CA2123809A1 - Multilayered barrier structures - Google Patents

Multilayered barrier structures

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Publication number
CA2123809A1
CA2123809A1 CA 2123809 CA2123809A CA2123809A1 CA 2123809 A1 CA2123809 A1 CA 2123809A1 CA 2123809 CA2123809 CA 2123809 CA 2123809 A CA2123809 A CA 2123809A CA 2123809 A1 CA2123809 A1 CA 2123809A1
Authority
CA
Canada
Prior art keywords
barrier
layer
multilayered
film
barrier layer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
CA 2123809
Other languages
French (fr)
Inventor
Debra L. Wilfong
Richard J. Rolando
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
3M Co
Original Assignee
Individual
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Publication of CA2123809A1 publication Critical patent/CA2123809A1/en
Abandoned legal-status Critical Current

Links

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/06Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/07Flat, e.g. panels
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/07Flat, e.g. panels
    • B29C48/08Flat, e.g. panels flexible, e.g. films
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/16Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with all layers existing as coherent layers before laminating
    • B32B37/20Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with all layers existing as coherent layers before laminating involving the assembly of continuous webs only
    • B32B37/203One or more of the layers being plastic
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/022Non-woven fabric
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/024Woven fabric
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04Interconnection of layers
    • B32B7/12Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61FFILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F5/00Orthopaedic methods or devices for non-surgical treatment of bones or joints; Nursing devices; Anti-rape devices
    • A61F5/44Devices worn by the patient for reception of urine, faeces, catamenial or other discharge; Portable urination aids; Colostomy devices
    • A61F5/445Colostomy, ileostomy or urethrostomy devices
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29KINDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0037Other properties
    • B29K2995/0065Permeability to gases
    • B29K2995/0067Permeability to gases non-permeable
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29KINDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0037Other properties
    • B29K2995/0068Permeability to liquids; Adsorption
    • B29K2995/0069Permeability to liquids; Adsorption non-permeable
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/70Other properties
    • B32B2307/724Permeability to gases, adsorption
    • B32B2307/7242Non-permeable
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/70Other properties
    • B32B2307/724Permeability to gases, adsorption
    • B32B2307/7242Non-permeable
    • B32B2307/7244Oxygen barrier
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/70Other properties
    • B32B2307/726Permeability to liquids, absorption
    • B32B2307/7265Non-permeable
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00Containers; Receptacles
    • B32B2439/70Food packaging
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00Containers; Receptacles
    • B32B2439/80Medical packaging
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2535/00Medical equipment, e.g. bandage, prostheses, catheter
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2555/00Personal care
    • B32B2555/02Diapers or napkins
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/08Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the cooling method
    • B32B37/085Quenching
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/15Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state
    • B32B37/153Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state at least one layer is extruded and immediately laminated while in semi-molten state
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/13Hollow or container type article [e.g., tube, vase, etc.]
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/29Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913Rod, strand, filament or fiber
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/31855Of addition polymer from unsaturated monomers
    • Y10T428/31909Next to second addition polymer from unsaturated monomers
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/31855Of addition polymer from unsaturated monomers
    • Y10T428/31935Ester, halide or nitrile of addition polymer

Abstract

Multilayered barrier structures (10) comprising a gas barrier layer (12) of a non-chlorine containing organic polymer which is substantially impermeable to oxygen gas and a moisture barrier layer (14) of a mesophase propylene-based material are provided. These structures are environmentally compatible and radiation resistant, and exhibit one or more additional properties, including gas barrier properties, moisture barrier properties, toughness, heat sealability, softness, and quietness during wrinkling. Also provided are methods of preparing and using such multilayered barrier structures, and articles, such as films, pouches, and tubings, formed from these structures, as well as multilayer barrier structures with additional graft layers affixed thereto through the application of a dose of ionizing radiation.

Description

W O 93/11938 PCT/US92/1~082 21238~9 ~u~TILayERED BARRIE~ STRUC~URES

5Cro~--R~f~ronce to R~13tod Ap~lic~tio~
Thi~ application i8 a continuation-in-part of pending application Serial No. 07/810,001, filed December 18, 1991.

Fi~ld of th~ In~ntion Th$~ invention relate~ to multilayered barrier ~tructure~
exhibiting on~ or more propertie~, includinq ga~ barrier properti~e, moisture barrier prop~rti~s, radiation resi~tance, toughne~s, heat ~ealability, quietne0~ during wrinkling, and environmental compatibility. The invention al~o r~late~ to method~ of preparing and u~ing such multilayered barrier structures, as well a~ to articl~s formed from ~uch ~tructures, and to multilayered barrier structures with addit$onal graft layers affixed thereto.

Background of tho In~utiou Multilayered structures whLch are both substantially imperviou~ to gases and/or moisture are well known in the medical and food packaging industrie~. However, current atructur~s 0uffer from a variety of problem~, including environmental incompatibility, rapid deterioration after exposure to ~terLl~zing radiation, lack of toughn~, ineffective heat sealability, and an embarrassing tendency for personal care article~ manufactured from these structure~, Huch as o~tomy p~uches, to make noi~e due to wrinkling during use.
Currently, poly(vinylidene chloride) ~PVDC) is used as one of the materials of choice for the ga~ barrier component of barrier film~. For ostomy application~, a film of PVDC
~andw$ched between opposing layers of low density polyethylene (LDPE) is widely u~ed, with PVDC functioning as the gas barrier, and LDPE a~ th* ~oisture barrier. Also, polyvinyl chlor~de (PVC) can be used in the moistur~ barrier layer, or other layærs, of ~uch a structure. However, disposal of the~e chlorine-containing material~ pre~ents a number of environmental concerns, e~pecially relat~ng to incineration of these material~ after use in ho~pital~ or otherwi~e.
Both PVDC and PVC are vi~wQd as hazardou~ to the environment hnd to personal health. lncineration of PVDC/PVC
re~ult~ in r~lease of hydrochloric acid (HCl), providing the ma~or portion of RCl in incinerator flue gaces. Al00, PVDC/PVC
~8 ~u~p4cted of contributing to polychlorinated dibenzodioxin and furan toxin~ formed during lncineratlon. Lovels of thece toxin~
are up to thr~e time~ qreater in modical infectiou~ waste as compnred to municipal wa~te stream~. See e.c., Staff Report, WO 93/11938 PCI'/US92/10082
2~23~ "propo8ed Dioxiu~ Control M~a~ure for ~edical waste - Incinerators", State of California, Air Resource~ Board, Stationary Source Division, pp. 1-40 (May 25, 1990);' Medical Waste Policy Committee, "Perspectives on Medical wa~ten, A Report of the Neleon A. Rockefeller Inetitute of Government, State Un$versity of New York (June, 1989). In addition to incineration concerns exposure to di-2-ethylhexylphthalate (DEHP), a common - plasticizer utilized with PVDC and PvC, may pre~ent a number of health-related concerns, including reduced blood platelet eff$cacy, and potential link~ to liver cancer. see e.~
Allwood, M.C., ~The Releaee of phthalate e~ter plasticizer from intravenou~ administration sets into fat emul~ionn, 29 International Journal_of Pharmacoloov, 233-6 (1986).
Examples of barrier ~tructures incorporating ~uch hazardoue chlorine-containing materiale can be found in variou~ U.S.
PatBntB, 8uch aB U.8- Patent No. 3,524,795, which diBCloBeB a layered packaging material with a ga0 barrier layer comprised of various vinyl chlorine-containinq polymers, and U.S. Patent No.
4,786,561, which discloses a heat-shrinkable barrier film of an oriented polyolefin film coated on one side with a vinylidene chloride copolymer. In addition, numerou~ oth-r patent documente, including U.s. Patent No~. 5,009,648, 4,983,171, 4,906,495, 4,880,592, 4,826,493; Briti~h Patent Application No. GB 2138431; and Europ an Patent Application No. EP 0433060;
all disclose multilayered films which utilize chlorine-containing polymere for the con~truction of oetomy pouches and other personal care articles.
Cry~talline polypropylene provides excellent protection from moi~ture and ie often a material of choice for barrier structures, and for medical articles manufactured therefrom. In addition, cry-talline polypropylene exhibits a numbQr of other de~irable properties, such as non-toxicity, chemical resistance and inertness to dNgs and liquid media used with drugs, as well as its low co~t and ease of proce~ing by means of extrusion, ~olding, and the like. However, a disadvantage of crystalline polypropylene i~ its inherent inability to be heat ~ealed to other materials. Thue, modical articles, uch as barrier etructure~, or packaging for medical articles, often cannot be effectively heat-sealed in the manufacture and/or ass~mhly of the components of the article. Furthermore, similar problems may al~o occur in the packaging of ph o aceuticals or medical articlo~ in an ffort to protect them from unde~ir-d exposure to nv$ronmental contaminant~, including pathogenlc organisms.

W O 93/tl938 PCT/US92/10082 21~38~!~
Even after manufacture and a~sembly, ~uch barrier Etructur~ ~nd/or m~dical articl~s often requir~ additional prctection beyond secure heat ~ealing and package pr~ce~sing.
Accordingly, ~uch materials ~hould ba 6terilized ~t the time of production, and thereafter maintained in a sterile condition during storage. While not all ~tructures or articles require ~terilization prior ko u~age, structural components whLch are - r~si~tant to radiation ar~ more versatile for u~es in medical articles and packaging than components unable to maintain structural integrity after irradiation. Thus, the moat desirable mater$al for ~ barrier ~tructur~, m~dical ~rticl~, or the packaging formed th~refrom, i~ one which poss~s~e~ r~i~tance to the structurally demanding for~ of ~erilization, ~uch a~ by gamma or electron-baam radiation, ~ven if current usage~ of the structure or articl~s do not regu$re such ~terilization.
A pref~rr~d method of ~terilization use~ gu~a radiation, ~uch as radioactive cobalt 60, since it can be p~rformed on packagee ~ealed by heat or other methods, insuring total and reliable sterility of the contents. In addit$on, sl~ctron beam rad$ation c~n al~o b~ utilized to et~rilize barri~r ~tructures, medical articles, and/or their packaging material~. Furthermore, el~ctron beam radiation can also be u~ed to graft additional layer~, ~uch ae adhe~ion promoting layers, onto polymer films and oth~r articles. See e.a., U.S. Pat~nt No. 4,950,549.
Unfortunately, a further disadvantage of cryEtalline polypropylene is that gumma-irradiation or electron-beam irradiation cau~es degradation of it~ ~tructural integrity (e.g., c~u~ing embrittlement, discoloration, and thermal sen~iti~ity).
~hus, barrier film~ incorporating cry~talline polypropylene in moisture barrier layers, or oth~r layer~, and the articles or packaging material~ formed therefrom, are incapable of maintaining their ~tructural intogrity for a useful period of ~time aft2r expo~ure to ionizing radiation.
Exumple~ of barrier ~tructure~ and/or the articla~ formed from these structure6 which incorporate cry~talline polypropylene are shown in num~rous U.S. and foreign patenta, including U.S.
Patant Nos. 4,217,161 and 4,511,610, wh~ch di~clo~e multil~yered pla~tic ve~sel~ or conta~n~r~, ~nd procease3 for making such container~. The films compri~ing the~e v~s~els or containers include an Lnner ga~ barrier layer and outer moisture barrier layer~ of a cryetalline polyol~fin, preferably crystalline polypropylcne or cry~talline polypropyl-ne/ethylene copolymers.
U.S. Patent No~. 4,239,826 and 4,254,169, both diwlose mult$-layex barrier films with a core ga~ barrier layer of a WO 93/11938 PCI'/US92~10082 ....

