ and a econd polymer, that exhibit $ncrea~ed r--istanc- to the degrading ~ff-ct- of ionizing radiation, including gamma and electron-beam radiation, a~ described in U S
Pat-nt No 5,140,073 Nonlimiting examples of uitable second polymers $nclude polybutylene, atactic polypropylene, polypropylene--thylene copolymer-, ~VA, EAA, poly(4-methyl penten ), and polyethylene, including polyethyl-ne copolymers, LDPF, LLDPE, and HDPE Furthermor-, these mesopolymer blende may exhibit other desirable propertie- attributable to the second polymer-, euch as $ncrea-~d toughne-s, heat eal~bility, oftn---, and qui-tne--, d psnding upon the particular second polym r comb$ned in th m~-opolym r blend Ae noted above, the polyol-fin component of the degradable compositions, st N cturQs, and art$cles can al~o compri-e a meeocopolymer In th$- regard, any moiety, or combination of mo$et$~, can be u-od $n con~unction with a propylene-ba-ed mater$al to form th me-ocopolymsr- u-ed in the mater$ale of th~
pr--ent invention For xampl-, tho propylene-based material can compr$se propyl-ne monomer and the moiety of a different monomer other than propylene, such a- ethylon- or butylene, that when polymer$zed, melt extruded, and guenched, form a mesocopolymer The mesocopolymers u-abl~ in the degradable materials of the pre-ent in~-ention genorally fall within thre~ classe~ The first clae- of copolymer comprises a me-ocopolymer wherein the other moiety comprie~- a monomer, such as ~thylene or butylene, that i~
in-erted between propylene monomer- in a copolymer chain (e g , Petrothanel~ resin No PP7300-XF ~Quantum Chemical, Inc.)) The ~econd clase of m~-ocopolymer- compr$se mesocopolymero of the above de-cribed clae- one copolymer-, with another moiety grafted to the copolymer chain (e g ~ Plexarl1~ resin No 420 (Quantum Chem$cal, Inc )) The th$rd, and final, general cla~s of me-ocopolymer- compri-- a mesomorphou- polypropylene homopolymer with a mo$ety, uch a- maleic anhydrido or acrylic acid, graft~d to the polymer cha$n (e g ~ Admerl~ resin No QFSSlA (Mitsui Pla~t$c-, Inc )) The combination of a m~sopha-e propylene-based material with th- prod~gradant y-tem prov$de~ a un$que composition according to tho pre-ent inv~ntion A- d -cribed abov~, m~-ophase propyl-n -ba-ed mater$al-, uch a- m ~omorphou~ polypropylenQ, me-opolymer blend-, or mssocopoly~ers, formed by quenching - W O 93/11941 212 ~ 5 7 2 PCT/US92/1071X

propyl-ne-baeQd materials from the melt etate, are ~ignificantly more r--i-t~nt to degradation by ionizing radiation than a comparabl- mat-rial or structuro ~ormed from a cry~talline propylene-baeed material See also U s Patent No~ 4,931,230, 4,950,549, and 5,140,073 and U S Pat~nt Applications, Attorney Docket No- 47990USAlB and 47991USA8B Surprisingly, these degradation resi-tant, mesophase propylene-based material~
oxidatively degrad- and/or eompost when combined with the prod-gradant system of the present invention Even more urpri-ingly, th 8- d-gradation r-si-tant materials degrade and/or compo-t at es-ont~ally th- ame rat-- a~ comparable cry-tallin~ propylene-ba--d mat-rial- Furthermore, such dogradation and/or eompoeting funetions equally well for m -opha-~ propylen--based mat-rials lacking the prodegradant sy-t-m that are layered or in contaet with another polyolefin layer cont~ining the prodegradant 4ystem of the preeent invention The degradable, radiation resistant composition of a m -opha-e propylen -bas d mat-rial wlth the prodegradant system can b formed via melt extru-ion, followed by quenching, into a nu0b r of ue-ful artiel -, uch a- films, fibers, tube~, and microflber- The-e article- can in turn be manufactured into, or b- u- d a- a eomponent part of, additional u-eful structures, uch a- taps-, multilayer-d barrier and packaging film~, a transdermal drug delivery patch, or an ostomy pouch The degradable compositions, st Nctures, and articles of the pre--nt invention may also optionally contain additional conv-ntional additiv-s, including fillers, dyes, pigmente, anti-blocking agents, plasticizers, and the like, as described in Section I of thi- application Of tb -e additives, it i~ often pr-f-rabl- that th s- degradabl~ materials include an anti-oxidant to help stabilize the t N ctures or articles, particularly wlth re-pect to helf lif- Preferred anti-oxidants inelude tho-- described above in Seetion I of this application Furth~rmore, the degradabl- materials of the present lnv-ntlon may l-o include naturally biod gradable polymers, uch a- poly(caprolactone) and poly(laetie aeid), as deseribed in S-ction I abov- ~h--- naturally biodegradable polymers can ither b- bl-ndod with th- d gradabl- eompositions into one or more of the layer~ of th tN ctur-- of the pre-ent invention, or ean be lnelud d as one or more -parate and di-tinet layers in a multllay r~d eon-tNetion Wh~n u- d a- the ga- barrier layer of d gradabl- and eompo-tabl~ barri-r fil~e aecording to the pres~nt invention, the naturally biodegradable polymers will typically W O 93/lt941 PCT/US92/10718 21 ~5~7 ~ 16 -comprie~ ethylene vinyl alcohol copolymer (EVOH) and/or polyvinyl alcohol ~PVOH) In th~ir most ba~ic form, th~ degradabl~ multilay~red ~tructur~ of tho pr--~nt invsntion comprise a firot polyol~fin layer conta$ning the prodegradant system contactinq a sQcond polyolefin laysr w$thout ths prodegradant ~yetem How~v~r, it ie within the scope of the preeent invsntion to provid~ a degradable and/or compostable tructure of virtually any combination or one or more polyolefin layer- w$th th- prodegradant eyetem with one or more lay~rs w$thout ths prod~qradant eystem~ Thu~, a tructur- of a polyol~f$n layer containing the prodegradant y~tem eandwich-d bstw -n two polyolsfin layere lacking the prod-gradant y-tsm, a- w ll a- other structures, is within the pr--ent $nv ntion A- long a- uch tructur ~ degrade and~or compo-t within the condit$ons de-cribed hsrein, thsy are cone$dsred to fall wlthin the pr-sent $nvention The polyolef$ns ut$11zed $n th~ee multilayered etructure~ can compriss the ame polyolsfin in all layer-, or different polyolef$n-, includ$ng bl-nd- and copolymers, in variou~ layers In addition, om~ or all of th~ layers can b~ comprieed of mesopha~- propylsns-based matsr$al- ~uch as mesomorphou~
polypropylQns, ms-opolymer blends, and/or mesocopolymers Furthsrmors, naturally b$odsgradabl- polymers can be blended into one or more layer-, and/or appsar a- sparat~ and distinct layers of the-e dsgradable multllay red tructur~s The thlckness of ths var$ou- lay~rs of the~e multilayered t Ncture- can be widely var$sd, and still provide a d~gradable and/or compo-table structure according to the present $nvent$on In this rsgard, the rat$o of the thickn~o~ of a layer containing ths prod~gradant y~tem to the thickness of a layer w$thout the prodegradant y-tsm can be from about 1:10 to about 1000:1, more prefsrably from about 1:2 to about 100 1, and most preferably from about 1:1 to about 10:1 In a pref-rrsd smbod~m~nt, the degradable multilayered structure accord$ng to ths prsssnt invent$on compr$s~s a dsgradable mult$1ay~r-d barri~r fllm of a ga~ barr$-r laysr of a chlor$ne-fr~, naturally biodegradabl- polym r and one or more moi-tur- barrier lay r- of me-opha-e propylen--ba-0d material-containing th prodegradant y-tem of the pr~-snt $nvent$on In this reqard, any mssophass propylene-based matsrial, such a~
me-omorphou- polypropylene, me-opolymer blsnds, me-ocopolymers, or combinationc th~r of, can srve a- moi-ture barr$er layers that protect the gas barr$er layer from mo$-ture that would reduce or eliminate it- ga- and odor impeding propertie~