~ 0 9 vinyl alcohol polymer or copoly~r between oppo~ing layer~ of a 2 polyolefin blended with a ch~mically-modified polyolef in containinq functional groupe add~d thereto. Example~ of chemically-modified polyolefine include vinyl acetate-vinyl alcohol copolymere, vinyl alcohol-ethylene vinyl acetate terpolymers, or higb deneity polyethylene w$th an uneaturated fueed-ring carboxylic acid grafted thereto. In addition, the filme can contain additional outer layers overlying the modified polyolefin layere of polyolefin polymere or copolymere, euch ae high, medium and low deneity polyethylene, polypropylene, ethylene vinyl acetate copolymere, ethylene acrylic acid copolymer~, nylon~, or blend~ thereof.
Other exemplary patentff include, Japane~e Patent Application No. Sho 60110851-217190, publlshed April 6, 1987, which diecloses a plaetic laminate comprioed of a polyvinyl alcohol gae barrier layer, with a plastic, olefin-containing, vapor barrier layer laminated thereto- A1BO~ U.S. Patent No. 4,064,296 discloeee a heat ehrir.kable, multilayer film having a gae barrier layer and outer moisture barrier layere of oriented olefin polymere, which have been croeelinked through expoeure to ionizing radiation. In addition, U.S. Patent No. 4,407,897 diecloeee a multi-layer polymeric etructure with a drying agent incorporated therein, and with outer moieture barrier layere of polymere euch ae polyethylene, polypropylene, or blends thereof.
Attempte have been made tc overcome degradation probleme aeeociated with crystalline polypropylene. For example, me~omorphoue polypropylene, ae de~cribed in U.S. Patent No. 4,931,230, and articles manufactured from meeGmorphou~
polypropylene, euch ae deecribed in U.S. Patent No. 4,950,549, provide reeietance to eterilizing irradiation. By controlling the method of preparing me~omorphoue polypropylene, throuqh the quenching of such polypropylene after hot-melt extrusion, the matarial or articlee formed therefrom eubetantially maintain their etructural int-grity after expoeure to ionizing radiation at do~agee sufficient to degrade crystalline polypropylene.
Unortunately, ~ingle-layer packaging filme and the like made from crystalline polypropylene, or even meeomorphoue polypropylene, are su-ceptible to tearing and puncturing which would disrupt the structural integr~ty of a- manufactured component or packaging film after assembly. Thue, the ueefulnee~
of a ~terilized medical article would be compromised by a puncture or t-ar in a polypropylene package. In addition, eingle-layer cry-talline polypropylene cannot be effectively heat eealed againet another material. Furthermore, even though W 0 93/11938 2 1 2 3 8 0 9 ~CT/US92/10082 - 5 - ~

me~omorphou~ polypropyl~n~ provide~ better heat ~eal~bility than cryotalline polypropylene, in certain inotance~ it ~till cannot provide A sufficient heat ~eal to manufacture a multi~omponent medi~al article, or to provid~ an effective radiation-~terilized package.
In an effort to overcome the~R d~ficiencie~, polymer blend~
of mesomorphou~ polypropylene and a polymer compatible with ~uch polypropyl~ne, a~ dascribed in Europ~an Patent Application No. O
405 793 ~as~ign~d to the same a~ignee a~ for thia appl$cation) have beQn devoloped. Th~e polymer blend~ exhibit enhanced phy~ical prop~rtie~, ~uch a~ heat ~ealabil~ty and t~ar ~trength, while maintaining the radiation rs~istance ~sociated with mesomorphou~ polypropylene.
Though ~esomorphou~ pol~propylene, or blend~ th~reoS, may be radiation re~i~tan~, the material~ compri~ing the gas barrier lAyer of barrier film~ typically are not. For example, as de~cribed in ~valca Technical Bulletin No~ 140 ~avail~ble from Evalca Co., of EVAL America, located in Lyle, Illinois), typical gas barrier polymers, such a~ ethylene vinyl alcohol ~EVOH) rapidly degrade after expo~ure to ionizing r~diation.
Furthermore, the polymer~c adhe~iv~ layer~ oft~n employ~d in ~uch barrier film~ would al~o be expected to rapidly degrade after exposure to ionizing radiation.
To date, no barrier film ex~ts which ccmbines radiation resi~tance with environmental compatibility. Furthermore, there are no ~uch barrier films which likewise exhibit one or more good packaging or component article propertie~, ~uch as heat sealability, toughness, softne~y and quietness.

8u arv of th- Inv~ntion There iB a need for an ~nvironmentally compatible multi-layer barr$er film capable of maintaining its structural integrity for a u~eful period of time after exposure to ionizing radiat~on at a do~age ~ufficiont to ~terilize such a film, a well a~ for article0 manufactured therefrom. Further, there is a need for ~uch a film w$th one or moro additional layera grafted thereto to modify the propert$e~ of the films, such as adhesion promotion. Profer~bly euch film~ would also be tough, h~at sealable, ~oft and/or quiet.
The pre~ent invention ovsrcom4s the dsficiencies of previous barrier f il~B and related articles by providing multllayored barrior structures which are both environmontally compat~bl~ and rosistant to ~torilizat~on via ionizing radiation, and which di~play barr~er properties to ga~os such a8 ~, C~, W O 93/11938 PCT/US92/1~082 2~3~ ~2S, and odore, a~ well as to moi~ture. In addition, these multLlayered barrier film~ exhibit one or more other desirable properties, including euperior toughness, heat eealability, quietneee and eoftn~es, ae well a~ ~nhanced or modified properti~e when additional layers ar~ grafted thereto through the appl~cation of a dose of ionizing radiation.
In particular, the preeent invention provides a ~ultilayered barri~r ~tructure having a gas barri~r layer of a non-chlorine containing organic polymer which iB eubetantially impermeable to oxygen gae; and a moieture barrier layor of a m~aophaee propylene-based materinl. Preferably, th~ ga~ barrier layer exhibits a permeability to oxygen ga~ of les~ than lO0 cc/m2/d-atm at 25C and 0~ relat~vz humidity. Since the multilayered barrier structures are chlor~ne-free, they can be dieposed of via inc~neration without pre~entinq a threat to the ~nvironment or pereonal safety.
The m2sophase propylene-based materials of th~ moisture barriex layer can compriee mesomorphous polypropylene, mssopolymer blends~ and/or mesocopolymers. In thie regard, the preeent invention can provide multilayered barrier structures wherein the moieturQ barrier layer comprises mesomorphous polypropylene homopolymer, or a meeopolymer blend of mesomorphous polypropylene and at leaet one eecond polymer. Preferably, the eecond polymer i- a compatible polymer wh~ch eynargistically increase~ one or more of the physical properties, euch as toughnes3, heat sealability, eoftness, and/or quietness, of the multilayered barrier ~tructure.
In another aepect, the present invsntion also can provide multilayered barrier etructures wherein the moisture barrier layer comprisse a m~eocopolymer. Like the mesomorphoue polypropylene and meeopolymer blends of the present invention, meeocopolymere can provide moisture barrier layer(e) of the multilayered barrisr etructurs of the present invention that are tougher, softer, guieter, and/or more heat eealable than a correepond$ng copolymsr with cryetalline propylene therein.
Th~ pr~e~nt Lnvsntion aleo prov$d~s a msthod for pr~paring a multilay~red barr$sr structurs by coextrud$ng a propylene-baeed material along w$th a non-chlor$ne conta$ning organ$c polymer which ie eubetant$ally impermsable to oxygen gae, to form a multilayered extrudate, and qu~nching the extrudate immediately after extruding to provide a multilayered barr$er etructur~ with a core layer of thQ nonchlorine conta$n$ng organ$c polymer and at leaet one layer of a meeophaee propylsne-baesd mater$al ad~acsnt thereto.

WO 93/11938 PCI`/US92/10082 21238~9 In add;tion, the pre~ent inv~ntion provides a multilayered barrier ~tructure for u~e as a barri~r film. Specifically, a method of interpo~ing a ~ultilayer~d barrier film, in~luding a ga~ barri~r layer of a non-chlorin~ containing organic polymer, and at le~t on~ mo~stur~ barrie~ layer of a me~ophas~ propylene-ba~ed m~terial, b~twean a protec~ed environm~nt and an external environment, such that gase~ and moisture cannot ~ubatantially ph~ therethrouqh, i~ provide~.
Further~ore, the pre~ent invention alMo provide~ variou~
ar~icle~ formed from the multilayered barrier ~tructure~ of the present invention, includinq, o~to~y pouche~, incontinen~e products, tapes, tubing~, tran~dermal drug-delivery patches and paokaging for medical and/or food product~. Although the de~ired applications for the~ multilayered ~arrier structurRs are in a film fonm, the multilayered con~tructions cculd also be u~ed for applications requiring riqid and ~e~i-rigid structure~, such as for Inedical ccntainer~, as well as for flexible structures, ~uch as tubings and tapes.
In yet another a~pect, the present invention provid2s a multilayered barrier structure h~ing a gao barrier laysr of a non-chlorine containing organic polymer which i~ ~ub~tantially impermeable to oxygen gh~, 2 moi~ture barrier layer of a me~ophase propylene-based material, and a graft layer affLxed to at lea~t a portion of the multilayered structure by a dosage of ionizing radiation. ~referably, the graft layer enhance~ one or more properties of ths multilayerod ~tructuro, including ~urface adhe~ion, coefficLent of friction, oxygen parm~ability, moi~ture permeability, or combinations thereof.
Al~o, the pre~ent invention also provides a method for preparing a multilayered barrier structure by coextruding a propylene-ba~ed material along with a non-chlorin~ containing organic polymer which i~ 3ubstantially $mpermeable to oxygen gae, to form a multilayered extrudate, quenching the extrudate immediately after extruding to provide n multilayered barrier structure w$th a core layer of the nonchlorine containing organic polymer and at leaet one layer of a me~opha~e propylene-based ~aterial proximato the core layer, and graftiny a graft layer to at leaflt a port on of the multilay~red ~tructure through expo~ure to a dosage of ionizing radiation.
Further, the preaent invention al80 provides radiation resi~tant articles formed from the multilayered barrier ~tructure~ of th~ pre~ent in~ention having a ga~ barrier layer of a non-chlorino containing organic polymer which i~ substantially impermeable to oxygan gas, at lea~t one moisture barrier layer of ,..i; ~
3 a ~ a m~ophase propyl~ne-bas~d material, and a graft layer ~ffixed to ~t l~a~t a portion of the ~ultilayered ~tructure by a do~age of ion$zing radiat~on.
For an additional appreciation of the 8cope of the pre~ent invention, a more detailed description of the invention follows, with reference to the drawings.

Definition~
For the purpo~ of thi~ invention the defin$tion of ~polymer~ $nclude~ a homopolymer, a copolymer, or an oligomer, as w~ll a~ any mixture~ or blend~ of one or more homopolymere, and/or one or more copolymer~, and/or one or more oligomer~.
The term "copolymer" refer~ to a polymeric material produced by the polymerization of two or more di~imilar monomere, e$th~r with or without another ~unction~l group, ~uch a~ maleic ~nhydrid~, grafted thereto, as well as to a homopolymer w$th a functional group grafted thereto. ~huc, the term "copolymer" includss, without l~mitation, random copolymers, block copolymers, ~equential copolymere, and graft copolymer~
~Propylene-ba~ed mat~rial~ refer~ to propylene monomer, or polypropylen~ polymer.
~he tenm "moiety" refer~ to any sub~tance which can be combined with a propylene-b~sed material to form a copolymer, and include~, without limitatLon, a monomer, a polymer, or a molecule.
"Me~opha~e propylene-ba~ed material", refer~ to a propylene-baced material, in tbe ordered, me~opha~e form~ which iB neither amorphous, nor 80 ordered ac to con8titute the isotactic I cry~talline form (e.g., cry~talline polypropylene) a~
descr$bed by G. Natta et al., "Structure and Propertie~ of Isotactic Polypropylene~, Del Nuovo Cimento, Suppl. Al, Vol. XV, Serie X, No. l, 1960, pp. 40-51, the disclosure of which i8 herein incorporated by reference. A mesopha~e propylene-based material ~ formed by quenching a propylene-ba~ed material from the melt state, aB defined below, and $ncludes, without lim$tat$on, me~omorphou~ polypropylene, me~opolymer blends, and/or m~ocopolymer~, as tho~e terms are defined below.
"guench$ng~, r~fer~ to the process of immediately and rap~dly cooling propylene-based mat~rial from the melt state such that me~ophase propyl~ne-based material iB obtained.
As u~ed herein, ~a non-chlor$ne conta$n$ng organic polymer which l~ ~ubetant$ally ~mpermeable to oxygen ga~ refers to polymer$c materials wh$ch are e~entially free from chlorine, and W ~ 93/11938 2123~D9 PCT/USg2/10~82 .~
_ g _ which have oxygen transmis~ion rate~ of le~ than about 150 ce/m2tday-atmo0phere at 25C and 0~ relative humidity.
nOlefin polymer~n or "polyolefin~n, refers to polymer~ of the unsaturated hydrocarbon~ of th~ gener~l formul~ CnH2n, 5 including copolymer~ of olefins with other monomer~ such a~
ethylen~ with vinyl acetate.
"M~somorphouc polypropylene" (mPP) rsfer3 to the polypropylen~ homopolymer in the mesopha~e form.
The t~rm "mesopolymer blend" refers ~o a mixture of 10 mesomorphou~ polypropylene with at lea~t on~ add$tional polymer (her~in~Ster a ~econd polymer").
The term "me~ocopolymer" refer~ to a copolymer of a propyl~ne-b~sed material and a di~cernable amount of at lea~t one moiety thnt iB quqnched from the melt ~tzte to form a ~opolymer 15 in the me~ophaue form.
The "Rule of ~ixturea" refers to a means for determining the hypothetical valuec for a given phy~ical property of a blend of two or more polymers. Ths hypothetical value reprecentc the cummat$on of the proportion~l contribution of the actual value~
20 of the phy~ical property from each of the const~tuent polymerc, baced on the we~ght percents of the constituent polymer~
incorporAt~d into the blend. Under the "Rule of ~ixturec", the value for a giYen phy~ical property (property "X") of a blend of two polymers (polymere A & B) can be calculated according to the 25 following formula: Hypothetical value of property ~X" for a blend of polymer~ A & B = (Weight percent of polymer A in the blend) x (actuAl value of property ~X~ for polymer A) + (Weight - percent of polymer B in the blend B) x (actual value of property "X" for polymer B).
A ~eompat~ble polymer~ refer~ to any eecond polymer which when combined with macomorphoue polypropylene, form~ a me~opolym~r blend wherein at least one weight fraction of the m~opolymer blend has a mor~ de~irable phy~ical property than would be expected under the Rule of Mixtures.
A ~graft layer~ refers to any additional layer affixed to at least a portion of the multilayered barrier structure~ of the prQsent invention by grafting a compound or compounds to the ~urface of th~ barr~r structuree througb the application of a do~age of ionizing radiation, preferably a dooage of electron 40 beam radiation. For example, an graft layer of acrylic acid and/or dimethylacrylumide can be grafted to at leaat a portion of the ~urfac~ of the multilayered barrier structures of the pre~ent invention through the expo~ure of such compound~s) and barrier 0tructure~ to a doeage of electron beam radiation between about 2J~,2,3~09 ,".,,.. ~, 5 kGy (0.5 ~rad) and about 200 kGy (20 Mrad). In ~uch an in~tance, th~ grat~d acrylic acid and/or dim~thylacrylamide layer would form a ~urface adhesion layer that prohotes the adhesion of other material~ to the modified surface of the 5multilayered barrier ~tructure.
A ~temporing additive" refer~ to any polymer, which when co0bined into one or more layor~ of a multilayered barrier ~tructur~ according to the pre~ent inv~ntion, functions to modify the f$1m propertie~, su~h as Young~ modulus, fracture strain, 10and/or the frequency in Hertz ~z) of sound emittsd from a multilayered barrier ~tructure when wrinkled, such that a soft, tough, and/or quiet multilayerod barri~r strueture is obtained.
The "structural integrLty" of a multilay2red atructure can be msa~ured by th~ percent ~longation to br~ak of that ~tructure.
15With resp~ct to radiation rQ~istance of such structure~, percent elongation to br~ak is u~ed to mea~ure th~ extent of degradation or embr~ttl~ment of these ~tructures after irradiation. A
Aub~tzntLally con~tant p~reent elongation at break over ~everal months after irradiation is indicat~ve of ~ubstantial maintenance 20of structural integrity of a ~ultilayered structure over that p~riod after irradiation.

Br~-f De~cri~tion of th- Drawin~
The invention may be further lllu~trated by reference to 25the accompanying Drawing wherein:
FIG. 1 is a croa~-sectional illustration of a first embodiment of a multilayered barrier etructure according to the pre~ent invention;
FIG. 2 iB a crose-sectional illustration of a second 30embodiment of a multilayered barrier structur~ according to the pre~ent invention;
FIG. 3 i~ th~ wide-angle x-ray diffraction pattern of me~omorphous polypropylene;
FIG. 4 is th~ wide-angle x-ray diffraction pattern of an 3580/20 mesopolymer blend by weight of ~e30morphous polypropylene with polybutyl~ne;
FIG. 5 is the wide-angl~ x-ray diffraction pattern of a 50/50 mesopolym~r blend by weight of mesomorphous polypropylene with polybutylen~;
40FI5. 6 i~ the wide-angle x-ray diffraction pattern of a 20/80 meaopolymer blend by weight of mesomorphoue polypropylene with polybutyl-ne;
FIG. 7 ie the wide-angle x-ray diffraction pattern of polybutylene;

wo 931-lg38 21 2 3 8 ~ 9 PCI/US92/100~2 ~ 11 -- .
FIG. 8 ia the widQ-angle x-ray diffraction pattern of a 50/50 m~opoly~er bl~nd by weight of me~omorphous polypropylene with polybutylenes FIG. ~ i~ thR wid~-angl~ x-ray diffraction pattern of cry~tall$ne polypropylene;
FIG. 10 i~ the wid~-angle x-ray diffraction pattern of an 80/20 blend by w~ight of cry~talline polypropyl~ne with polybutylen~;
FIG. 11 ~ the wide-angle x-ray diffr~ction p~ttern of a 50/50 blend by weight- of cry~tallLne polypro~ylene with polybutylQn~
F~G. 12 i~ another wide-angl~ x-ray diffraction pattern of a 50/50 blend ~y weight of crystalline polypropyleno with polybutyl~n~;
FIG. 13 ~ B a graph comparing Young's modul~ of the multilay~red barr~er ~tructure~ of ~xample~ 1-4 and Compariaon Example 5 (line A) with hypothetical linear value~ for Example~
1-4 and Comparison Example S (line B~;
FIG. 14 i- a graph comparing the yield ~tr~s~ of the ~ult~layer~d barrier otructure~ of Example~ 1-4 and Compari~sn Exampl~ 5 (l~ne A) wit.h hypoth~tical linear value~ for Example~
1-4 and Comparison 2xample 5 (line B); ~-:
FIG. 15 iB a graph comparing Young' B modulu~ of thQ
multilay~r~d barri~r 0tructuros of Example~ 56-60 ~line A) with hypothetical linear value~ for Example~ 5S-60 (line B);
PIC. 16 iB a graph comparing Young' B ~OdUlUB of the multilayer~d barrior ~tructures of Example~ 60-64 (line A) with hypothetical line~r value~ for Example~ 60-64 (line B);
FIG. 17 .iB a graph comparing the fracture strain of the multilayered barri~r ~tructure~ of Examples 51 and 58-61 (line A) with hypothetic~l linear value~ for Examples 51 and 58-61 (line B);
FIG. 18 i~ a graph comparing the radical decay as measured in normalized radical poak hsight in spin~/gram as a function of elap~ed time in hour~ for the multLlayar barrier ~tructures of Example 46 ~lin~ A) and Comparlson Example 52 ~line ~) after expo~ure to a 50 kGy do~ge of electron beum radiation;
FIG. 19 i~ a graph co~paring the radical decay a- measured in normalized radical p~ak height in ~pins/gram a~ a function of elap~ed time Ln hour~ for tho multilayered barrier structuros of Ex~mple 47 ~line A) and Compar~on ~xamplo 53 ~line B) after 0xpo~ure to a 59 kGy do~age of electron beam radiation;
FIG. 20 ~ a graph comparing the r~dical docay a~ measured in normalized rad~cal peak height in epins/gram as a function of 2 ~ 2 3 ~ 9 - 12 -elapsed time in hour~ for the multilayered barrier ~tructure~ of ExamplQs 48 and 50 (line A) and Compari~on Example~ 54 (line 8) and 55 (line C) after expoeure to a 50 kGy dosage of'electron beam radiation;
FIG 21 iB a graph of the noise ~pectra intenoity (v~
v~r~us frequency (Hz) of the multilayered barrier atructure of Example l;
FIG 22 i~ a graph of the noise spectra inten~ity (V) ver~us freguency (Hz) of the multilayered barrier ~tructure of Compari~on Example 7;
FIG 23 i~ a graph of the noi~e ~pectra inten~ity (V) ~ersus frequency (Hz) of the multilayered barrier structure of Example 2;
FIG 24 is a graph of the noise spectra inten~ity ~V) ver~us frequency (Hz) of the multilayered barrier ~tructure of Compari~on Example 8;
FIG 25 iB a graph of the noise ~pectra intensity (V) ~ersus frequency (Hz) of the multilayered barrier structure of Example 6;
FIG 26 iB a graph of the noise spectra inten~ity (V) versu~ frequency (Hz) of the multilayered barrier etructure of Comparison Example g;
FIG 27 ie a graph of the noi~e spectra intensity (V) versue frequency (Hz) of the multilayered barrier ~tructure of Example 57;
PIG 28 i8 a graph of the noiee spectra intensity (V) ~ersu~ freguency (Hz) of the multilayered barrier structure of Compari~on Example 73;
FIG 29 is a graph of the noise ~pectra intensity (Y) versus frequency (Hz) of the multilayered barrier structure of Example 63;
FIC 30 i8 a graph of the noise spectra intensity (V) ~ersu~ freguency (Hz) of the multilayered barrier ~tructure of Comparison Example 78;
FIG 31 iB a graph of the noise spectra intensity (V) versus fregu-ncy ~Hz) of the multilayered barrier ~tructure of Example 64;
FIG 32 ia a graph of the noise spectra intensity (V) vQr~us fr-guency ~Hz) of the multilayered barrier structure of Exampls 79;
FIG 33 is a graph of the noise spectra intensity ~V) versus frequency ~Hz) of th- multilayered barri-r structure of Example 66;

W O 93/11938 2 1 238 ~ 9 PCT/US92/10082 . ~.

FIG. 34 i~ a graph of th~ noi~ ~pectra int~n~ity (v) versus fr~quency (Hz) of the multilay~red barr~er ~tructure of Compari~on Example 81;
FIG 35 is a graph of the nois2 ~pectra inten~ity (V) versue frequency (Hz) of the multilayered barrier etructure of Example 69; and FIG 36 ie a graph of the noise epectra inten~ity (V) versus frequency ~Hz) of the multilayered barrier ~tructure of Comparieon Example 84 D-t~iled D-~criDt~on of ~mbodim nt~ of th- In~ntion ~ult~la~-r-d Barri-r Structur-~
FIGS 1 and 2 ~how cro~c-eectional viewe of two embodiments of multilayer-d barrier etNcturee 10,30 according to the prasent invention FIG 1 showe a firet embodiment The multilayered barrier etructure 10 comprieee a gas barrier layer 12, with a moisture barrier layer 14 contacting oppoeing cide~ 16,18 of the gas barrier layer 12 While it is preferable that the multilayered barrier etructure 10 include moieture barrier layer~
14 on ach of the oppoeing eidee 16,18 of th- gae barrier layer 12, it will be appreciated that in c-rtain applicatione, that the multilayered barrier etructure 10 n-ed only include a single moieture barrier layer 14 on one of the oppoeing eidee 16,18 of the gae barrier layer 12 FIG 2 showe a eecond embodiment of a multilayered barrier structure 30 having a gae barrier layer 32 and oppoeing moieture barrier layere 34 proximate the opposing sides 36,38 of the gae barr~er layer 32 In addition, this embodiment includee an -~
optional adhe~ive layer 40 contacting the oppoeing eidee 36,38 of the gae barrier layer 32, in between th gas barrier layer 32 and moi~ture barrier layere 34 Thue, the second embodiment contemplatee a five layered barrier structure, comprieing a central gae barri-r layer 32, w~th adhesive lay r~ 40 on each of the opposing side~ 36,38 of the ga- barrier layer 32, and a moieture barrier layer 34 contacted with æach of the two adhesive laysrs 40 However, it will be appr-ciated that any multilayæred barrier ~tructure 10,30 with two or mOrQ layers, which includes at læast one gae barrier layer 12,32, and at least one moisture barrier layer 14,34, is considered to fall wtthin the scope of the prosent invontion Throughout tho remaining de~cription of the embodlments of the invention, primary referenco will be had to the embodiment illustratod in FIG 1, unl-se otherwiee indicatod ~owover, it WO 93/11938 PCl`/US92/10082 ?, ~23~9 - 14 - ;
~ will be appreciated that thi~ description also applies to the ~mbodiment illu~trated in FIG. 2.

Oa~ snrri~r L-voF
The ga~ barrier layer 12 of the ~ultilay~red atructure 10 i~ compri~ed of a non-chlorine containing organic polym~r which i~ subs~ant~ally impermeable to oxygen ga8. Preferably, the non-chlorin~ containing organic polymQr exhibits a permeability to oxygen (2) ga~ of 123~ than 100 ccfm2/day-atmoaphere (hereinafter oxpressed a~ "cc/m2/d-atm"), mDre preferably leqs than 30 cc/m2/d-atm, and most preferably le~ than 5 cc-25 y/m2/d-atm, where the permeability measurement~ are taken at 25C
and zero percent (0~) relative humidity. It will al~o be appreciated that the 2 permeability mea~urem0nts are expressed for a ~ultilayered barrier ~tructure with a gas barrier layer thicknesa of 25 ~ (microns). Accordingly, appropriate adju~tment of the penmeability valu~s muot be made, depending upon the thi~kne~s of the gas barrier ~mployed in a structure, a~ well as the number of ga~ barrier layers utilized therein. In either ca~e, the value~ ~hould be normalized to a total gas barri~r layer thicknes~ of 25 ~. All value~ were normalized to standard gaB barrier layer thickno~ of 25~ by multiplying thR oxygen transmission rate value by the ratio of barrier layer thicknes~
to 25 ~. In addition to ~ubatantial impermeability to ~ gas, it will further ~e appreciated that the gas barrier layer 12 also exhibits barrier properties to C02, N2 and H2S gases, a~ well as to other ga~e~ and odors.
Nonlimiting ex~mple~ of non-chlorine containing organic polymers in accordance with the pre~ent invention include vinyl alcohol containing polymer~, such a~ ethylene vinyl alcohol copolymer (EVOH) and polyvinyl alcohol ~PVOH), polyacrylonitrile, polystyrene, polye~ter, and nylon, either alone, or blended with each other, or another polymer. Preferably, the non-chlorine containing organic polymer compr~see a vinyl alcohol containing polymer euch as EVOH or PVOH, w~th EVOH being particularly preferred. Aleo, the 9aB barrier layer 12 should preferably be comprieed of ~ubetantially pure EVOH, moet preferably comprieing 99% or more EVOH. However, it aleo within the scope of the present invention to utilize blende of EVOH with other polymers, such ae ethylon~ v$nyl acetat~ copolymer.