- W O 93/11~41 ~ PCT/US92/10718 For oxample, the dsgradable barrier film may be comprieed of a layer of a chlorine-free, naturally biodsqradable copolymer, such as EVOH, contacted on oppo~ing ~ides by moi~ture barrier layers of mesomorphous polypropylen~ containing the prodegradant system of th~ present invention In addition, such a ~tructure may also contain optional adhe~ive layers, such as an Admer adhesive resin in a me~ophaee form, interposed b~tween the gas barrier layer and moi~ture barrier layers to pro~ide additional structural int grity to th overall barrier film Howev~r, it will be appreciated that any degradable multilayer~d barrier structure with two or more layers, wh~ch includ~ at lea-t ons ga~ barri-r layer, and at l-ast one moisture barrier layer, iB
consider-d to be within the present invention The gas barrier layer of the degradable multilayered barrier film iB compri-ed of a chlorine-free, naturally biodegradable polymsr which ic ub~tantially impermeable to oxygen gas Preferably, the chlorine-free naturally biodegradabla polymer exhibits a pe ability to oxygen (2) gas of le~s than l00 cc/m2/day-atmo-ph re (hereinafter expressed a~ ~cc/m2/d-atm~), more preferably le-- than 30 cc/m2/d-atm, and most preferably 1-B~ than 5 cc/~/d-atm, where the psrmeability mea~uremsnts are taken at 25~C and zero percent (o~) relative humidity It will also be appreciated that the 2 permeability meaourements are xpre~sed for a multilayer-d barrier film with a gas barrier layer thickness of 25 ~ (microns) Accordingly, appropriate ad~ustment of the permeability ~alues must bs made, depending upon the thickne~ of the ga~ barrier employed in a ~tructure, as well as the number of ga~ barrier layer~ utilized therein In either ca~e, the value~ ~hould be normalized to a total gas barrier layer thickne-- of 25 ~ All values were normalized to standard ga- barrier layer thickne~s of 25~ by multiplying the oxygen transmi--ion rate value by the ratio of barrier layer thickne~s to 25 ~ In addition to ub-tantial impermeability to 2 gas~ it will further be appr-ciated that the gas barrier layer al-o exhibit~ barrier propertie~ to CC2, N2 and H2S gaoe~, ao w~ll a- to other ga--- and odor-Nonlimiting exampleo of ~uitable chlorine-free, naturally biodegradable polymer- in ccordance with the preoent invention include vinyl lcohol containing polymero, such ao et ffl lene vinyl alcohol copolymer ~VO~) and polyvinyl alcohol ~PVOH) Pr-ferably, th- chlorine-fre- polymer compri-e~ EVOH In this regard, the gao barrier layer ohould preferably be compri~ed of 2~2~57~

ubstantially pure EVOH, mo~t prefsrably compri-ing 99~ or more EVOH However, it al~o within the ecope of the preeent invention to utiliz- blende of EVOH w$th other polymere, ~uch ae ethylene vinyl ac-tat- copolymer In anoth-r pr-ferred ~mbodiment, the preeent invention provid-e a compostable multilayered barri~r film of a gas barrier layer of a chlorino-free, naturally biode~radabl- polymer and one or mor~ moi-ture barrier layer- of polyolefin polymers conta$ning the prod~gradant y-tem of the presant invention In such an e~bodiment, the prod gradant y-tem i- epecifically comprieed of from about 5 ppm to about 2000 ppm of a transLtion metal in the form of a ealt, and an auto-oxidative component comprising a fatty scid, ubetituted fatty acid or derivatives, or blends thoreof, having l0 to 22 carbon atom- Th~ auto-oxidatLve lS componont compri-e- between about 0 l to l0 weLght percent based on the total compo-ition of the moistur barrier layer~), and prov$de~ at l-a-t O l weight porc~nt of uneaturated epociee and at least 0 l weight percent of free acid ~pecie~ in the total compo-ition Th tran-lt~on metal portLon of the salt L~
-locted from the group con-i~ting of cobalt, mangane--, copper, c-r$um, vanadium and iron The polyolef~n polymer- ueed Sn the moieture barrLer layer~) can be any of thoee disclooed herein, including meeophaee propylen -ba-ed material-, uch a- meeomorphoue polypropylene, m -opolymor blend-, m -ocopolymer-, or combination- thereof Furthermore, the chlorine-free, naturally biodegradable polymere of the ga- barrier layer compr~-e the eame materialfl, including the preferrsd EVOH copolymer de-cribed above for the degradable multLlay-red barrier film Importantly, th degradable and compo-table multilayered barrier f$1m~ of the pre-ent invention eliminate chlorine-containing compound- a~ componente of the gas barrier layer, moi-tur- barrier lay-rs, optional adhe~ive layQrs, or ae additi~e~ to the-e layers, and thereby provide environmentally compAtible f ilmB that can be disposed of; euch as through compo-ting, without ndangering humane This is in direct contra-t to typical barrier filme, using materials such ae poly~vinylid ne chloride) (PVDC), and poly(vinyl chloride) (pvc)~
which can pr--ent both human and en~ironmental hazards In particular, materials such As PVDC and PVC can releaee hazardou- ub-tanc-e, such ae hydrochloric acid (HCl), polychlorinated d~b nzodioxin, and furan toxine into the environment S-e ~,, St-ff Report, ~Propoeed Dioxiu- Control M a-ure for Medical Waet- Incineratore~, State of California, Air r WO g3/11941 2 1 ~ 5 ~ 7 2 PCT/US92/10718 R -ourc~- Board, Station-ry Sourca Division, pp 1-40 (May 25, 1990)~ Medical Wa-te Policy Committee, ~PeropectiYe~ on M~dical Wa-te~, A R port of the N-l~on A Rockefeller Institute of Gov rnm~nt, st-t~ Univ-r-ity of New York ~June, 1989) In addition, xpo-ur~ to di-2--thylh xylphthalate (D~HP), a common pl-etieiz-r utilizod with PVDC and PVC, may pre-ent a number of h alth-r-lat d eonc-rn-, including r~duced blood platelet fficacy, and pot-nt$al link~ to liv-r cancer Sc~ e a , Allwood, M C , ~Th- R-l-a-- of phthalate e~ter pla-ticizer from intrav-nou- admini-tration -t- into fat emul~ion~, 29 International Journal of Pharmaeoloov, 233-6 ~1986) In contra-t, th mat-rial- compri~ing th degradabl- and compoetable mult$1ay-red barrier film- of the pr--ent invention do not use DEHP, and after u--, ar- ultimat-ly broken down to environmentally compat~bI- wat-r and carbon dioxide The artiel-- and multilay r ~t Ncture- of the present inv ntion can be formed by a variety of t~chniques, including ext N-ion, co xt N-ion, laminatlon, or conventional coating t-ehnigue- Preferably, hot _ lt eo xt Nsion i- used to form the multilay r d t Nctur - aceording to th pr~--nt invention Coext N-ion i- a poly~ r proc--~ing m thod for bringing div-r-e polymcric material- togother to form unitary layered t N cture-, ueh a- film , heet-, fiber-, and tubing This allow- for unigue combination- of materials, and for structure~
with mult$ple function-, uch a~, barrier characteristics, radiation r--i-tance, and h at -alability By combining coext N sion with blown film proee-~ing, film structures can be made which hav- no inh r-nt wa-t- and much lower capital inve-tm nt ov-r flat film co xt N ion ~owever, flat film 30 ~ proee--ing t-chnigue- provid an ~xcellent method for making the d gradabl- multilay r d film!, ineluding barricr film-, according to th pr ~-nt invention Component poly~ r or copoly~cr matcrial- according to the pr---nt inv ntion can be eo xtrud d from th- melt tate in any hap~ which can be rapidly cool d to obtain a multilayered tructur-~, uch a- barri-r film-, with a moisture barrier layer which includ-- ~ -opha-- propyl-n -ba-ed material- The hape and/or thickn -- of th co xtrud~d tructur- will be dependent upon th- ffieiency of th- particular extru-ion equipment mployed and th gu-nching y-t m- utilized aenerally~ films and tub - r- th pr-f-rred co xtruded tructure- Only under appropri-t-, low t-~p ratur- eonditlon- (i e , b~low 60C), can multilay r d tructur-- b uniaxi-lly, biaxially or multiaxial~y orient-d to furth r nbance their physical propertiee without ' !
2 1 ~ S J 7 2 2 0 -lo~$ng the me-ophaee form of polypropylene, m~sopolymer blend~, or me-ocopolymer-To obta~n multilayered structures ha~$ng mesophase propylene-ba~-d mat-rial-, ~uch a~ m somorphous polypropylene, mo~opolym~r S blende, and~or m -oeopolymers, the coextruded etructure- muet be quenched $n a manner euch that the meeophaee form of polypropyleno and/or me-ocopolymer ie obtained~ Miller, ~On th~
~x$-t-ne- of Near-Range Order in I-otactic Polypropyl-nes~, in Polv~er, on~, 135 ~1960), and U S Pat~nt No 4,931,230, both of th d$sclo-ur-- of wh$ch are herein incorporated by reference, di-cloee uitabl- ~ thod- kQowQ to thoee ekillod in tho art for the preparat$on of meeophase form of polypropylene Ae d -cribed by the-e publicat$one, varioue known methode of quenching a- eoon a- po--$bl-, and pref-rably, immediat-ly after lS extrue$on, can be u-ed to obtain a meeomorphous polypropylene homopolym r, me-opolymer bl-nd, and/or m -ocopolymer hav$ng the me-opha-e form of polypropylene and/or me-ocopolymer there$n Quench$ng method- includ- plunging the coextruded structure into a cold liquid, for exa~ple, an $e- water bath ($ e , quench bath), rpraying th eo xtruded etructure w$th a l$qu$d, euch a~
water, h$tt$ng th film with a tream of cold air, and/or running the co~xtrud-d tructure ov~r a cool~d roll, quench roll, or drum The coextruded multilayered etructures of the present inv ntion, euch a- barrier or packaging film~, are preferably quench~d $mm diat-1y after xtru-$on by contact w$th a quench roll, or by be$ng plunged $nto a quench bath For a film thickneee of from about 6~ to about 625 ~, where a quench roll ie u-ed, roll t mperature ie maintained at a temperature below about 38 C, pref-rably below about 24C, and the eosxtrudat~ ie generally $n eontaet with the queneh roll until ~olidified The quench roll ehould be poeit$oned relatively cloee to the coext N der di-, the di-tance being depsndent on the roll temp~rature, th- extrueion rate, the film thicknese, and the roll epe-d Gon rally, the dictance from th~ die t~ the quench roll i- bout 0 25 em to 5 em Where a quench bath iB ueQd, the bath temp~ratur i- pr ferably maintain d at a temp rature below about 4 C Th bath hould b po-ition d relat$vely cloee to the die, g-n rally from about 0 2S em to 13 cm from the die to the quench bath Th d-yradable compoeit$one and multilayered structuree of the pr --nt invention w$11 prov particularly uceful in a number of manuf-ctur d articl~e and etructures, ~uch ae multilayersd packag$ng f$1me, d$eposabls msdical ganments, bage, and other wo 93/llg4l 2 1 ~ S ~ 7 2 P ~ /US92110718 compon-nt-, and variou~ hygiene articlee Packaging f$lms of a polyolefin lay r containing th prodegradant cy-t~m contact~d with one or two polyolefin lay-r- wlthout the prod gradant ~yetem could -rv~ to contain variou- p r~-hable product-, while at the S ame t~ ub-tantially pr-venting the di~per-al of the prodegradant y-t-m component- into th peri-hable mat-rial For xampl-, a baby bottl- lin-r could b~ formed from a degradable p ckaging film si~-ording to th- pr -ent in~ention In uch an in-tance, the p~- -habl- product (i e baby formula, ~uice or wat-r) would b- hi-lded from the prodegradant containing layer of the fllm by a econd lay r not containing th prodogradant y-t-m Aft-r u--, uch bottl- lin r could b- di~card d into a municipal wa-t- tr am to b- co~po-ted or oth rwi-e oxidatively d grad d Sh d grad bl- and compo-tabl- multil-y-r d barrier film-according to tho pr - nt inv ntion will b -p cSally u-eful in o-tomy pouch applicationc, where -curity from odor, integrity of th d vice, and int grity of the underlying material- are r-quiromont- ~ultilay r d barri r filme can b- die cut and heat al d with conventional ~quipmont, and are oompatible with curr-nt attachm nt y~ ~m- and o-tomy pouch~ manufacturing practic-- Since th ~; tilayer d barrier fiLme are moieture r--i-tant both in-ld -~d out, th re-ulting o-tomy pouch io capabl- of b ing wor during w~mming and how ring In ddition, oth r u-eful rticle- uch a- tape-, tubinge, contain r-, tr n-d rmal drug-d livery patche- and variouc p cXaging m~t-rial- can al-o b- formsd from th~ multilayered tructur - of th pr---nt invention Th d grad ble and compo-t ble multilayered barrier filme of the pr-- nt inv ntion ar- u-eful to form or cover a prot-ctive nvlron~ nt from an xt-rn-l nvironment, uch that moieture and/or ga--- c nnot ub-tantially pa-~ through to a p ri~hable product contain d th r in, or a urf-ce covered thereby For xample, th~ muiti1ayer d barri r films can b u-ed to contain a food product or a phar~aceutical product in a protected nviron~ nt, to which moi-ture and/or ga-e~ fso~ th~ xternal nviron~ nt cannot ub-tantially p ~- into Similarly, the ~ultil-y r d barri-r fi~m- can compri-- a tran-d rmal drug d-liv-ry patcb, or ~odical tap-, or an o-to~y pouch, which prot-ct- th body of a a~mal, or the wa-te product- g-n rated by th ~am~al, fro~ d gradation due to xposur- to mo~-ture and/or ga--- in th xt-rnal nviron~nt Th following xumpl-- ar- provided to illu-trate pre-ently cont-~pl-t d pr f-rred mbodim-nt- and the b-~t mode for 2 ~ 3~ ~ PCT/US92/10718 practicing the invention, but are not intended to be limiting thereof T~ST PROCEDURES
Embrittlement ~mbrittl ment wa- determined by hand teeting the ~amplee A
state of ombrittl-m~nt wae defined ae the tim~ at which the sample~ had little or no tear or t-n~ile strength remaining or would crumble when folded With softQr or lower melting polymers, euch as polyethylene, the films did not generally di-$ntegrate or crumble but rath r became eoft and loet all t-n-ile tr-ngth.
Oxidative degradation WaB te-ted in dry forced-air OvQn~
maintained at variou- temperature- Compost conditione were simulated by placing th~ film- into a ~ar of water which was then buffered to a pH of 6 by a pho~phate buffer and heated to varioue temperatures Sampl-- were removed at various times from the dry oven~ or simulated compost conditione and tested for embrittlement Generally, th~se ample- were teeted at intervals of 8-24 hours Film Pre~aration The single layer film~ of Examples 1-101 were prepared on a 3/4~ (1 9 cm) HAAREI~ extruder, having a L/D ratio of 24 1 ueing 3 zone~ having temperature- of 390F ~ 199C), 410F ~210C), and 430F (221C) with a die temperature of 430F Theee films were formed on a casting roll at a temperature of 70F (21C), and were taken off the roll ~o as to have a total thickneee of 4 0 `~
mils (102~) The two and threo layer films of Examples 102-160 were prepared on conventional xtru~ion equipment u~ing dual and triple manifold coextru~$on die- maintained at a melt temp~rature of 232C ~he coextruded film- were made at a total thicknese of 2 0 mils (51~), and w-re formed on a casting ~oll maintained at a temperature of 50C for th~ quenched films~ or a temperature of 150C for the nonquenched films Th thickness of the reepective layer- of the two and thre- layer film~ were varied to determine the effect of layer thickne-- on overall film degradability Ex~m~le~ 1-14 The film~ wer- pr-pared a~ d -cribed above using 566 parte per million of mangan-s- st-arate (i.e , 50 ppm manganese)~ and 1 w-iqht p rc-nt of th indicated natural oils (T~bl- 1) in - polypropyl~ne ta Sh-ll 5A95 9 5 NFI homopelymer with an anti-~ W O 93/11941 2 ~ ~ i3~ PCT/US92/10718 oxidant available from Shell Chemical Co., Houeton, TX) with the exception of Example 14 which utilizsd 2 percent of a styrene-butadiene rubb~r (SBR) ae an auto-oxidant. The SBR wae incorporated ae a concentrate con~i~ting of 28~ SBR in 72~ Shell 7C04N PP/PE lmpact copolymer ~35 MFI, 9~ polyethylene).
Two inch (s cm) by sLx inch (15 cm) ~amplee were placed in traye in dry forcsd air ovene. The traye were r~moved periodically and the filme were creased by hand. Embrittlement wae defined as the point in t~ m~ when the eample~ wo~ld fir~t crack and fall apart when creaeed. In the Tables provided the greater than eign indicatee that the testing was terminated at the noted time (in houre). The sample~ were te~ted at 60C, 70C, and 88C ae noted in Table l below.

21~557~2 . , _ Table 1 ~ ._.~."................ ,_ Example Auto-Oxidant Time to Embrittl~ment 88c 70c 60C
_ _ . _ _ ~
1 Coconut Oil _55 257 600 2 Almond Oil 12 202 31 3 _Olive Oil 36 202 410 4 Caetor Oil _ 55 179 317 ¦ 5 Safflower Oil _31 161 245 1 6 SoY Oi~ 5 161l291 _ ¦ 7 Wh at Germ Oil 4 5 161 358 ¦ 8 Walnut Oil 6 130 291 ¦ 9 Dehydr ____ Castor Oil 4 5 130 317 ¦ 10 Cod Liver Oil 12 94 190 ¦ 11 Sardin- Oil 11 57 149 ¦ 12 Tung Oil 7 53 150 ¦ 13 ~in-e d Oil 6 20 59 ~ _ .. ;
All samples were approximately 1-2 weeks old when teeted The tablo indicate- that the oile containing more highly unsaturated fatty acid eeter~ provide the faatest high t-mp rature dogradation at typical dry condition~

Exam~les 15-28 Variou~ films were prepared and tested, as de~cribed above for ~xamplee 1-14, ueing 1 weight percent of various fatty acids and fatty acid derivatives ae the auto-oxidants All auto-oxidante were C18 fatty acide or fatty acid derivativee with 0, 1 and 2 doubl- bonds (~tearic, oleic and linoleic, respectively) Ths ample- wcre ~pproximatoly 1-2 weeks old when teeted The reeult~ are gLvon in Tabl- 2 The r~-ulte indicat- that eubstitution of tho fatty acid g~nerally doe- not eignificantly ~ffect tho d-gradation rate of compoeitione u-ing derivatives of typical fatty acids ~' Table 2 ~ ~, - r- -Example Auto-Oxidant ¦ B8C 70c 60c --~.................. ".,.", " _ , . ...
Stearic Acid tC18, O DB) 8-23 217 155 16 Methvl Stearate ~800 ~800 ~800 ¦ 17 Ethyl Stearate ~800 800 ~800 ,, ¦ 18 Propvl Stearate 8-23 103 155 ¦ 19 Stearamide 8-23 265 348 StearYlamine 8-23 >800 ~800 . _ 21 St-aryl Alcohol 8-23 103 204 22 Ol~ic Ac$d ~C18, 1 DB) 3 5 9-23 48 ~;~
23 Propyl Oleate 8-23 48 120 24 Ol-amid- 30 48 102 ~`
_ ,,, OleYl Alcohol 8-23 38 10 26 Linoleic Acid (C18, 2 DB) 5 5 23 38 ,~
27 HethYl Linoleate 10 38 78 j 28 Propyl Linoleate 10 38 116 I