W O 93/11938 PCT/US92rlO082 ,, 21238og ~b~tur~ ~arri-r ~A~er Th~ barri~r propQrtie~ of the ga~ b~rrier layer 12 of tAe multilayered barr~er ~truct~re lO arc reduced in high' ~oi~ture condition~. Accordingly, a moi~ture barrier l~yer 14 in accordance with the principles of the prR~ent invention i8 contacted w~th at laaAt one ~ide 16,18 of the gas barrier layer 12 to provid~ moi~ture protection for the ga~ barrier layer 12.
The moi~tur~ barr$er layer l4 iB compri~ed of a mesophase propylene-ba~ed material, ~uch as mesomorphous polypropylene, mesopolymer bl~nds, and/or me~GcopDlymers. ~ncorporation of the mo$sture barrisr laysr 14 comprieed of me~omorpbous polypropylene homopolymer, me~opolymar blend~ containing m2somorphous polypropylene, a~d/or me~ocopolymer~, into the multilayered barrier structur~ lO accordlng to the pre~ent invention un~xpectedly enhance~ th~ o~er~ll properti~ of tho multilayered barrier ~tructure lO. In addition, by com~ining ~e~omorphoua polypropylene with ~elected second polymers (i.e., compatible polymers) according to the prasent invention, me~opolymer blends may be obtained which exhibit ~nhanc~d prop~rtie~ over what would b~ expected of ~uch blend~ under the Rule of Mixture~, as dafined above. Furthermor~, m~ocopolymers used in the isture barr~er layer 14 al~o exhibit enhanced properties over that of copolymers incorporating the sa~e moietieE with propylene in a cryotalline form. When thess me~opolymer blends and/or mesocopolymero are incorporated into the multilayered barrier structure lO via the moioture barrier layers 14, the overall properties of the multilayered barrier otructure lO ie likewioe enhanced.
For exumple, ao deocribed in European Patent Application No. 0 405 793, published January 2, l99l, t`he disclo6ure of which is herein incorporAted by reference, polymer blendo of mesomorphouo polypropylene and a ~compatible~ polymer exhibit increaoed reoistance to the degrading effect~ of ionizing radiation, including gamma and electron-beam radiation, which are typically employed to oterilize packaging materials and medical articleD. Furthermore, the meoopolymer blendo may exh~bit other desirabl~ propertie~ attributable to the compat~ble polymers, as that term io deflned here~n, euch a- increaoed toughneoo, heat oe~lability, ooftn~s, and quietneoo, depending upon the particular compatiblo polymer combined ~n the meeopolymer blend.
Surprioingly, ut~lization of meeomorphouo polypropylene, mesocopolymers, and/or meoopolymer blendo, euch ao thooe dioclo~ed ln European Pat~nt Application No. 0 405 793, in the moicture barri~r layer(o) 14 unexpectedly impart- increaeed radiation reoiotance to the overall multilayered barrier 2 3 8 ~tructure lO, in~luding the gas barr~er layer 12 and optional adhesive layers 40, and ~nhance~ other overall propertie3 of the multilayered barrier ~tructure lO of the pre~ent inven~ion, ~uch a~ toughne~s, heat ~ealability, ~oftne~ and/or quietneE~. See alao, Applicants' copQnding and co-filed U.S. Patent A~plications, Attorney Dockat No~. 47990USA2A and 47990USAlB
(Rolando et al.) and 47~9lUSAlA and 47991USA3B (Wilfong et al.).
Al~o, the me~opolym2r bl~nd~ employed in the present invention neod not be limited to comb$nation~ of mesomorphou~ polypropylene with ~ompatibl~ poly~er~ that term is defin~d herein.
In~tead, any of on~ or more ~econd polymer~ which can be combined with polypropylene, melt extruded, and quenched, ~uch that the re~ulting mesopolymer blend includes mesomorphou~ polypropylene i~ considered to be within the scope of the present invention.
However, it i~ preferable that the second pclymer ~nhance the phycical propertieA or characterict~c~ of th~ me~opolymer blend when combined with m~omorphous polypropylene.
Nonlimiting example~ of ~econd polymers include polybutylene (PB); polybutylsne copolymere; ata~tic polypropylene re~in~ available from Himont USA Inc., of WiLmington, D~laware;
polypropylene-ethylene copolymer~; ethylene vinyl ac~tate copolymer (EVA); acid modified EVA; anhydride modified EVA;
acid/anhydride modified EVA; ethylene acrylic acid copolymer (EAA); acid modified ethylene acrylate; anhydride modifi~d ethylene acrylate; poly(4-methyl pent~ne); polyethylene, polyethylene copolymer~, low den~ity polyethylene (LDPE), linear low density polyethylene (LLDPE), high density polyethylene (HDPE); and ~cid/anhydride modified polypropylenes. Particularly preferred second polymer~ include polybutylene, EVA, and EAA. It will be appreciated that thia li~t of second polymers is not exhau~tive of second polymers which can be combined with me~omorphous polypropylene to form the mesopolymer blends utilized in certain smbodiments of the moi~ture barrier layerl6) 14 of the multilayered barrier structure lO of the present invonticn. See~ e.c., Applicant~' copending ~nd co-filed U.S.
patent application, Attorney Dockot No. 47991USAlA, assigned to the Aa~ignee of the pre~ent invention, the d$ wlosure of which is here~n incorporated by reference.
As notod above, the moi-turo barrier layer( B ) 14 may be formed solely of mosomorphous polypropylene. However, in other em~odiments, a moi~turo barri-r lay-r 14 comprised of a mo~opolymer bl-nd of ~e-omorphou- polypropyl-ne and one or more econd polymor will bo proferred. In such ombodiments, the optimum weight fraction of the socond polymer with the W 0 93/ll938 P ~ /Us9 /10082 ... 2l238o9 me~o~orphou~ polypropylane dep~nds upon the intended u~e and deaired propertie~ for the moi~ture barrier l~yer 14, and the final multilayared b~rrier ~tructure 10 fonmed t~erefrom.
Generally, when a me~opolymer blend i~ to be ~mployed, it ie d~irabl3 to ~dd ae much ~econd polymer a~ poe~ible to provide th~ needed etrength, heat sealability, ~oftneff~, quietneee, and/or other dee~rable propertie~, without compromising the radiation ræ~i~t~nce provided by the meeomorphou~ polypropylene of the m~Bopolym~r blend-However, when utilizing a m~opolymer blend, it i~ within th~ acop* of thie invention to ~dd a di~cernibly ~inimal amount of the sscond polymer to the meeomorphoue polypropylene to provide a mesopoly~r blend, and re~ulting moieture barrier layer 14, guenched to preaerve the m~omorphou~ pnlypropylen~, having exc~llent re~ietance tv terilizing radiation, and betterphy~ical properti~e, ~uch a~ heat senlability and toughnes~, than when the me~omorphoue polypropylene homopolymer i3 utilized alone.
Optionally, ae little ae one percent ~1~) by weight of the eecond polymer to the weight of the me-opolymer blend, quenched to preserve meeo~orphoue polypropylene, can form an acceptable meeopalymer blend util~zed to form the moisture barrier layer(e) 14, and resulting multilayered structure 10, of the pre~ent invention. Such a m~opolym~r blend can prove acceptable for certain medical applications requiring superior radiation resistance, and can also 6xhibit other de-irable barrier and/or packaging propert$es.
It ie also within the cope of the present invention to add a discernibly minimal amount of polypropylene to the second polymer to pro~ide a me~opoly~er blend, quenched to preeerve mesomorphous polypropylene, wh~rein the moisture barriar layer 14, and reeultinq multilayered barrier etructure 10, exhibits excellent barrier and/or packaging properties, and acceptable radiation re~istance. Thue, when a meeopolymer blend is called for, opt$onally, as much ~ ninety-nina percent (99%~ by weight of the eecond polymer to the welght of the meeopolymer blend, may for~ an acceptabl~ mseopolymer blend according to the preeent invention.
It ic de-$rab1e that the weight fraction range of the eecond polymer i~ from about f~ve percent (5~) to about ninety-five percent (95%) by weight, and more de~irably from about ten p~rcent (10%) to about ninety percent (90~) by weight of the me~opolymer blend.

2~3~ Preferably, when it iG de~irable to balance the be4t propert$Q~ of the meaomorphou~ polypropylene and the 6econd polymex in tha meaopolymér blend, the weight fraction of the ~cond poly~er ~hould rang~ from about twenty percent (20~) to S About eighty p~rcent ~80%) by welght, more pr~ferAbly from about twanty-five p~rcent ~25%~ to about ~eventy-fLv~ percent (75~) by wei~ht of ths me~opolymer blend, and mo~t preferably from about - forty parc~nt ~40~) to about sixty percent (60%) by weight of the maaopolymer bl~nd.
Pre~iou~ly, it was unknown for copolymer~ of propylene-based material~ wlth other moieties to form a mesopha~e form upon quenching. How~ver, it ha~ now been surpri~ingly discov~red that th~ me~ocopoly~ers provide many, if not all, of the same advantage0 a~ omorphou~ polypropylene and mesopolymer blend~, 6uch as incr~ased resistanc6 to ionizing radiation, toughne~s, softness, heat ~ealability and/or quietness. Accordingly, mesocopolymer~ can be used to form the moiature barrier layer(s) 14r and/or optional adhesive layer(s) 40, of the multilayered barrier 3tructure 10 of the present invention.
Any moi~ty, or combination of moieties, can be used in conjunction with a propylene-ba~ed material to form the mesocopolymers according to the pre~ent invention. See~ e.~., Applicant~' copending and cofil~d U.S. patent application, Attorney Docket Nos. 47990USA2A and 47990USAlB, a4~igned to the As~ignee of the pr eBent invention, the disclo~ure of which i~
herein incorporated by reference. For example, the propylene-based material can ccmprise propylene monomer and the moiety of a different monomer other than propylene, ~uch as ethylane or butylene, that when polymerized, melt extruded, and quenched, from a mesocopolymer within the ~cope of the present invention.
The mssocopolymer~ ~ccording to the pre3ent invention generally fall within three cla4~es. The first clas~ of ~opolymer comprises a mesocopolymer wherein the other moiety comprise~ a monomer, such a~ ethylene or butylene, that iB
inserted between propylene monomer~ in a copolymer chain.
Accord~ngly, cla~ one copolymer~ according to the present invent~on include, without l~mitation, random, eeguential, and block copolymer~- A commercially availabl~ exumple of such a copolymer, which when quenched forms-n me~ocopolymer according to the pra~ent invention, 18 Petrothane1~ ro~in No. PP7300-XF
(Quantum Ch~m~cal, Inc.).
Thc ~econd clas~ of copolymer~ according to the pre~ent inventio~, which when quenched can provide th~ m480copolymers of the above described class one copolymer~, with another moiety WO 93/1193~ PCI/US92/10082 .: ~ 21~3~og yrafted to the copolymer chain. For example, the other moiety can comprine a functional group, such as maleic anhydride or acrylic acid, qrafted to the copolymer chain, to provide'enhanced melt flow rat~ e well a~ other properti~s. See! e.~., U.S.
P~tent No. 4,003,874, and Britiah P~tent No. 1,393,693, the di~clo~ure~ of which are herein incorporated by reference. A
commerci~lly availabla ex~mple of ~uch a copolymer i~ Plaxar 420 ~Qu~ntum Chemical, Inc.).
The third, and final, general cl~ of Gopolym~rs according to the pre~ant invention, which when guenched can provide the me~ocopolymer~, compri~e a polypropylene homopolym~r with a moiety, such as male~c anhydride or acrylic acLd, grafted to the polymer chain. A commercially ~vail~bl~ example of such a copolymer i~ Admerl~ QF551A (~it~ui Plastic~, Inc.).
In a pref~rred embodiment, the mesocopolymer comprises a claes one copolymer of propylene monomer with a d~scernable amount of at lea~t one other monomer. Pref~rably, the propylene monomer will compri~e from about 1~ to about 99%, more preferably from about 50~ to about 99~, and mo~t preferably from about 91%
to about 99~ by weight of tho mesocopolymer, with the reMainder of the me~ocopolymer compri~ing the other monomer, or monomers.
The monomers to be combined with propylane to form the mesocopolymers according to the pre~ent ~nvention can include any monomar that would polymerize with propylene in the prosence of a suit~ble catalyst, includinq ethylane, butylene, pentene, methylpentene, and the like. Preferred monomers include ethylene ~nd butylenQ, with ethylene being particularly preferre~.
In a particularly preferred embodiment, the mesocopolymer according to the pre~ent invention compriae~ a copolymer of an ethylQne monomer with a propyl~ne monomer, that i~ qu~nched to provide the ~e~ophase form of the copolymer. Prefarably, the ethylene monomer compri~es from about 1~ to ~bout 25%, more preferably from about 1% to about 20%, and most pxeferably from about 1% to about 10~ by weight of the mesocopolymer, with the remaining monomer compxi~ing propylene.
The ~Q~ocopolymer of the pre~ent invention can alao be formed when the copolym0r i~ blended in polypropylene homopolymer at from bout on- porcent to about ninety nine percent by weight.
A commer~ially ~vailable exampl~ of ~uch a mixture iB Shell re~in FC05N, an ethylene-propylene copolymer mixed at a level of 14 perc~nt by w~ight to 86 perc~nt by weight of a polypropylene homopolymer. A~ w~th the copolymer alone, the blend of copolymer and homopolymer mu~t be quenched immediately after extru~ion to provide a me~ocopolymer according to the precent invention.

W O 93/11938 PCT/US~2/100~2 ~3S~9 OPti~nal Adh~iv~ ~a~r~
A~ noted above, the ~ultilayered barrier ~tructure 30 according to the present invention may also include' optional adhe~ive layers 40, a~ illustr~ted Ln FIG. 2, interposed between th~ moi~ture barrier layer( B ) 34 and the ga~ barrier layer 32.
~he adhe~ive laysrs 40 ~rve to adhere thG ga3 barrier layer 32 and moi~ture b~rrier layer~ 34 together, when the ~elected material~ comprieing thD~e layers are not naturally compatible, and therefore, not able to adhere to one another after coextru~ion. For example, when the ga~ barrier layer 32 in compri~ed of EVOH copolymer, and th~ moi~ture barrier layers 34 are comprised of a me~opolymer blend of m4somor~hous polypropyl~ne and polybutylene, adhe~ive layero 40 are required to adhero the layer~ into a unit~ry, multilayer~d barrier structure 30 according to the present invention.
When an adhe~ive l~yer 40 iB emp~oyed, the adhesive layer 40 ~hould be comprised of material~ which provide ~tructural integrity to the ~ultilayered barrier structure 30 of the present invention, without ~ubstantially affecting the barrier properties of the ga~ b~rrier l~y~r 32 ~nd moisturQ barrier layers 34. In thi~ r~gard, it will be proferred to use a me~ocopolymer in the adheaive layer 40, ~ince adhe~ive mesocopolymer~ exhibit the ~ame advantageou~ properties as the meoomorphous polypropylene, me~opolymer blend~, and/sr me~ocopolymers comprising the moisture barrier layer 34 of the multilayered barrier structure 30 of the pre~ent invention. -~
It will be appreciated that adhesion between the gas barrier layer 12 and moioture barrier layer(s) 14 can always be achieved by utilizing a blend of polymer in either, or both, of th~se layers, wherein at least one of the polymers employed i~ a conotituent polymer of both the ga~ barrier 12 and moi~ture barrier 14 layers. For example, in a structure such a~
illuotrated in FIG. l, by uoing meeomorphouo polypropylene ~mPP) in the moioture barrier l~yer(o) 14 and a blend of EVOH and mPP
in the ga~ barrier layer 12, the mPP appearing in both layers will r~ult in a natural adheoion between the moioture barrier layer(o) 14 and gas barrier layer 12, such that the need for an additional adhesive layer(~) 40 will be eliminated. However, it will aloo be appreciated that util$zation of blends of polymers in the ga~ barrier layer 12 may reoult in a reduction in the barrier properties of the multil~yered barrier etructure l0.
Nonlimiting ~xampleo of adh~oive layero 40 according to the pr~eent invantion includs functionaliz~d polyolefino, euch as anhydride modifi~d polypropyleneo, acid modified polyolefino, WO 93/11938 2 1 2 3 8 0 9 PCI/U~92/10082 , .. ., ~

acid/anhydride modified polyolefin~, or other similar adhesive polymer~, copolymer~ or blend~, ~uch ae ethylene vinyl acetate copolymer (EYa). Examples of preforred adhesive polym~r's include AdmerT~ QF551A, a polypropylene graft copolymer adhesive (Mitsui Plastics, Inc.l, and PlexnrI~ 420, a propylene/ethylene copolymer adhesive ~Quantum Chemlcal Corp.).
It will be appreciated that the adhe~ive layers 40 can comprise functionali2ed derivatives of me~ocopolymers that ~xhibit many or all of the advantageous properties, such as radiation r~siotance, and incr-ased toughne~s, hoat-sealability, softness ~nd/or guietn~ss, ~s well aB providing sufficient adhesion to af~ix the moi~ture barrier layer 34 and gas barrier layer 32 together. For Example, it is within the ~cope of the present inv~ntion for funct~on~lized adh~sive copolymers, such as AdmerI~ and Plexarl~ to compri~e the moisture barrier layer 14 of the pr2sent invention, quench~d to preserve the mesophase form of thE me~ocopolymer after hot melt extruaion. In ~uch an embodiment, the adheaive moisture barrier layer 14 could be affixed to other layers or surfaces to provide for speci~lized multilayered barrier ~tructure~ lO according to the pre~ent invention 10. For example, an Adhesive moisture barrier layer 14 could have a woven or nonwoven layer affixed thereto, to provide a more comfortable surface against a wear~rs skin when the multilayered barrier structure 10 is incorporated into an ostomy pouch or the like. ~owever, it will also b~ appreciated that any adhesive which i~ compatible with the ga~ barrier layers 12 and moisture barrier layers 14 according to the present invention, i~
considered to fall within the scope of the pre~ent invention.

TomD-rin~ Additi--~
AB noted above, utilization of mesopha~e propylene-based materials, such as m~somorphou~ polypropylene, mesopolymer blends, and/or masocopolymers, in the moisture barrier layer 14 of the multilayered barrier structure 10 can result in a ~ofter and/or quieter ~tructure than a compar~ble structure containing crystalline polypropylene. It has also been discovered that incorporation of a temperinq additive, as that term is defined herein, into one or morQ of the layers of the multilayered barrier structure 10 results in a structure which i8 quieter when wrinkled or ru~tled, and/or which is softer in term~ of compliability and drape, than the correspond~ng ~tructure lacking in the tempering additive. ~onl~miting examples of tempering additive~ include ethylene copolymer~, ~uch as ethylene vinyl W O 93/t1938 PCT/US92/10082.

acetate copoly~er (E~A) and ethylene acrylic acid copolymer ~ (~AA) r polybutylene, polybutyl~ne copolymer~, or combinations thereof. Pr~f~rred tempering additives ~n~lude ~A, EAA, polybutylQne, and combination~ thereof.
In a pr~ferr~d smbodim~nt, an eff~ctive amount of the tempering additive iB incorporated into the mo$~ture barrier layer 14, either as the ~econd polymer of the mesopolymer blend, or a~ an optional additive w$th the mesomorphous polypropylena, me~opolymer blend, and/or me~ocopolymer of the moi~ture barrisr lay~r 14. For examplo, th~ moi~ture barrier layer 14 of the pr~ent invention can compri~e a me~opolymer blend with EVA
copolymer incorporated therein. Incorporation of EVA copolymer into the moioture baxri~r layer 14 of the multilay~r~d barrier structure 10 according to the present invention result~ in a multilayered barxier ~tructure 10 which i~ sub~tantially guieter (ae measurQd by frequency of sound emitted in Hertz) when wrinkled or ru~tled, than a comparable structure containing cry~talline polypropylene and/or crystalline copolymer~.
Furthermore, incorporation of EVA copolymer into th~ moi~ture barriar layer 14, or other layer~ of the mult~layerod barrier ~tructure 10, can lower the modulus (Young's Modulu~) of the moisture barrier layer 12, re~ulting in a ~ofter multilayered barrier ~tructure 10.

Other Additi~--Totally optionally, to provide ~pecific additional properties to the multilayered barrier otructure 10 of the present invention, the moisture barrier layer(s) 14, the gas barrier layer 12, snd/or the adhesive layer~ 40, may also contain con~ntional additives such as antistatic materials, pigments, dy~s, fill~rs, pla~ticizer~, ultraviolet ab~orbers, quenching agents ~uch as mineral oil, and the like. However, the ~esophase propylene-based materials, including the me~omorphou~
polypropylene, mesopolymer blends, and/or mesocopolymers, of the moisture barri-r layer 14 do not require any stabilizers, anti-oxidants or ths like to nable the mesopha~e propylene-based materials, and accordingly, the resulting moistur- barri-r layer 14 and multilayer-d barrier structur~ 10, to withstand the ~ffect~ of ionizing radiation, and st$11 substantially maintain the ~tructural integrity of the multilayered barrier structure 10 for a useful period of time after irradiation.

.

~ro~-rti-- ~f ~ultlla~rod sarri-r ~tructur~
In general, non-chlorine containing organic polymers, ~uch as the preferred ~OH copolymer comprising the ga~ barrler layer 12 of the ~ultilayered barrier ~tructur~ l0 of the pre~ent invention, rap$dly degrade after being exposed to ionizing radiatio~, such as gamma or electron-beam radiation.
Furthermore, the penetrating nature of ionizing radiation would be exp~cted to cau~e auch a d~gradation of non-chlorine containing organic polymers, even when layer~d within a mult~layered ~tructure or film. Surprisingly, incorporation of a gaB barrier layer 32 and optional adhe~ive layer~ 40, in conjunction with one or mor~ moi~ture barrier layer~ 34, into a multilayered barrier ~tructure 30 according to the pre~ent $nvention, resulta in a multilayered barrier ~tructure 30 with increased resi~tance to ionizing radiation. Sp~if~ally, even after ionizing radiation dosage~ from about 1 kGy (0.l Mrad) to 200 XGy (20.0 Mrad), the multilayered barrier ~tructure 30 degrade~ at a ~ubstantially slower rate than a comparable ~tructure with moisture barrier layer~ lacking mesomorphou3 polypropylene, me~opolymer blende, andJor me~ocopolymer0.
In addition to incraased radiation reFi~tance, the combination of a moisture barrier layer 14 and a ga~ barrier lnyer 12 into a multilayered barrier ~tructure l0 according to the present invention ~ynergi~tically incr~es the ~oftness (i.e, decrea~e~ the stiffnes~, as measured by the Young'~ Modulua and the yield stre~), the toughnesa (as measured by the fracture ~train), and the quietness (a~ measured in Hertz (~z) of sound emitted), of the multilayered barrier structure l0 above that which would be expected under the Rule of Mixtures, as that term 30 iB defined above. In addition, this ~ynergi3tic effect on the softneas, toughne~s, and/or quietne~s of the multilayered barrier structure l0 can be further enhanced when a tempering additive, ~ as that tenm is defined above, is incorporated into the moi~ture barrier layer 14 of the multilayered barrier ~tructure l0. Al~o, when u~ing a moisture barrier layer 14 formed from mesopolymer blende according to the pre~ent invention, the multilayered barrier structure~ l0 can exhibit enhanced propertie~ which are, at l0ast Ln part, characteri~tic of the ~econd polymers used in the me~opolymer blends of th~ mO~sturQ barrier layers 14. For example, use of polybutylene along with me~omorphous polypropylene in a me~opolymer blend comprising the moisture barrier layer~ 14 enhanc-s the heat sealability and tou~hne~s o~
the overall multilayered barrier etructure l0.

~ ~ ~Furthermor~, the radiation re~istance provided by me~ophaae -propylens-based ~aterial~, ~uch ~ mesomorphou~ polypropylen~, me~opolymer blonds, ~nd/or ~ocopolymer~, s~rv~a to'maintain these enhanced char~cterietic~ for a u~eful period of time after ionizing irradiation at et~rilization do~age~. Thus, the multilayered barrier structure ~0 of the pr~sant invention can withetand ion$zing radiat$on, euch as gamma radiatio~, which ie employed to sterilize the etructur~ or an article formed th~refrom. Generally, it ie deeir~bls that the doeage of gamma radiation be in the rang~ from about 1 kGy (O.l Mrad) to about 200 kGy (20 Mrad), and prefersbly in the range from about lO kGy (1 Mrad) to about 60 kGy ~6 Mkad) for ~terilization of medical articles .
Importantly, the elimination of chlorine-containing compound~ ae compon~nte of th~ gas barrier layer 12, moieture barrier layers 14, optional adheeive laycrz 40, or ae additives to these layers, provides an environmentally compatible, multilayered barrier structure lO, which can be dispoffed of, euch h~ through incineration, without endangering humans. Thue, varioue environmental hazards aceociated with th~ diepoeal of typical barrier materiale, euch ac polyl~inyl~ene chloride) (PVDC) ~nd poly(vinyl chlorid~) ~PVC), can be avoided. In particular, ~aterials such ~e PVDC and PVC releae~ hazardoue substance~, such as hydrochloric acid ~HCl), polychlorinated dibenzodioxin, and fuxan toxine during incineration. In contra~t, the material~ couprie~ng the multilayered barrier etructure lO, according to the preeent invention are broken down to environmentally compatible water and carbon dioxide during incineration.
~et~od~ of Pr-~aration The proceae of blending known mixturee of polymere ie well known to thoee ekilled in the art. See e.~., Mathews, PolYmer Mix~nG TechnolooY, Chapter 3 (Applied Science Publiehers, Eesex, England, 1982), the di~closure of which $e herein incorporated by reference. In the caes of the pseeent invention, the ~ethod of blending involvee the ue~ of an xtruder by feeding the polymers (in ~he proper waight percentagee, and where need be, after being dry-blended or compounded together) through a heatod coextrueion proce~e. Thue when a me00polymer blend ie to be employed, polypropylene and the Hecond polymer ar~ firet dry blended togethor prior to being melt extrud-d a0 tha moieture barrier layer 14. Furthermore, the non-chlorino containing organic polymer of the gae barrier layer 12, and functionalized WO 93/11938 21 2 3 ~ o 9 PCr/US92/10082 polyol~fin of the optional adh~ e lnyer 40, are h~ated and cosxtruded with th~ ~oisture bar ier layer 14 to for~ the multilayered barrier atructure 10 according to th~ preeent in~ention.
coextru~ion L~ a polymer proce~eing method for bringing diver~e polymeric mat~rial~ togeth~r to form unitary layered structures~ ~uch a~ f ilm8, ~heet~, fibers, and tubing~ This - allows for unique combination~ of materials, and for etructures w~th multipl~ function~, euch aa, barrier characterist;c~, radiation re~tance, and heat sealab~lity. By combining coextru~ion w$th blown film proce~sing, film ~tructure~ can be made which have no inhersnt waste and ~uch lower capital inv~stment over flat film coaxtrusion. However, flat f$1m proc~s~ing technigus~ provid~ an oxcellent method for making the multilayered barrier ~tructur~ 10,30 according to th~ present invention.
Component polymer or copolymer materials according to the present invention can be coextruded from the melt ~tate in any shape which can be rapidly cooled to obtain a multilayered b~rrier structur~ 10 with a moioture barrier laysr 14 whioh include~ me~ophas~ propylene-baend mat~rials. The shapa and/or th$ckness of the coextruded ~tructure will be d~pendent upon the efficiancy of the particular extrucion equipment amployed and the quenching syst~m~ utilized. G~nerally, films and tubes are the preferred coextruded ~tructures~ Only under appropriate, low temperature condition~ (~.o., bolow 60C), can multilayored barrier ~tructures 10 be uniaxially, biaxially or multiaxially oriented to further enhanco their barr~er and phy~ical propertios without losing the mesophase form of polypropylene or m~socopolymers in tho ~oisturo barrier layer(s) 14.
To obta$n multilayored barrier structure~ 10 with a moisture barrier layer 14 havin~ mesopha~e propylene-based material~, such a~ mosomorphou~ polypropylene, me~opolymer blond~, and/or mo~ocopolymer~, the coextruded ~tructures must be quenched in a mannor such that the mesophaee form of polypropylane and/or ~qsocopolymer i~ obtained. ~iller, ~On the Exi~tence of Near-Range Order in Isotactlc Polypropyleno~", in ~y~, one, 135 (1960), and U.S. Patent No. 4,931,230, both of tho disclo~uree of wh~ch are h~ro~n incorporated by referonce, di~cloeo ~u~table methods known to tho~o skilled in the art for the proparation of mesophaoe form of polypropylans.
A~ doscr~bod by th-s~ publlcations, variou~ known mothods of quenching a~ Boon A~ po8Biblo~ and proforably, imm~diatoly after extrusion, can be usod to obtain a mesomorphous ~3 polypropylone homopolymer, meeopolymer blend, and/or meeocopolyner having the mesophaee form of polypropylene and/or meeocopolymer therein Quenching methods includ~ plu~ging the co~xtruded etructurs into a cold liquid, for example, an ice water bath (i Q , quench bath), epraying the coextruded structure with a liquid, such as wnt~r, hitting th~ film with a str~am of cold air, and/or running thc coextrud~d etructure o~r a cooled roll, qu-nch roll, or drum The coextrud~d multilayered barrier structure lO of the preeent inv~ntion iB prefQrably quenched immediately aftsr extrucion by contact with a quench roll, or by boing plunged into a quench bath For a film thicknee~ of from about 6 ~ to about 625 ~, where a quench roll ie used, roll temperature is maintained at a t~perature below about 38C, proferably below about 24C, and the coextrudate is gonerally in contact with the quench roll until eolidified Ths quench roll ehould be positioned relatively closQ to the coextruder die, the distance being depQndent on the roll temperature, the extrusion rate, the f~lm thicknese, and the roll epeed Gen~rally, the dietanc~ from th die to the quench roll ie about 0 25 cm to 5 cm WherQ a quench bath ie ueed, the bath temp~rature is preferably maintained at a temp~rature below about 4C The bath ehould be poe$tioned relatively cloeQ to the die, generally from about 0 25 cm to 13 cm from th- dio to the quench bath Ae noted above, the coextruded multilayered barrier etructure lO according to the preeent invention should not be eub~ect~d to any tr~atment, euch ae orientation or stretching, at temperaturee above 60C Specifically, the employment of such treatment tochniquQ~ at t~mperaturee above 60C would transform the meeophaee form of propylene-baeQd materiale in the moisture barri~r layer 14 of th multilayered structure lO to predominantly undeeir~d cryetalline form of propylone-based materials .