The example- were also checked for degradation after ~toring at room t~mp ratur- for 8 5 month- Examples 22 and 24-28 showed igns of embrittlemQnt, however, Examples 15-21 and 23 were not e~brittled at thi~ date Exam~les 29-62 Sampleo were prepared, as deecribed above for Example~ 1-14, using variou- polypropylene- (unstabilized and ~tabilized, i e , commercially available r~-ins with anti-oxidant~ tabilized -~
polyethylene- and blend~ ther-of a- indicated in Table 3 using the proc dur- outlined above All metal- were added as metal t-arate~ to provide th- indicated concontration of metal Sample- were then placed in water ~ar- and b,uffered to a pH of 6 u~ing a pho~phate buff-r The ample- were teeted for embrittlem~nt a- d -cribod aboqe except for the polyethylenes and blend~ which w re t--ted for oftness and loes of tensile ~trength Th- time for embrittl~ment i~ hown in Table 3 below The ample- were te-tod within ono week aftor extru-ion '~

PCI`/US92/1071X

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. WO 93/11941 2 1 2 ~3 ~i 7 ~ PCI/US92/10718 O ~ r c u r u ~ ~ u c r 07 ¦ ~

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I I I A ~ ~1 ~1 4 ~ 5 '5' L~ ~ ~ 5_ W O 93/11941 2 1 2 ~ 5 7 ~ PCT/US92/10718 Samplee from Examples 29-62 were ~tored at room temperature for ~pproximately 1900 hours and checked for ~mbri~tlement.
Examples 29-41 ~mpleB ~howed ev~dence of embrittlement, while Examplee 42-62 sa~ple~ showed no 3ign~ of embrittl~ment.
S Table 4 ehow~ the Q~brittlement time for Example~ 29-62 :~
~ample~ in a dry ov~n.

WO 93/11941 PCI~US92/10718 ~ 1 2 S ~ 7 l t~
I i fl 1 1 I,~r ~

I I 13 ~ 1 3 oi 1 ~`
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2 1 2 5 ~ 7 ~ PCr/US92/107t8 - WO 93/lt~41 ~ ::
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W O 93/11941 PCT/US92/107t8 21~1Ss~

EXamD1e~ 63-79 Samples were preparod u-ing variou~ polypropylenes (un-tabil~ed and ~tabilized commorcial polymer~), tabilized poly-thyl-n-- and tabilized blend- thereof a- defined in Table 3 u-ing the procedure outlined abo~e Sample~ were then placed in wator ~ar- and buffored to a pH of 6 u~ing a pho-phate buffer The camplo~ were toetod for embrittlement as de-cribed above except for the polyethylene~ and blend~ which were te-ted for eoftne~- and lo-- of ten-ile etrength The t;m~ for ombrittl-ment i- shown in Table S below The ~ample- were te~ted ~oon after extru-ion WO 93/11941 2 1 2 S ~i 7 2 PCI/US92/10718 ~+~
ll~t~ tl~

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21 ~ r 7 ~ PCI`/US92/10718 - W(~ 93/11941 h~ 3 Tabl~ 6 ~hows the embrittlement time for Example~ 63-79 samples in a dry oven~

WO 93/11941 PCI`/U~i92/10718 21~a7~ - 38 -I ~; ~
~ _ _ _ _ _ _ _ ~Ul -;
1~ ~

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W 0 93/11941 PCTtUS92/107t8 ~1~5~7~ 40 -Exam~les 80-94 Th-se filma ~4 m$1 caliper) wer- prepared in accordance with Examplec 1-14 w$th th~ exception of Examplee 83-89 which were l mil film~ (25 4 micrometer~) The compooitiono includ~d variou~
5naturally biodegradable polymero (Tonel~ P-700 and Tonel~ 767P
ar~ poly---caprolactoneo (PCL) availAble from Union Carbide of Danbury, CT; Bipoll~ PHBV is a poly(hydroxybutyrate valerate) (12~ val-rate) available from ICI Americas, Inc ; Vin~xl~ 2025 and 2025U aro polyethylen /vinyl-alcohol copolymer- available 10from Air Product- ~ Ch~micals, Inc of Allentown, PA; Elvax1~ 260 i- an thyl-n /vinyl acetate copolymer (EVA) (28~ vinyl acetate and 6 MFI) ava$1abl~ ~rom DuPont Co , Wilm$ngton DE; Nucrell~ 960 iB a polyothylQn-/methylacrylate copolymer (density ~ 0 94, MFI
- 60) availabl- from DuPont Co The poly-L-lactide has an 15intrin~ic vi-co~ity of l 04 and iB available from Birmingham Polym ro, Inc The polyesteramide - 10,2 (PEA) has an intrinoic vioco-ity of 0 7 and i- available from 3M Company, St Paul, MN, and Pamolynl1~ lO0 (PAM) i- an oleic acid (9l~) available from Herculoo, Inc , Wilmington, DE) 20Film- from Examplo- 81 and 82 w r~ te~ted for degradation in water and air ao deocribed above at 60C The Example 81 films b camQ embrittl d at 43 hour- in air and 112 houro in water The Exampl~ 82 film~ bec~ms embrittled at 53 hours in air ~nd 332 houro in wat~r The times to embrittl~ment in air for Example~
2583-94 are given in Table 7 below ~17 S ~ 7 ~ PCI/US92/10718 WO 93/tl941 ;~

t ;~ :

~ r _ a _ _ ~ o~ o --I

W O 93/11941 PCT/US92/1071~.
21~55~'2 Examo~e~ 8Q-82 80) Shell 5A95 88.94 Ton~ P-700 10.00 Tung Oil 1.00 ~angan~ Mn) Stearate 0.06 81) Shell SA95 85.94 Ton~ 767P 10.00 Pamolynl~ 100 4.00 MnStearut~ 0.06%

82) Shell 5A95 85.94 Bipoll~ PHBV 10.00 Pamolyn1~ 100 4.00%
NnStcarat~ 0.06%

~ xample 82 wa~ of poor quality becau~e of th~ incompatibility of P~BV with polyol~f~n~.
~xamDle~ 83-89 (1 mil LDPE Films) 83) Ten~tel~ 1550P 94.94 poly-L-lact~de 3.00%
PAmolynl~ 100 2.00 MnStearate 0.06%

8i) T~nitel~ 1550P 91.94 poly-L-lactida 6.00~
Pamolynl~a 100 2.00%
MnStearat~ O.Q6%

85) Tenitel~ 1550P 88.94 poly-L-l~ctide 9.00~
P~molynl~ 100 2.00%
35 . . M~St~arate 0.06~

86) Ten~te1~ 1550P 88.94 poly~steram~de-10,2 9.00 Pamolyn1~ 100 2.00 ~nStearat~ 0.06 W 0 93/11941 2 L ~2 ~ 7 ~ PCT/US92/10718 87) T~nitel~ 1550P 72.94 Tone P-700 5-00%
Sh~ll 7C50 PP/PE copolymer 20.00 Pa~olyn~ 100 2.00 MnStearate 0.06%

88) T~nitel~ 1550P . 72.94 V$nexl~ 2025U 5.00~
Shell 7C50 PP/PE 17. 50 Elvaxl~ 260 2. 50 P~mclynl~ 100 2.00 Mns~Barats 0 . o696 89 ) T~niteTM 1550P 72 . 94 Bipoll~ PHBV 5.00 Shell 7C50 17.50 Elvaxl~ 260 2.50 P D lynl~ 100 2.00~
~nSt-arat4 0 . 0696 ~x~m~lea 90-04 (4 mil PP/PE coDolvmer film~) 90) Shell 7C50 78.35 ToneTM p_700 19 . 59 Pa~olynl~ 100 2.00%
}fnStearate 0 . 06 91) Shell 7C50 78.35 Vin~xl~ 2025 19.59 P D lynl~ 100 2~00~
~snStoarat~ 0 . 06%

92) Shell 7C50 68.56 Vin~xl~ 2025 19O59 NucrsllD~ 960 9.79 P D lynl~ 100 2.00~
MnSt~arat~ 0.06%

W O 93/11941 PCT/US92/107t8 ;;
'~ 12 5 'a ~ `2 93~ Shell 7C50 68.50~
Vinex1~ 2025U l9.59%
Elvaxl~ 260 9.79%
Pamolynl~ lO0 2.00%
MnStearat~ 0.06 - 94) Shell 7C50 82.95 Bipoll~ PHBV lO.00 Blvaxl~ 260 5.00 Pamolynl~ lO0 2.00 MnStearate 0.06 ~xam~lee 95-98 F~lm~ were propared and ts~ted as deecribed above for Examploe 1-14, ueing un~tabilized polypropylene with 2~ added Pamolynl~ lO0 and 400 ppm Fe (ae Fe Stearatæ) at variou~ levele of Irganoxl~ lOlO. The films were ta~ted for ~mbrittlement at various tempsraturee as indicated in Table 8 below.
~ , Tabl~ 8 ~ ~ , ., ~ , -~xample Irganoxl~ 88C 70C 60C 49C
(PPM) Hrs. ~re. Hre. Hrs.
0 4 l3 40 96 _ 96 200 _ _7.5 34 96_ 215 1 97_ 600 20 ao 260 650 98 lO00 39 2l5 1500 I~ _ _ ~ _ _ _ The films were also kept on a ehelf at room temperature for approximately 3,900 hour- and teeted- for embrittlement. The Bxamples gS and 96 filme had embrittled at this tLme, but the Examplee 97 and 98 fllme had not.