U--fuln-~ of th- In--nt$on In a preforrQd conetruction, the multilayered barrier etructure lO according to the pre~ent invQntion compriees a five-lay-r barri-r film 30 euch as illuetrated in FIG 2, with a core gae barrier layer 32 of ~VOH copolymer, two intermediate adheeive layere 40 of a functionalized polyolofin, and two outer moi-turo barrler layere 34 compri-ed of a me-ophaee propylene-bae-d material-, uch ae me-omorphoue polypropyl-ne homopolymer, a me-opolymer blend of me-omorphoue polypropyleno and 2 1 2 3 ~ 1) 9 polybu~ylena, EVA copolymer, EAA ~opolymer, a me~ocopolymer, or combination~ of any of these polymerH or copolymers.
Multil~yered barrier films 10 according to th~ pre~ent inv~ntion will b~ ~Mpecially useful in o~tomy pouch appl~cation~, wh~re ~curity from odor, int~grity of ths d~vice, and integrity of the underlying material~ are requirement~. Multilayered barrier films 10 can be die cut and heat ~aaled with conventional - equipmant, and ar~ compatible wLth currant attachment sy~tems and o~tomy pouch manufacturing practice~. Since the multilayered barriex films 10 aro moi~ture re~i~tant both inside and out, the r~ult$ng o~tomy pouch i~ capabla of being worn during swimming and ~howering. Optionally, w$th incorporation of a polymeric tomper~ng additive, ~uch a~ EVA copoly~er, EAA copolymer, polybutylene, pclybutylene copoly~er~, or combination~ thereof, into variou~ layer~ of the barrier film 10, the re~ulting o~tomy pouch can be quieter when wrinkled .or ru~tled during the movem~nt~ of a waarer of ~uch a pouch. In addition, other u~eful articles such a~ tapes, tubings, containers, tran~dermal drug-delivery patches and variou~ packaging material~ can also be formed from the mult~l~yered barrier film 10 of the pr~ent invention. Thus, the multilayered barrler film 10 of the pre~ent invention i~ useful to form or cover a proteçtive environment from an external environment, euch that moi~ture and/or ga~e~
cannot ~ubstantially pas~ through to a degradable product contained the~sin, or a ~urface covered thereby. For example, the multilayered barrier film lO can be u~ed to contain a food product or a phanmaceutical product in a protected environment, to which moistur~ and/or gaae~ from the external en~ironment cannot ~ub~tantially pas~ into. Similarly, the multilayered barr~er fiLm lO can comprise a transdermal drug delivery patch, or medical tape, or an ostomy pouch, which protects the body of a mammal, or the waste products generated by the mammal, from degradation due to exposure to moi~ture and/or ga~e3 in the external environment.
Oth-r LaY-r! nd ~bdif~cat$ons Article~ formed from the multilayered barrier structure~
10,30 need not be limited to throe-layered and five-layered axamplc~ illustrated in FIGS I and 2. In addition, the~e mult$1ayered barrier ~tructures 10,30 can be further modified for ~pecialty applicAtions by adding additional layers thereto. For ex~mple, a specialty oetomy pouch compri~ing a multilayered barrier Htructure lO o~ the prasent in~ention could be formed by laminating a fabric backing of a wo~en or nonwo~en material tnot W O 93/1l938 PCT/US92/10082 ~3~a9 - 28 - -`
ohown) to a ~urfhce of the ostomy pouch. ~his fabric backing would act ~o provide a ~oft layer again~t a wearer'~ ~kin, and thuo make the ootomy pouch more comfortable and non-cl3nging.
A f~bric back~ng could b~ applied to the multilayered barrier otructure l0 of the preeent invention in a number of differ~nt way~. For example, a layer of a nonwoven material, formed from a poly~r such as polypropylene, could be affLxEd to the multilayered barrLer structure l0 of the present invention by an intervening adhesive layer. Preferably, ouch an adheoive layer would compri~e a functionalized meoocopolymer according to the present invent~on. In addition, a fabric baeking could be affixed to th~ multilayered barrier atructure lD by running both layero through hot rollers or nips, that would heat oeal the fabric and barrier layer~ tsgether. In such a heat oealing operation, it would be preferred to maintain the hot rollers at sufficient temperature to provide an effective heat seal between the layer~ without oubstantially affecting the mesophace form of the mesomorphous polypropylene, meoopolymer blends, and/or meoocopolymer~ of the moioture barrier layer( B ) 14 of the multilayered barrier structure l0.
AB an alternative, a fabric backing could be applied to the multilayered barrier structure l0 of the preoent invention by affixing a web of melt blown microibers thereto. For example, melt blown polymer microf~bers could be hot melt extruded from a die into a high velocity air ~tream, and onto a surface of the multilayered barrier structure l0 according to the present invention. See, e.q., Report No. 4364 of the Naval Research Laboratorieo, published ~ay 25, 1954, entitled "Manufacture of Superfine Organic Fibers~, by V.A. Wente et al., and V.W. Wente et al., ~Superfine Thermopla~tic Fibers", 48, Indu3trial EnG$neerin~ Chem~strv, 1342 (1956), both of the disclooures of which are herein incorporated by reference. In a preferred embodiment, the meit blown microfiber web affixed to at least one side of the multilayered barrier structure l0 could be formed of mescmorphoue polypropylene, meoopolymer blends~ and/or mesocopolymer~, by guenching the hot blown microfibers immediately after extruoion. For example, the microfibers could be quenched by opraying the f~ber~ with a liguid such as water, or by collectlng the fibero on the multilayered barrier structure 10 thnt $o in contact with a cooled collector drum or roll.
In addition, the outer surfaces of the multilayered barrier structure of th~ pre-ent invention may aloo deoirably have one or ~ore graft layerc affixed thereto to enhance other propertie~
ouch ao surface adheoion, oxygen and/or moisture permeability, W 0 93/l1938 2 1 2 3 ~ O 9 PCT/US92/10082 coeffici~nt of frict~on, or oth~r propertie3 dQsirable to tho~e ~killed in th~ ~rt. For ~x~mple, not be way of limitation, ~urface adhe~ion i~ desirable in ord~r to provide the application of primera and oth~r coating~ that would not otherw$~e adhere well to the ~tructures of th~ present invention.
Pref~rably, a graft layer, ~uch as a ~urface adhe~ion layer, is grafted to th~ outer ~urfaceq of th~ multilayered barri~r ~tructure~ 10 by al~ctron beam radiation at do~ages of frQm about 5 kGy (0.5 Mrad) to about 200 kGy (20 Mrad), and preferably at about 50 XGy (5 Mrad), according the procedure~
prov~ded in U.S. Patent No. 4,950,549, the di3closur~ of which iB
her~in incorporated by r~f~rencQ. Nonlimiting oxamples of compounda that can be graft~d ~o tha ~ultilayer~d structures of th~ pr~ent invention to for~ a ~urfacs adhesion lay~r include acrylic ac~d ~AA), dimethylacrylamide (DMA), N~vinyl-2-pyrrolLdone (NVP), ~nd a copolymer of NVP and trimetnylolpropane-triacrylate (NVP/TMPTA)r Other pot~ntial compounds that can also be usQd a~ a graft layer include glycidyl acrylate, hydroxyethyl acrylate, hydroxymethyl acrylate, 2-vinyl pyridine, ~ulfoethyl methacryl~t~, diisopropylacrylamid~, or N,N-diæthylamino acrylate. Particularly preferred grafting compound~ usQd to form a ~urface adhesion layer on a least a portion of the multilayered structurQ~ according to the pre~ent invention include AA (Aldrich Chomical Co., Milwaukee, NI) and DMA (Chem Services, Inc., 2ii; Westche~ter, PA).
The following non-lLmit$ng examples are pr3vided to further illuatrate the invention.

~SAMPLES 1-4 aND 6. AND
CO~PARI80N EYAMPL~S S AND 7-10 Ten, fivo-layered coextruded barrier films were made using a flat film proce~ con~isting of 3 extruder~, a 5-layer CloerenT~ feQdblock (cloeren Company, Orange, Texa~3, and a ~inglo manifold film extrusion die. ~he barrier films w~re generally coextrudcd at a fil~ thickness of about 75 ~, with each moisture barrier layer ~hereinafter layer ~A~) being about 30 thick, each adhe~$ve layer (hereinafter layer ~B~) being about 4 thic~f and the gas barrier layer ~hereinafter layer ~C~) being about 8 ~ thicX. ThQ con~truction of the fi~e-layered barrier film~ corre~ponded to the multilayered ~tructure illu~trated in FIG. 2 herein.
Layer A compri~ed mixtures by weight of polypropylone re~in (hereinafter ~PP~) (PP3576; Fina Oil and Chomical Co.; melt index - 9 g/10 min.) , and polybutylene resin (hereinafter "PB~) ~3~ 3~ - ~
~PB400; Shell Ch~mical Co.; melt index = 20 gJlO ~in.). Layer B
compri~ed a polypropylen~ ba~ed adhe~iYe layer of Admerl~ QF551A
re~in (Mit~ui Pla~tic~, Inc.; melt index = 5.7 g~lO min.~. Layer C was made of an ~thylone-vinyl alcohol copolymer (her~inafter ~EVOHn) ~EVA~T~, El05 Evalca Co.; melt ind~x = 5.5 g/lO min.).
The ~P/PB mixture~ wer~ dry blended before being melted and co~xtruded. Film extru~ion condition~ for Example~ 1-4 and 6, and Co~pari~on ~xumple~ 5 and 7-lO are given in Table l. Table 2 list~ specific film c4nstructions for layer A of th~ Exu~ple and Compari~on Example filme and their casting roll (quench) temperaturee. The te~perature of the quench roll for Examples 1-4 wa~ maintained at 10C, and at -1C for ~xampl~ 6, in order to control the mesomorphou~ structure of the polypropylene in the polymer blend. The multilayered films were co~xtruded onto a qu~nch roll ~paced 2.54 cm from the extru~ion di~. Th~ films w~r~ in contact with the quench roll for about 2 seconds and were coextruded at a rate of about 17 meters per minute~ (mpm). The adhe~ive layer and barrier l~yer constructione were kept conetant Across all of the~Exampl~s and Comparison Example~.
Thicknes~ of each layer in th~ multilayered barrler film~
of Examples 1-4 and 6, and Comparison Example~ 5 and 7-lO waff determined via optical microacopy from film cross-~ections.
Samples of each of the Example film~ were cut and trimmed, and then embedded in 3N Scotchcastl~ Brand electrical resin No. 8 (3M, St. Paul, Minnesota). The films were then cut into crosa-~ection0 u~ing a microtome. Specimens were placed on a glass slide in immer~ion oil with a cover slip placed on top.
Layer thickne~ses were then determined via tran~mitted bright field optical microscopy. Values for the moi~ture barrier layer thicknes~e~ (designated a~ layers lA and 2A), adhQsive layer thickne~e~ (deaignated ae layers lB and 2B), core ga~ barrier layer thickne~ (de~ignated a~ layer C), and total film thickne~
are ~hown ln Table 3.