Ex~ s 99-101 ImmaturQ compoet wae allowed to dry until it contained only 5~ wat-r. To lO00 g of thi~ compoet wer~ added 200 g of dried, ehredded maple leave-, 6 g of Compoet Plue (Ringer ~orporation, Minneapolie, MN) and euff$c$ent water to yield of mixture of 54 water. The compoet mixtu~ wae pla~ed in a wire mesh basket in a Nalg-ne tank (Nylon - 14~xlO~xlO~ fro~ F~eher) in a forced air oven at 50~C. The compo-t wae aeratad from the bottom by eu~pending th~ wire baBket over two glaB~ frit~ ~lOnxl.5") in a W O 93/llg41 PCT/US92/10718 ` 2125~;7~

pool of wat-r through wh$ch air wa- bubbl~d The compoet mixture containing th film sample wa~ piled in the wirs basket--o that th- ample- w r- complotely cov r~d S~veral ampls~ could bs - t--t-d in on uch apparatu-S Th~ t~-t period wa- one month The initial carbon-to-nitrog n ratio of the compost mixtur- was 40 1 Th- pH of the y-t m r main d r lativoly neutral, ranging from 5 5-7 0 Moi-tur- wa- maintain d at 45-55~ by adding water a- nece~ary Th compo~t wa- manually turned daily and film ampls- wers checked for mbrittl _ nt EmbrittlQment was not a- pronounced in th~ imulatod compo-t test as it wa~ in the dry oven test~
howev r roughly corr-lated to the wat~r ~ar te-t re-ult~ Films u-ually tor- fir-t in one direction, and th~n both, b~fors b coming brittl- ~mbrittl~ment ti~e~ for Example- 99-101 ars lS li-ted in Tabl- 9 b low Table 9 x~pl- _Film 99 SA95 PP + SOppm Co + 4~ Oleic 10 day-100 Un-tab SA95 PP + 50 ppm Mn + 27 day-4~ Ol ic acid 101 5A9S PP/Ton l~ 767P PCL 26 day-~9 1) + 50pp~ Mn + O!oic Acid ~ e~
~xamDle- 102-12~
Two-layer film- w~r- prepar-d a- de-crib~d above The fir~t layer of ach film wa- approximateIy 1 75 mil (45~) thick, and the econd layor wa- approximately 0 25 mil (6~) thick, for a total film thiekn -c of approximately 2 mil (Sl~) A
prodegradant y tem of 2840 p~rt~ per million (ppm) of manganeee t-arat~ 250ppm mangane-e, 50ppm Mn (568 ppm Mn terate) for ~xa~pl- filn No 118)~oon y Ch-mical, Cleveland, OH), and 2 w ight p reent of Oleic acid (OA)~Xodak Chemical Co , Rochester, NY) wa~ incorporat!d into ith r the first layer or tho first and c-cond l~y r of the two-layer fiLm- The polyolefin polym~r r ~ine u- d to form th -- fil~- included, Shell polypropylen~
r--in No SA95 (8h 11 Ch ~ical Co , 80u-ton, TX), T-nit~ low d n~$ty poly thyl-n r -in No 1550P (Ea-tman Chemical, Xing-ton, TN), and Quantu~ Ch mical polyethylene re~in No NA 952 (Quantum Co , Rollin~ N-adow-, IL) Two ineh ~S cm) by ix inch (15 cm~ umpl - of each of the f~lm~ w r plae-d ~n tr-y- in dry forced ir oven-, and were t--ted for mbrittl-ment at 49C, 60C, and 70C, according to ~5 r~ ~ 46 -the proceduree of Examplee 1-14 In addition, the eamplee were al~o placed in water ~are and were tested for embrittlement according to the procedure- of Examplee 29-62 The epecific compo-it$on and time to mbrittl _ nt in hour- for ~ach of the ~xumpl~ film- i- ehown in Table lO below The l-tter "Qn indicate- filmè that were formed by guenching at 50C, while ~NQ"
indicate- filme that w~re nonqucnched by being formed at a t-mp rature of 150C

WO 93/11941 21~ ~i 5 7 ~3 PCl/US92/10718 _ ~ ~ N ~t N N N

U~ N N ~1 rl N N ~`
I
~ ~ '~
O ~ ~ .
~ ~ ~ ~' 0~ 0~ ~` ~' ~ ~¢`

J~ ~ c~ ~ + + ~ d~ ~P d~
~_ + ~ _ ~ ~ ~ ~ +
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:~ ~n ~ In U~ In U~ n In O U~ O In u~ c> In J~ ~ O~ O~ O~ O~ ~ O~ O~ O~ U~ ~ U~ a~ o~ u~ o~
0 ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ U~ ~: U~ ~ ~ ~ ~:
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t~ ~ ~1 ~1 ~r o h 3 1~_ _ _ ~ ~
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rGr i I 1¦ I n O C.~ /~ ¢ ~ .:
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P. P~ P4 1~
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~ ~ _ _ U~ - O~ . ~ ~
O 11 11 _~ ~ _~ _ ~ ~ Pi P ~ ~ ~ -: ' .. ~ 5~ ~ ~ ~ P~
O q~ P. P~ P~
u7 ca ~ Q ~ o m ~0 cn ~n o~ u~ ~ u~
1 ~ In ~¢ u) ¢ I
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_ __ _=. = __ _ ~S~7~

Table 10 hows a~ong other thing~ that two-layer polyolefin film~, wherein one of the layer~ doe~ not contain the prodegradant y~t m of the pr---nt inventLon, will oxidatively d gr-de under a varLety of condition-, including simulated compo~ting conditiono In fact, degradation for uch films occur- at compar-ble rates with tho~o film~ that contain the prodegradant sy~tem in all layers (e g Example fLlm No8 112-115) Purth-rmore, radiation degradation-re~istant films formed of ~esophas- propylen~-ba-Qd materials can bo made to degrado at comparabl- rato- to the samo film~ for~ed from crystalline polypropyl-n u-ing the prod gradant y~tem of the pre~ent invention (compar- e g ~xample film Noc 102 ver~u~ 103, and 108 v-r-u~ 109) ExamDlQs 122-142 Two-layor films were pr~parod using the same methods and matorial- a- Examples 102-121, excopt that the first layer of oach film wa~ appxoximately 1 00 mil (51~) thick, and the ~econd lay r wa- al-o approximat-ly 1 00 mil ~51~) thick, for a total fil~ thiekn -- of approximately 2 mil (51~) Bxumpl- film~ 122-142 w r- t--t d und r th- am eondition a~ for ~xample- 102-121 Th pecif~e eompo-ition and time to embrittlem~nt in hour~ for each of th Pxample film- i- shown in Table 11 bslow :., , .... - :

WO 93/11941 2 ~ ~ 5 5 7 2 PCI/US92/107t8 _ ~ O ~ ~O In ~ U~ ~D O~
o ~ 3 N N _ _ N _ _ N
C>~ ~ D .~ ~1 ~O ~ ~

o ~ C U~ ~ N Ul ~ r~ ~'1 i~ ~ tl ~ ~ ~
~ ~' ~ ~ :
''-';
~1 _ _ I C ~: ~: ~'~
o ~ O :z Q Z
.Y~ ~ ~ ~ ~ o o 1 . ~ N ~> N ~ ¦ _ +
It~U ~ ~ ~ ~ ~ I~ ~i ~ X

N ~ N ~ N

o n 1l ~ ~ P. P~ P~ P- P~ P- P~ ~ P' P. P4 li3 p e~
. , ~ ~ ~ ~ u~ o ~ u~ ~ u~ o u~ o u~ o u~ ~o u~ o ~ u,~u~ u~ ~uu~ ~u~ ~u~ u~u~ ~u~ ~u~) ~:' ~ ~ C ~ ~ ~ ~ ~ ~o ~ ~ ~ ~ ~ ~ JJ ~
~.) ~ N ~ t~ ~ ~ ~1 ~ I ~ ~ ~1 _ I ~ ~ N N N r N N _ WO 93/11941 PCI'/US92/10718 _ ~_ _ _ _ _ ~_ _ _ ~ L~ ~ u o _ L~ N