Film extrusion condition~ for Exampl~ 4 and 6, and for Comparison ExamplQs 5 and 7-10.
;_ . . ...... ~ ~
Melt Screw Die ¦
Temperature SpeedTemparature A 221 (RPM) 232 . 11 C ~7 _ 20 _ 232 WO 93tll938 2 1 2 3 8 0 9 PCI/US92/10082 . ~

`, . .. ,., ,, .. , ,.. , ." , , , . __ ~ -Tabl~ 2 Weight percentage ratio of polypropylene ~PP) to polybutylene IPB), and ~a~ting (quen~h) roll temporaturo~ layer A of Exa~ple~ 1-4 and 6, and Compl .ri~on Ex~mple~ 5 and 7-10.
Rat$oCasting Roll Example PP: PBTemp~rature Number _ !wt ~ ) ( C!
Ex. 1 100/0 10 .-Ex. 2 80/20 10 _ _ :
Ex. 3 50/50 10 Ex. 4 20/80 10 Comp. Ex. 5 0/100 10 Ex. 6 _ 50/50 -1 Comp. Ex. 7 100/0 66 Com~. Ex. 8 80/20 _66 Coml~. Ex. 9 50/50 _ 66 Comp. l:x. 10 50!50 66 W O 93/1193~ PCT/US92/10082 3 a ~ 9 - 32 -. ~ ... .
Table 3 Noistur~ barrier layer thickn~es (lA and 2A)' adhesive layer thicknesses (lB and 2B), ga~ barrier 5lay~r th~ckneos ~c)~ and total film thickn2~s {n micron~ (~) for ~xamples 1-4 and 6, and for Comparison Examples 5 and 7-lO.
G .~ . ~r _ . _ : .
Layer Layer Layer Layer Layer Film lA lB C 2B 2A Th~ CknB8B
Exampl (Y) (P) (Y) (~) (Y) Toea Ex. l 37 5 ll 2 40 95 . _ . .
Ex. 2 38 4 12 5 39 97 ~x. 3 37 3 8 4 35 87 ... . ...... _ _ , .
lS Ex. 4 32 3 ll 3 39 86 Comp. .. .....
E:x. 5 3? 2 14 5 40 98 Ex. 6 35 2 lo 3 35 85 Comp.
Ex . 7 38 5 12 3 3? 94 comp.
3x~ 8 31 5 11 5 30 81 comp. _ :
Ex. 9 26 4 _ 12 7 31 80 --Comp.
Ex. lO 27 5 12 5 34 82 l ~ _ --.
The crystalline structure, or mesomorphou~ ~tructure, for each of the multilayered barrier filma of Examples 1-4 and 6, and for Comparison Examples 5 and 7-lO was determined by wide-angle x-ray diffraction (WAXD). Graphical illustration~ of the WAXD
ecan~ for each of the Example and Comparison Example films are ~hown in FIGS. 3 through 12 herein. Th~ mesophase form (i.e., mesomorphou~ polypropylene) i~ clearly shown in FIGS. 3-6 and 8.
FIG. 7 show~ the sharp peaks associated with crystalline polybutyl~ne, while the very sharp p2aks in the ~AXD scan shown in FIGS. 10-12 are due to the crystalline phaass of both polypropylene and polybutylene. The WAXD data for polypropylene present in the Example and Comparieon Example films ie eummariz~d in Table 4.

21238~9 - ~3 -. , . -Table 4 Structure of the polypropylene homopolymer 5and polymer blends o~ ~xamples 1-4 and 6, ~nd ~or Compari~on Exampl~n 5 and 7-10, a~ determined by WAXD.
~ -- , ~, - -- I - _ _ Ratio ¦ Casting Roll ¦
Example PP/PB I Temperature Number (wt ~) I WAXD PP (C) ~. ., . .- - ...... - . il Ex~ 1 100/0 Me~o~or~hous 10 Ex. 2 80/20 Me~omo hous 10 , rp ~x. 3 50/50 Mesomorphous 10 . -- ... .
Ex._4 20/80 Mesomorphou~ 1 D
C . Ex. 5 0/100 na 10 omp _ ~
Ex. 6 50/50 Mesomorphoue -1 i , .
Comp. Ex. 7 100/0 CrY~talline 66 ---- .... ~
Comp. Ex. 8 80/20 Crystalline 66 Comp. Ex. 9 50/50 Cryetalline _ 66 _ Comp. Ex. 10 50/50 Cryatalline 66 - -, The tensile properti~ for the barrier films of Example~
1-4 and 6 and Comparison Exampl~ 5 and 7-10 were detenmined on an Instronl~ 1122 machine using 5 cm x 2.5 cm ~amples of the Example and Co~pari~on Example multilayered barrier films. Each ~ample wa~ deformed at ~ 3trai~ rate of one thousand percent (1000%) per minute (sample gauge length of 5 cms and a crosshead speed of 51 cms per minute) using AS~M D882-88 procedures. In each case, at least thrss sample~ of each of the Example and Comparison Exsmple film~ were meaeured for each Yalue reported.
Effect of mQ~omorphous polypropylene (mPP) compo~ition on modulus (Young'~ Modulu~, a~ measured in Mega Pa~cals (HPa)) i8 shown in FIG. 13 (line A). A~ mPP concentration is reduced (3r PB
concentration in the mesopolymer blend i~ increased) the multilayered barrier film becomes lese stiff (i. e., ~ofter). As can be ~een in FIG. 13, the modulus value~ for the meaopolymer blends are lower than would be expected from the ~ule of Hixture~, ae defined herein, and illustrated at line B. Thi~
synergy in ~oftnes~ is further reflected in the yield ~tre~s re~ults as shown in FIG. 14. As with FIG. 13, th~ actual yield ~tr~ss value~ illuotrat-d by line A are cons$derably 1eBB than - tho~e which would be predicted under the Rule of Mixtures illu~trated at line B. Furthermore, quenched (casting roll W O 93tll938 PCT/US92/10082 3~Q temperature of 10C or les~) multilayered barrier films containi~g mPP in the outer layer bl~nd were found to be 24 to 30~ 1~B~ st~ff than simiiar compo~ltion~ w~th ~ry~talline PP
(caating roll temp~rature at 66c), a~ shown in Table 5.

~ ; I
Table 5 Young's Modulus in Mega Pa~cals (MPa~ of the I
multilayered barrier films of Example~ 1-4 and 6, and 1-Comparison Examples 5 and 7-10.
. . ., .... ....
Ratio Ca~ting Example PP/PB Modulus Roll Number (wt~ (MPa) T~mperature Ex. 1 100/0 376 10 ~Ex. 2 80J20 273 10 _ Ex. 3 50/50 _ 231 10 ¦EX. 4 ~ _203 10 ¦ComP. Ex. 5 0/100 193 10 ¦EX. 6 50/50 226 -1 ~C . Ex. 7 100 0 492 66 I omp /
¦ Comp. Ex. 8 80/20 390 66 ¦ Com~. Ex. 9 50/50 311 66 ~Comp. ~x. 10 50/50 300 66 Resistance to perm~ation of oxygen and moi~ture vapor was measured for the multilayered barrier films of Examples 1-4 and 6. Oxygen tranamission rate (O2TR) was determined using an Ox-Tranl~ 1000H machine (Mocon, Inc., Minneapolis, Minnesota).
O2TR was collected at 25~C and zero percent (0~) relative humidity. A square sAmple of each multilayer film was placed in the testing cell of the Ox-Tranl~ oxygen permeability tester.
Two oample~ of each film were te~ted in adjacent cells. Since the Ox-Tran1~ 1000H machine has ten te~t cells, up to five films could ~e examined at any one time.
~ ach cell wa- purged for at lea-t 24 hour- with a ~carrier~
gao of nitrog-n containing 1-3~ hydrogen prior to testing, to remove any re~idual oxygen in the oample, cell and syotem. After purging was completed, a sample of the gaoes in each cell was teoted for re~idual oxygen content or oxygon ~leak rate~. The leak rate value determined at each cell was used as the coll~ 8 residual oxygen baoeline.

W O 93/tl938 _ 2 1 2 3 ~ o 9 PCT/US92/10082 Next, each cell was conditioned for another 24 hours by pa~sing 100~ oxygen ovær one side of the sample. Oxygen on the other side of the sampls wa~ ~ea~ur~d after thi~ conditioning period. Thi~ total oxygen content included the amount of oxygen which psrmeated through the film plu~ any rQsidu~l oxygen $n the ~y~tem. To obta$n oxygen tr~nsmis~ion rate through the film, the leak rate value wa~ subtracted from the total oxygen ~easured.
Oxygen tran~m$~0ion rate datA wa~ collected for each film at 25C and 0~ r~lative humidity. The values reported are the av~rnge of rates determined for two eample~. S$nce oxygen tran~mi~ion ratQ i8 in~er~ely proportional to th~cknes~, all values were normalized to a standard ga~ barrier layer thicknes~
of 25 y by multiplying the oxygen transmi~ion rate value by the ratio of barrier layer thickneas (a~ reported in Tabl~ 3 herein) to 25 y.
Moi~ture vapor transmis~ion rate (MV~R) for the Example films wa~ determined u~ing a PenmatranT~-W6 (Mocon, In~., Minneapol$s, ~inne~ota). MVTR data was collected at 38.6C and one-hundred percent ~100~) relative humidity. The reported values are th~ average of the ~alue~ obtained for at lea~t three ~ample~ of each Example film. Sinc~ MVTR i~ inver~ely proportional to thickness, all values were normalized to a ~tandard ~oiatur~ barrier layer thickn2ss of 25 y (mi~rons) by multiplying the MVTR ~alue by the rbtio of moisturs barrier layer thieknese (being the sum of the moi~ture barrier and adhesive layer thicknessss, as reported in Table 3 herein) to 25 y. The oxygen tran~mi~sion rate~ (O2TR) and moisture vapor transmis~ion rates (MVTR) for Example~ 1-4 and 6 are reported in Table 6.
These rate~ d~monstrate good oxygen and moi~ture barrier propertie~ for the Example film~ of the present invention.

W ~ 93/11938 PCT/US92/10082 t , 3 ~ a 9 - 36 -Table 6 Oxygen transmis0ion ratea (O2TR), ae expressed in 5cc/m2/day-atmoephere, and moisture vapor transmi3sion rate~ (MVTR), a~ expre~s2d Ln g/m /day-atmo~phere, for Examples 1-4 and 6.
_ Caetlng Ratio Roll Ex. PP/PB Te~p. ~TR
No. (Wt%) _ ~ (cc/m~/d-atm) (g/m /d-atm) !I
1 ~00/0 ~ 0 2.0_ _13 8 11 2 80/20 10 2.214.5 _ 3 50l50 10 1.5 _16.4
4 _ 20~80 10 2.1 14.9 6 50/50 1 2.018.3 CO~PARI80N ESA~PL~S 11-16 Six, five-layered coextruded barrier fLlms were made on a ~tandard polyethylene type, blown-film proceefiing line ueing a five-layer blown film die. The barrier filme were coextruded at a thickne3s of 75 ~. The construction of the five-layered barrier films wa~ analogou~ to the multilayered barrier structure construction illu~trated in FIG. 2 herein. In part~cular, each moisture barrier layer (hereinafter "layer A") comprised a 50/50 mixture by weight of polypropy}ene (PP) (pp 3150; melt index = 0.
8 g/10 min.; Fina Oil and Chemical Co.) and polybutylene (PB)(PB
200; melt index 1.8 g/10 min. for Comparieon Examples 11-13; and P8 1710A; melt index 1.0 g/10 min. for Comparison Examples 14-16;
Shell Chemical Co.). Each adhesive layer ~hereinafter ~layer Bn) comprised a polypropylene copolymer (Plexar ~ 420; melt index =
2.5 g/10 min.; Quantum Chemical Corp.). The gae barrier layer (hereinafter ~layer C~), compri~ed an ethylene-vinyl alcohol 3S polymer tEVOH) (EVALl~ E151B; melt index = 1.6 g/10 min.; Evalca Co.). The PP/PB me~opolymer blend~ were precompounded beore being melted and coextruded.
The ~ix barrier film conetruction~ of Compari~on Examplee 11-16 are given in Table 7. Each of the filme wa~ croes--e~ctioned, and ind~vidual layer thickneeeee were determined byoptical microscopy according to the eame procedure~ ae for Exampla~ 1-4 and 6 and Comparieon Examplee 5 and 7-10. Extrue~on proceeeing conditione for each of the layer~ of the multilayered barrier films of Comparison Examplee 11-16 are ehown in Table 8.