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O J~ ~I N rl r V ~3 ~ N

L 1~ Z C~ ~ r rl ~ 1~ ~ . ~
~:

WO 93/11941 212 ~ S 7 ~ PCI/US92/10~18 I

_ _ _ ~ U~ U~ U~ Ul O ~ 3 N d d d d C) ~ ~n ~ N ~ 5 ~ o o o~ a~ ~ , :~
~ C _ _ _ _ d : :
~--_ _ O~ O~
r ~ CN _ _ N _ ~ ~ ;~ ~ ~' ~
~ N N N +
~ + + . ~ :

U ~i ~ ~ N

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:~
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_ W ~ r r v r N

3 7~
W O 93/11941 PCT/USg2/10718 The filme shown in Table 11 demon~trate analogou~ d~gradation result~ to tho~e of Ex~mple filme 102-121, Table 10 In addition, the data aleo ~how that even when the non-prodegradant containing lay-r of the two-lay-r film~ iB a~ thick a~ the prodegradant containing layer, the overall film~ ~till oxidativoly degrado under a vari~ty of condition~, including ~imulated compo~ting condition- In fact, degradation ~or tbe~e film- occurs at comparabl- rate- with film~ of Example~ 102-122, wherein the non-prodegradant containing layer i~ ~even time~
thinnor than the prodeqradant containing layer ¦Sx~Dl~ 143--152 Thre~-layer film- w r~ prepar-d u~ing the ~ame methods and material- a- ~xample~ 102-121 Additional polym~r~ u-od include Sh ll polybutyl-n re-in No 400 ~Sh-ll Chemical Co ) and Vinex~
polyvinylalcohol re-in No 1003 ~Air Products, Allentown, PA) The fir~t layer of sach film was approximately 0-25 mil (6~) thick, tho ~econd layer wa- approximately 1 50 mil (38~) thick, and tho third layer was approximat-ly 0 25 mil (6~) thick, for a total film thickn -- of approx~at-ly 2 mil ~51~) Example f$1ms 143-152 w~re te~ted under the ame condition a- for ~xample~
102-121 Th pecific compo-ition and time to embrittl~ment in hour~ for each of the Example film- i- ~hown in Tnble 12 belo~
'` ' : . ~

PCI`/lJS92/10718 wo 93/t 1941 2 1 ~ 5 5 7 2 _ ~ N O U ~ O

~ N C ~1 ;
t ~ ~t ~ ~ ~
I I I I I
~ . o + C
N & ~ ~ _ ~;

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.~ ~ ~i ~

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. O ~ , ~ ~ Do. OU~ ~ ¢ O

~ N ~ ~ N '1 . . . . ~ N
_ 1~ ~ ~O r~

WO93/11947 ~ PCI/US92/10718 r ~ ~ o~ ;;

~ - I ..
o ~ t~ t~ N ~ I~ -:
~ . _ I .
o ~ It~ In ~ 10 t~
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~ _ N N N~ N-- N N
'D ~ 'D X ~ X ~ o ~_ ~ ' ~: ~ ' -' ~, &W ~ &,, ~o & ~ ~
10 N U~ N O ~ O O X O U) X--O O O ¢ 01 :
N U~ N ~ 1 N 1~ N N _ O ~1 0 1 ) _1 ~ ~ ~ ~ ~'7 ~
O U 11 U ~ ~ ,0~ + ~ O + O p~ ,0~ 0 ..~. ~v~ ¢~ ~x ~x ~x ~xx ~ ~ ~ . -- -- - -- -- .. - ... - -- --g ~ N ~ ~ ~ ~ ~ ~ ~'O ~ ~ ~ ~ J~ ~O
C,~ ~I N~1 ~ O ~1 N ~ N ..
X z ~ ~r u~ 1 _ W O 93/t1941 2 1 2 S ~ 7 ~ PCT/US92/10718 Table 12 shows among other thinge that three-layer film~, ~uch as Exampl~ film No 143, that contain two layer~ without the prodegradant sy-tem, degrad at comparable rat~e to ~n analogoue two-lay-r d ~tructur~ (i e Example fil~ No. 109) containing only one layer without th~ prodegradant sy~tem of the present invention Furthermor~, barrier film structures using a Vinex poly vinyl alcohol ro-in No 1003 a- a gas barrier layer (i e Example film- No~ 149-152) degrade and compost within the requiremente of th~ pr---nt inv-nt$on Ex~ g_ com~ gl~c~eb~ es 155-156 The crystalline st Nctur , or me~omorphou- tructure, for two ingle-layor film-, and two five-layered barrier films containing polyprow len- polymer wa- d-t-rmined by wide-angl~ x-ray diffraction (WAXD) Th~ ingl- layer films were formed as deecribed abov from Fina polypropyl-n- r-~in No 3576 (Fina Oil and Chemical Co ) containing the prodegradant system of the pr---nt inv ntion at a film thickn -- of approximat~ly 100~
Exampl- film No 153 wa- qu-nch d (Q) after extru-ion on a ca-ting roll maintained at 10 C, ~o a- to form predominantly me-omorphou- polypropyl~ne, while Comparativ~ Example film No 155 wa- ca~t onto a roll maint-in d at 66C (NQ), thereby yielding cry-talline polypropylon tructure The fiv~-lay~red barrier film- were prepared as described above, except that 3 xtruder-, and a 5-layer CloerenI~ feedblock (Cloer~n Company, Orange, T-xa-) connected to a single manifold film extru~ion die w re utiliz-d to form the filme The barrier film- were gonorally co~xtrud~d at a total film thicknees of about 75~, including a cor- layer of EVALI~ brand ethyl~ne vinyl alcohol (EVOH) re-in No 105A (~valca Inc ; npprox 8~), followed by oppo-ing polypropyl-n -ba-od adh -ive layere of AdmerI~ re-in No QF551A (Mit-ui Pla-tic-, Inc ), and finally by oppoeing lay re of Fina polypropyl-n~ r-ein No 3576 with the prodegradant er-tem of th- pr eent invention incorporated therein The conetruction of Exampl- film 154 wa- qu-nched at 10C, whLl- that of Comparativ Exampl- film 156 wa- ca-t at 66C
Th- pecific con-truction- of Example films 153-154, and ComparatLv ~xampl- fLlm- 155-156 ar- ehown in T~ble 13 In addition, graphical illu-tration- of the WAXD can~ for each of th Exampl- and Compari-on Exampl- films are shown in FIGS
through 4 her-in Th ~e-opha-~ form ~i e , ms~omorphou~ ;
polypropylQne) i- clearly ehown in FIGS 1 and 2 In contrast, 3 ~ r7 ~
W O 9~/11941 ~ ~ PCT/US92/10718 FIGS 3 and 4 how the h~rp p~k~ ~s-oc~ated with cry~talline polybutyl-ne "","",. , , . :' Table 13 Specific film conetructione of Example film~ 153-154, and ¦
Comparativ~ Example filme 155-156, and etructure --of the filme ae det-rmined by WAXD
(Neeo - me~omorphic5 Cry- - cry~tallin-) , ~
~x. ':
No Film Compo~ition WAXD l ~ I ..
153 3576 PP + 250pPm Mn + 2~ oa (Q) _ Meeo lS l-t layers 3576 ~ + 250ppm Nn + 2~ OA ~Q) 2nd layers ADMER QFSSlA
3rd layers EVALl~ 105A (EVOH) 154 4th lay~rs ADNERl~ QF551A Me o 5th lavers 3576 PP + 250pPm Nn + 2~ OA ~Q) lSS 3576 PP + 250ppm Nn + 2~ OA (NQ)_Cry~
l~t layers 3576 ~ + 250ppm Nn + 2~ OA (NQ) 2nd lay rs AD~R QF551A

6 3rd layors EVALl~ 105A ~EVO~) 15 4th layer: ADMERl~ QFSSlA C e ...... 5th l-y r: 3576 PP + 250ppm Nn + 2~ OA (NQ) ry ¦

ExamPlee 157-161 Five, five-layered barrier films were made according to the eame methode a~ for the film~ Example 154 and Comparative Example 156 In addition to the polymer- utilized in Example 154 and Comparative Example 156, several of the barrier films of Examplee 157-161 aleo u-ed Shell polybutylene reein No 0400 (Shell Ch~mical Co ), PRIMACORl~ brand ethylene acrylic acid reein No 3340 (Dow Chemical Co ), QUANTUMI~ brand ethylene vinyl acetate re~in No UE656-033 (Quantum Chemical Co ) In addition to the prodegradant ~ystem of th pre~ent invention, Example f,lm 161 al~o incorporated IRGANOXl~ brand antioxidant No 1010 (Ciba-G igy, Inc ) into it- outer lay-rs (i c th firet and ~ifth layer-) ~h ~pecific con~tructions of ~xample films 157-161 are ~hown in Table 14 below WO 93/11941 ~ ) 7 2 PCl /US92/10718 : `` , Table 14 Sp~c~fic f~lm con~tructione of Example fil~e 157-161.
. . ~
Ex.
No. Film Compo~ition for each Layer _ ~,............... ".. ,.,.. _ _ . I
lot layer: 3576 PP/0400 PB (1:1) + ~SOppm Co + 2% OA
(NQ) 2nd layer: ADMERl~ QF551A -157 3rd layer: EVALl~ 10SA ~EVOH) 4th layer: ADM~Rl~ QFSSlA
5th layer: 3576 PP/0400 PB (1:1) + 250ppm Co + 2% OA
_ (NQ) l~t layer: 3576 PP/0400 PB/U~656-033 EVA (3:3:2) +
250p ~ Mn + 2~ O~ (Q) 2nd layer: ADMER QF5SlA
lS8 3rd layer: EVABll~ 105A (~VOH) 4th layer: ADH~Rl~ QF551A
5th layer: 3576 PP/0400 PB/UE656-033 EVA (3:3:2) +
250ppm Hn + 2~ OA (Q) _ 1st layer: 3576 PP/0400 PB/3340 EAA 53:3:2) + 250ppm Mn +_~ OA ~Q) 2nd layers ADMER~nn Q~551A
159 3rd layers BVALlD~ 105A (BVOH) 4th layers ADMERl~ QFS51A
5th layer: 3576 PP/0400 PB/3340 EAA (3:3:2) + 250ppm Mn + 2~ OA (Q~
let layer: 3576 PP/0400 PB ~3:1) + 250ppm Mn + 2%
OA ( ~
2nd lay~r: AD~R QF551A
160 3rd lay~r: ~V~LI~ 105A (gVOH) 4th layer: ADMeRI~ QF551A
5th layer: 3576 PP/0400 PB (3:1) + 250ppo Mn +
2~ OA (Q) l~t layer: 3576 PP/0400 PB (1:1) + 250ppm Nn +
2~ oa~,+ Irganox 1010 (Q) 2nd layer: ADNeRl~ QF551A
161 3rd layer: ~VALI~ 105A (EVOB) 4th layers ADM~RI~ QF551A
5th layer: 3576 PP/0400 PB ~1) + 250ppm Mn +
2~ OA + IRGANOX 1010 (Q) , .. ~ .-Re~istance to perm~ation of oxygon and moisture vapor wa~ ~-mea-ured for th multil-y r d barri r films of ExampleA 157-161 oxygen tran-mi--$on rat- (O2TR) wa- det-rmined u-ing an Ox-Tran 1000H mach~ne ~Nocon, Inc , M~nnoapoli~, Minnesota) O2T~ wa~
collected at 25C and zero percont (0~) relative humidity A
quare ample of each multilayer f~lm was placed in tbe te~ting cell of the Ox-TranI~ oxygen p rm~ability te-ter Two saMpl~s of ach f~lm were t--ted in ad~acent c~ Since tho Ox-TranI~

1000B mach$ne ha- tcn test cells, up to fiv- film~ could be examin d at any on- time ~ ach c-ll wa- purged for at l-a-t 24 hour- with a ~carrier~
ga- of nltrog n containing 1-3~ hydrogen prior to te-ting, to remov any r--idual oxygen in the ~ampl-, cell and y~tem After purging wa- co~pl-ted, a ample of the ga-e- in ach c-ll wa~
te-t-d for r--idual oxyg-n cont-nt or oxyg~n ~l-ak rate~ The l-ak r-t- valu- d t-rmin d at ach cell wa~ u--d as the cell'~
r--idual oxygen ba--lln Noxt, ach c-ll was conditioned for another 24 hours by pa--ing 100~ oxyg n ov-r on id of the ampl- Oxyg n on the oth r ld of th ampl- wa- mea-ured after thi~ conditioninq p riod Thi- total oxyg-n content includ-d th amount of oxyg-n which p-r at d through th- film plu- any residual oxyg-n in the y-t m To obtain oxygen tran mi-sion rate through th- film, the l-ak rat- valu~ wa- ubtracted from th- total oxygen mea-ured Oxyg n tran-mi--ion rat- data wa- coll-cted for each film at 25C and 0~ r lative humidity The values reportod are the av rag of rat-- d t-rmin d for two ampl-- Sinc- oxyg-n tran~ ion rat~ i- lnv r--ly proportional to thlckn --, all valu-- w r- nor~aliz d to a tandard ga- barri r lay-r thickn -~of 25 ~ by multiplying th oxyg-n transmission r~te value by the ratio of barrler layer thickn -- to 25 ~
Noi-tur vapor tran-mi--ion rat- (NVTR) for the Example films wa- d t-rmin~d u-ing a P rmatran~ W6 (Nocon, Inc , Ninn apolis, Ninne-ota) NVTR data wa- coll-cted at 38 6 C and one-hundred perc-nt (100~) r l-tive humidity The reported value- are the v rag- of the v-lu-- obtain d for at l~ast thre ampl-~ of each Ex mpl- f~lm Sinc- NVTR i- inversely proportional to thickness, all valu-- wer~ normaliz d to a tandard moi-tur- barri r layer thickn -- of 25 ~ (micron~) by multiplying the NVTR valu- by the ratio of moi-tur- barri r layer thickn-ss (being th um of the moi-tur barri r and adh -iv- layer thickness--, a- r port-d in Tabl- 3 h r-in) to 25 ~ The oxyg~n tran-mi-~ion rat-- (O2TR) and moi~tur vapor tran mi-sion rat-- (MVIR) for Exampl-s 157-161 are -~
r-port-d in Tabl- 15 Th 8~ rate- demonstrate good oxyg-n and moi-tur- barri-r prop rti-- for th Bxampl- barrier film- of th-pr -ent lnventlon W093/llg4l2 1 ~ S ~ 7 2 P ~ /US92/10718 ___ __ Table lS
Oxyg-n tran-mi--ion rat-- ~02TR), a- xpre--ed in cc/m2/day-atmo-ph r~, and ~oi-tur- vapor 5 tra~mi--ion rate- (NVTR), a- xpr --ed in g/m~/duy-a~o-pher , for ~xumple- 157-161 Ca-tin~ _ ~x T mp C~TR ~VTR
No (-C) (cc/ ~/d-at~) ~9/~ l lS7 66 38 2 5 7 I ~-160 10 6 8 ___ 161 10 8 4 _ _ Th v riou- modification- nd alt-rution- of thi- invention will b appar-nt to tho - kill-d in th art without d parting Sro~ th cop and pirit of thi- inv ntion, and thi- invcntion hould not b- re-tricted to that et forth hcrein for illu-trative purpo~

'. '.

Claims (55)

PCT/US92/10718

1. A degradable multilayered structure comprising:
(a) a first layer of a polyolefin polymer containing a prodegradant system comprising from about 5 ppm to about 2,000 ppm of a transition metal in the form of a salt; and (b) a second layer of a polyolefin polymer contacting the first layer of the multilayered structure;
wherein the polyolefin polymer of the first layer, the second layer, or the first and second layers comprises a mesophase propylene-based material.

2. A degradable multilayered structure according to claim 1, wherein at least one of the polyolefin polymers is selected from the group consisting of polypropylene polymer, polyethylene polymer, polybutylene polymer, and combinations thereof.

3. A degradable multilayered structure according to claim 1, wherein the ratio of the thickness of the first layer to the thickness of the second layer is from about 1:10 to about 1000:1.

4. A degradable multilayered structure according to claim 1, wherein the ratio of the thickness of the first layer to the thickness of the second layer is from about 1:1 to about 10:1.

5. A degradable multilayered structure according to claim 1 wherein the mesophase propylene-based material is selected from the group consisting of mesomorphous polypropylene, a mesopolymer blend, a mesocopolymer, and combinations thereof.

6. A degradable multilayered structure according to claim 1 wherein the mesophase propylene-based material of the second layer contains the prodegradant system.

7. A degradable multilayered structure according to claim 1, further comprising a third layer of a polyolefin polymer contacting the surface of the first layer of the multilayered structure opposite from the surface contacted by the second layer of the multilayered structure.

8. A degradable multilayered structure according to claim 7, wherein the ratio of the thickness of the first layer to the thickness of the third layer is from about 1:10 to about 1000:1.

9. A degradable multilayered structure according to claim 7, wherein the ratio of the thickness of the first layer to the thickness of the third layer is from about 1:1 to about 10:1.

10. A degradable multilayered structure according to claim 7, wherein the polyolefin polymer of the third layer comprises a mesophase propylene-based material selected from the group consisting of mesomorphous polypropylene, a mesopolymer blend, a mesocopolymer, and combinations thereof.

11. A degradable multilayered structure according to claim 1, further comprising a layer of a naturally biodegradable polymer contacting the first, the second layer, or the first and second layers of the multilayered structure.

12. A degradable multilayered structure according to claim 1, wherein the structure will oxidatively degrade to embrittlement within about 14 days at a temperature of about 49°C.

13. A degradable multilayered structure according to claim 1, wherein the transition metal is selected from the group consisting of cobalt, manganese, copper, cerium, vanadium and iron.

14. A degradable multilayered structure according to claim 13 wherein the prodegradant system further comprises an auto-oxidative component.

15. A degradable multilayered structure according to claim 14, wherein the auto-oxidative component is selected from the group consisting of a fatty acid, a substituted fatty acid, a derivative of a fatty acid, and combinations thereof.

16. A degradable multilayered structure according to claim 15, wherein the fatty acid has 10 to 22 carbon atoms.

17. A degradable multilayered structure according to claim 16, wherein the auto-oxidative component comprises from about 0.1 to about 10 weight percent, based on the total weight of the first layer, and provides at least about 0.1 weight percent of unsaturated species and at least about 0.1 weight percent of free acid species in the first layer.

18. A degradable multilayered structure according to claim 17, wherein the fatty acid comprises an unsaturated fatty acid.

19. A degradable multilayered structure according to claim 17, wherein the auto-oxidative component comprises an admixture of saturated fatty acids and unsaturated fatty acid esters.

20. A degradable multilayered structure according to claim 18, wherein the unsaturated fatty acid substantially comprises species having two or more double bonds.

21. A degradable multilayered structure according to claim 17, wherein the structure will oxidatively degrade to embrittlement within 14 days at 60°C and a relative humidity of at least 80%.

22. A degradable multilayered structure according to claim 1, wherein the transition metal is present at a concentration of from about 25 to about 500 parts per million.

23. A degradable multilayered structure according to claim 1, wherein the first layer, the second layer, or the first and second layer, further comprises an anti-oxidant at a concentration of from about 0.02 to about 0.2 weight percent.

24. A degradable multilayered structure according to claim 1, wherein the first layer, the second layer, or the first and second layers further comprise a naturally biodegradable polymer at a concentration of from about 5 to about 50 weight percent.

25. A degradable multilayered structure according to claim 1, wherein the structure comprises a tube, a pouch, a bag, a tape, or a transdermal drug delivery patch.

26. A degradable multilayered barrier film comprising:
(a) a gas barrier layer of a chlorine-free, naturally biodegradable polymer, the gas barrier layer being substantially impermeable to oxygen gas; and (b) a moisture barrier layer of a mesophase propylene-based material contacting the gas barrier layer, and containing a prodegradant system comprising from about 5 ppm to about 2000 ppm of a transition metal in the form of a salt.

27. A multilayered barrier film according to claim 26, wherein the chlorine-free, naturally biodegradable polymer is a vinyl-alcohol containing polymer.

28. A multilayered barrier film according to claim 27, wherein the vinyl-alcohol-containing polymer is selected from the group consisting of ethylene vinyl alcohol copolymer, poly(vinyl alcohol) copolymer, and combinations thereof.

29. A multilayered barrier film according to claim 26, wherein the chlorine-free, naturally biodegradable polymer exhibits a permeability to oxygen gas of less than about 100 cc/m2/d-atm at 25°C and 0% relative humidity.

30. A multilayered barrier film according to claim 26, wherein the chlorine-free, naturally biodegradable polymer exhibits a permeability to oxygen gas of less than about 30 cc/m2/d-atm at 25°C and 0% relative humidity.

31. A multilayered barrier film according to claim 26, wherein the mesophase propylene-based material is selected from the group consisting of mesomorphous polypropylene, a mesopolymer blend, a mesocopolymer, and combinations thereof.

32. A multilayered barrier film according to claim 26, wherein the transition metal is selected from the group consisting of cobalt, manganese, copper, cerium vanadium and iron.

33. A multilayered barrier film according to claim 26, further comprising a layer of a polyolefin polymer containing the prodegradant system contacting the gas barrier layer.

34. A multilayered barrier film according to claim 33, wherein the polyolefin polymer is selected from the group consisting of polypropylene polymer, polyethylene polymer, polybutylene polymer, and combinations thereof.

35. A multilayered barrier film according to claim 33, wherein the polyolefin polymer comprises a mesophase propylene-based material selected from the group consisting of mesomorphous polypropylene, a mesopolymer blend, a mesocopolymer, and combinations thereof.

36. A multilayered barrier film according to claim 26, further comprising a layer of a polyolefin polymer contacting the moisture barrier layer.

37. A multilayered barrier film according to claim 26, wherein the prodegradant system further comprises an auto-oxidative component comprising a fatty acid, a substituted fatty acid, a derivative of a fatty acid, or combinations thereof.

38. A multilayered barrier film according to claim 26, wherein the barrier film will oxidatively degrade to embrittlement within about 14 days at a temperature of about 49°C.

39. A compostable multilayered barrier film comprising:
(a) a gas barrier layer of a chlorine-free, naturally biodegradable polymer, the gas barrier layer being substantially impermeable to oxygen gas; and (b) a moisture barrier layer of a mesophase propylene-based material contacting the gas barrier layer, the mesophase material containing a prodegradant system of an auto-oxidative component comprising a fatty acid, substituted fatty acid or derivatives, or blends thereof, the fatty acid having 10 to 22 carbon atoms, said auto-oxidative component being at between about 0.1 to 10 weight percent based on the total composition wherein the auto-oxidative component provides at least 0.1 weight percent of unsaturated species and at least 0.1 weight percent of free acid species in the total composition, and from 5 to 2,000 ppm of a transition metal in the form of a salt wherein the transition metal is selected from the group consisting of cobalt, manganese, copper, cerium, vanadium and iron.

40. A compostable multilayered barrier film according to claim 39, wherein the chlorine-free, naturally biodegradable polymer is a vinyl-alcohol containing polymer selected from the group consisting of ethylene vinyl alcohol copolymer, poly(vinyl alcohol) copolymer, and combinations thereof.

41. A compostable multilayered barrier film according to claim 39, wherein the chlorine-free, naturally biodegradable polymer exhibits a permeability to oxygen gas of less than about 100 cc/m2/d-atm at 25°C and 0% relative humidity.

42. A compostable multilayered barrier film according to claim 39, wherein the naturally biodegradable polymer of the gas barrier layer comprises ethylene vinyl alcohol copolymer containing the prodegradant system.

43. A compostable multilayered barrier film according to claim 39, wherein in a film form the film will oxidatively degrade to embrittlement within about 14 days at a temperature of about 60°C and a relative humidity of at least about 80%.

44. A degradable, radiation-resistant composition comprising a mesophase propylene-based material containing a prodegradant system comprising from about 5 ppm to about 2000 ppm of a transition metal in the form of a salt.

45. A degradable composition according to claim 44, wherein the transition metal is selected from the group consisting of cobalt, manganese, copper, cerium, vanadium and iron.

46. A degradable composition according to claim 44, wherein the prodegradant system further comprises an auto-oxidative component comprising a fatty acid, a substituted fatty acid, a derivative of a fatty acid, or combinations thereof.

47. A degradable composition according to claim 44, wherein in a film form, the composition will oxidatively degrade to embrittlement within about 14 days at a temperature of about 49°C.

48. A degradable composition according to claim 44, wherein the composition comprises a film, a fiber, a microfiber, or a tube.

49. A method of containing a perishable material with a degradable packaging film comprising:
(a) providing a degradable multilayered packaging film comprised of a first layer of a polyolefin polymer containing a prodegradant system comprising from about 5 ppm to about 2,000 ppm of a transition metal in the form of a salt and a second layer of a polyolefin polymer, wherein the polyolefin polymer of the first layer, the second layer or the first and second layers comprises a mesophase propylene-based material; and (b) contacting the perishable material with the second layer of the packaging film, wherein the second layer serves to prevent the dispersal of the prodegradant system from the first layer of the packaging film to the perishable material prior to disposal of the packaging film.

50. A method of forming a degradable, radiation resistant article comprising:
(a) extruding a propylene-based material containing a prodegradant system comprising from about 5 ppm to about 2000 ppm of a transition metal in the form of a salt to form an extrudate;
and (b) quenching the extrudate immediately after extruding to provide a radiation-resistant article of a mesophase propylene-based material containing said prodegradant system therein.

51. A method of forming a degradable, radiation resistant article according to claim 50, further comprising, coextruding a chlorine-free, naturally biodegradable polymer that is substantially impermeable to oxygen gas along with the propylene-based material containing the prodegradent system to form a multilayered extrudate, and quenching the multilayered extrudate immediately after extruding to form a multilayered article having at least one layer of a mesophase propylene-based material containing the prodegradant system proximate at least one layer of a chlorine-free, naturally biodegradable polymer.

52. A method of using a degradable multilayered film as a barrier film comprising:
(a) providing a degradable multilayered film comprised of a gas barrier layer of a chlorine-free, naturally biodegradable polymer, the gas barrier layer being substantially impermeable to oxygen gas, and a moisture barrier layer of a mesophase propylene-based material contacting the gas barrier layer, the mesophase propylene-based material containing a prodegradant system comprising from about 5 ppm to about 2000 ppm of a transition metal in the form of a salt; and (b) interposing the degradable multilayered film between a protected environment and an external environment such that gases and moisture cannot substantially pass through the degradable multilayered film.

53. A method of using a degradable multilayered film as a barrier film according to claim 52, wherein the degradable multilayered film comprises a packaging film containing a perishable product in the protected environment.

54. A method of using a degradable multilayered film as a barrier film according to claim 53, wherein the perishable product comprises a food product or a pharmaceutical product.

55. A method of using a degradable multilayered film as a barrier film according to claim 52, wherein the compostable multilayered film comprises a transdermal drug delivery patch, medical tape, or an ostomy pouch.