WO 93/11~38 PCI/US92/lOU82 . . .~

Th~ film~ were ~ade 0.24 m wide at a 21 ~ter~ p2r min. (mpm) line ~peed. Non~ of Compari~on Examples 11-16 were quenched after hot melt co~xtruaion. ~hu~, the~e ~ample~ did no~ include any di~c~rnable amount of m~omorphou~ polypropylene in the ~oL~tur~ b~rr$er layers.

~ . , ~ .
Table 7 Ind~vidual lay~r thickne~e~ in micron~ for the barrier fllm con~tructions of Comparison Example~ 16.
Co~pari~on L-yer C Layer Bx2 Lay-r Ax2 ~xumple Thickne~ Thickne~Q Thickness ¦
Numbex (Micron~) ~Microns) ~Microns) I
. , _ -11 4 4 x 2 33 x 2 .
1~ _ 8 x 2 ~1 x 2 13 15 4 x 2 27 x 2 ..
14 4 _ 4 x 2 33 x 2 lS 8 4 x 2 31 x 2 1 . ~... ,..
16 15 4 x 2 27 x 2 WO 93/11938 PCI/USg2/lOOX2 2123809 - 38 ~
_ _ , ¦ Table 8 ¦ Indi~idual proce~ing ~ondition~ for each of the layers ¦ of the multLlayered barrier film constructiona of Compari00n Examples 11-16.
,, _ . , ._ , -- _-.
Individual l ¦ Layer Comp. Comp. Comp. Comp. Comp. Comp- ¦
Proce~ Ex. Ex. Ex. Ex. Ex. ~x.
Cond$tion~11 12 13 14 15 16 ,_.~._ . ............ . .. _ ,.,.~ . ,._ ~ayer C Extruder (4 cm) Screw Speed ~ _ _ (rmp~ _ 25 50 100 25 50 100 Melt T~mperature l (C~ 219 219 220 222 220 223 I., ._ ... _ -.__ Amps ~ 12 15 19 11 15 19 Layer B Extrc der ~4 c m) _ Screw Speed (rm~) 75 75 75 75 75 75 Melt Temperature (~C) 217 217 217 219 219 219 AmD8 14 14 14 14 14 14 ...__ .._ 25 1 La er A ~xtruder l6 cm) Y
Screw Speed (rmp) 97 97 97 9? 97 97 Melt l Temperature (C) 238 ~38 238 256 254 257 Ampe 102 102 102 108 108 108 Die l l .. _ _ Temperature l l (C? - 216 216 216 216l 216l 216 Blow Up ~at$o ~ 2:1l ?:1l 2:1l 2:1l 2:1l 2:1 , , , , ,-- -r -Frost Line l l l l l I
(cm) I 61 1 61l 61l 61l 61l 61 I ~

The ten-ilo propertia~ of each of the s~x barrier films of Compar~son Exampl~ 16 were perform4d on an In~tron 1122 mach$ne according to the same procedureB a8 employed ~n Examples 1-4 and 6, and Compar$~on Examples 5 and 7-10. Y~eld strain, ~ 2123~0!~
:

fracture strain, yield stress, fracture ~tress and Young'~
modulus wa~ obtained for each of Compari~on ~xample~ 16, and are ~hown in Table 9. At least three ~amples of each of the Compari~on ~xample films were meaeured for each value reported.

~ - - I
¦ Table 9 ¦ Yield ~train, fracture strain, yield st_e~, fracture ~tre~, and Young~s modulus in Mega Pa~cal (Mæa) for ¦
¦each of Comparison Example~ 16.
. _ ...... _ ,. ...... ~ - , ,. ,~ ." . . ___ j lLayer C Yi~ld Fracture Yisld Frncture l ¦ Comp Thickne~ Strain Strain Stres~ Stres~ Modulus ¦
Ex. ~) ~%) (~) (MPa) ~Pa) (MPa) j ... , .. ",~.~. ~ ...... , I , I_ I . ..__ ~

I .. __ . _. . .

r 1 16 - 15~ 20 372 32 27 405 Comparison Exumples 11-16 illu~trate that multilayered barrier film~ can be made on a blown film coextru~ion line, and have properties ~imilar to tho~s produced via flat ilm coextrueion proceH~ing. For example, the modulu~ values for non-quenched Comparison Examples 12 and 15 are comparable to those of Comparison Example~ 9 and 10. Furthermore, since quenched multilayered barrier structures in accordance with the preeent invention can be made by flat film coextrusion, as shown in Examples 2-3 and 6, it iB reasonable to expe~t that with appropriate modification to include quenching of tbe extrudate, that the blown film coextrusion processing disclosed in Compari~on Example~ 16 could also be utilized to form the multilayered barrier structures of the present invention.

~SAKPL~8 17. 19. 21. 23. 25 and 27-31. and CO~PAR~ON ~SAMPL~S 18. 20! 22. 2~ aND 26 Fifteen, five-layered, coextruded barrier film~ were made according to the same procedures as for Examples 1-4 and 6, and Compari~on Examplea 5 and 7-10 herein. Layer A was made from 50/50 mixturee by weight of polypropylene and polybutylene ba~ed re~$n~. The polypropylenes u~ed w re No~. PP3374 (melt index ~
2.5 g/10 min.) and PP3576 ~melt index - 9 g/10 min.)~ (Fina Oil and Chemical Co.). The polybutylenes employed were NOB- PB 8310 (melt index - 3 g/10 min.)~ DP1560 (melt index ~ 4 g/10 min.)~ PB

2i2~80 9 PCT/US92/10082 300 (melt index s 4 q/10 min.), PB 8340 (melt index = 4 g/10 minA), and PB 400 ~melt index = 20 g/10 min.), (Shell Chemical Co.). Numbers P~ 8310 and PB 8340 are poly~utylene'ethylene copolymer~, and No. DP1560 i~ a polybutylene-ba~ed ~pecial formulation ~Shell Chemical Co.). Lay~r B wa~ made of Plexarl~
420 (melt index ~ 2.5 g/10 min.) (Quantum Ch~mical Co.) Layer C
wa~ made of EVOH, (~VAL1~, E105A) (melt index 5.5 g/10 min.) (Evalca Co-) (Note: ~xampl~s 17 and 18 were made uBing a precompounded mixture of Pina PP3150 (m~lt index = 0.8 g/10 min.), and PB1710A~ melt index - 1.0 g/10 min.).
Th~ barrier ~ilm rolls were extruded onto casting roll~ at either temperature~ of 10C for Example~ 17, 19, 21, 23, 25 and 27-31, or 66C for Compari~on ~xamples 18, 20, 22, 24, and 26.
. All filma were coextruded at the rate of 10 meter0 per minute (mpm). Accordingly, for those Comparison Example films cooled at 66C, the cry~tallin~ pha~e of polypropyiene wa~ pr~sent, in~tead of the mesophaee of polypropylene found in the Example~ quenched at 10C. The f$1m coextru~ion eond;tions employed for eac~ of Examples and Comparison Example~ are giv~n in Table 10, The tensile propertie~ of the barrier film~ of thR Examples and Comp~ri~on ExAmple~ were obtained as in Examples 1-4 and 6, and Comparison Example~ 5 and 7-10. Yield ~train, fracture ~train, yield stre~a, fracture stre~s and Young' B moduluB~
expre~ed in (MPa), for Ex~mples 17, 19, 21, 23, 25, and 27-31 and Compari~on Examplea 18, 20, 22, 24 and 26 are ~hown in Table 11. At least three ~ampleB for each of the Example and Compari~on Example~ barrier film were mea~ured for each value reported.

WO 93/11938 212 3 8 0 9 PCl/US92/lOOB2 1 -=~ ~ ~
~ 14 2 ~ 2 3 8 0 9 - 42 ~
~ , ~ ,, . . I
Table 11 Yield strain, fracture strain, yield ~tres0, ' I fracture ~tr~ and Young~ 8 modulu~ for Bxamplas 17, 19, 21, 23, 25 and 27-31 and Comparieon Examplee 18, 20, 22, 24, and 26.
. . ~ . . . _._ .
Yield Fracture Yield Fracture l Strain strain Stre~s Stres~ ¦ ~odulu~
I Example(%) (~) ~MPa) (MPa) I (MPa) j__ .. _~ . ~_ .. ,",.. -Ex. 1? ~_ , 18 430 16 28 227 Comp. Ex. 18 8 447 21 32 286 Ex. 1920 426 14 _ 23 190 Comp. ~x. 20 21 411 17 25 225 Ex. 2116 429 16 ~4 246 comp. Ex. 22 18 406 23 28 310 Ex. 23 _ 17 418 15 25 223 Comp. Ex. 24 23 345 20 26 248 Ex. 2518 462 15 27 213 Comp. ~x. 26 22 387_ 23 32 286 Ex. 2717 473 14 25 208 !
~ . ;--Ex. 2815 427 17 24 234 Ex. 2917 420 16 24 227 Ex. 3015 468 17 26 254 Ex 3114 470 15 25 222 _ _ The Example and Comparison Example film~ illustrate that multilayered barrier films can be made with outer layer~
comprieed of blQnds of polypropylene of varying melt index combined with various polybutylene and polybutylene copolymer~
The mechanical property data of Table 11 show~ that those guenched multilayered barrier filma made in accordance with the principle~ of the present invention ~i.e., Exa~ple NOB . 17, 19, 21, 23, 25, and 27-31) have modulue value~ 10-26% le~s than their corresponding nonquenched f$1ma (i. e., Comparison Example Nos.
18, 20, 22, 24, and 26), and accordingly, are softer (less stiff) than the nonquenched filme.
.

~AKPL~S 32-41 Ten, f$ve-layered, coextruded barrier films were made using a flat film proces~ consieting of three extruders as descr$bed $n Examples 1-4 and 6. Layer A was made from mixturQs of polypropylene (No. PP3576, melt index = 9 g/10 min.; or NO.

W O ~3/11938 2 1 2 3 ~ O 9 PCT/US~2~10082 . . ~
;

PP3374, melt index = 2 . 5 g/10 min.; Fina oil and Chemical Co. ) and poly~utyl2ne (No. PB400, melt index s 20 g/10 min.; or No.
PB8340, melt index - 4 q/10 min., Shell Chemical Co. ) . Layer B
waE~ of PlexarTM420 tmelt index = 2.5 g/10 min.; Quantum Chemical Co. ~ or AdmerTM Q~551A (melt index = 5 . 7 g/10 min.; Mitsui Plastic~, Inc. ) . Layer C waa an EVO~ copolymer (No. E105, melt index s 5.5 g/10 ~in; or No~ G115, melt index - 14 g/10 min., or No. ES-GllO, melt index = 16, g/10 min.; Evalca Co.). The procR~s condition~ for each layer of ~xampla 32-41 are ~hown in Table 12. The film~ were all made at 12 meters per minut~ (mpm), and wer~ quenched on a 14C ca~tinq roll to a 75 ~ thickne~.
The ~pecific compo~ition~ of each film of Example~ 32-41 are given in Table 13.
; - - . I
Table 12 .
Procesa condition~ for each layer of Example film~ 32-41 .
Melt Screw Temperature Speed ~ayer (C) (RPM) ~5 C I 227 ~ ~ 2 3 ~ 0 9 - 44 - ~
-Table 13 Compo~ition~ of each film of Example~ 32-41
5~all Example film~ were quenched at a temperature of_14C).
T Layer A 1 Layer B T ¦ Layer B ¦ ~ayer C
Example _ PP PB PP:PB Adhesive EVOH
32 3576 400 80/20 PLEXAR ~ 420 E105 ~ . _ _ 3576 400. 80/20 PL~XARIh~ 420 G115 34 3576 400 50/50 PLEXARI~ 420 G115 3576 400 50/50 P~EXARI~ 420 E105 36 3374 400 50/50 PLEXAR7~ 420 E105 37 3374 400 50/50 PLEXARI~ 420 G115 38 3576 8349 20/80 PLEXARI~ 420 G115 39 3576 8340 20/80 PLEXARI~ 420 3105 _ _ _ . I
3374 8340 50/50 ADMERI~ QF551A E105 41 3374 8340 50/50 ADMER~ F551AES-GllO

The tensile properties of each of the Example barrier film~
were obtained a~ in Example and Compari~on ~xample Number~ 31.
Yield ~train, fracture strain, yield ~tres~, fracture ~tres~ and Youn~'~ modulus are ~hown for Example~ 32-41 in Table 14. At lea~t three sample~ for each of the ~xample barrier film~ were mea~ured for each value reported.

W O 93~11938 2~ 23 s o 9 PCT/US92/10082 ~ ~ . I
Table 14 ¦
¦ Yield ~train, fracture ~train, yield ~tr~, fracture 1 ~tre~ and modulus for Exumple~ 32-41.
_. ....... - - . ..................... ..
Yiald Fra~ture Yield Practure Strain StrainStres~Stre~s Modulu~
¦ Example ~) (~) (MPa)(MPa) (MPa) _ ~ . ~. ~ il 32 16 634 1834 _ _ ~ 266 33 ~6 831 17 37 238 r . ~ __ - __ , _ .

__ .- .... _ - _ ,. _ _ 35 17 618 13 30 ___ 92 _ .-. __ . - . .. _ _ 38_ 20 605 12 37 134 . __ _ __ _ ~. ~ ---n~G~ _ ~__ . . - _ ExampleB 32-41 illu~trate that multilayered barrier film~
can b~ made with outer layer~ comprised of blend~ of vaxying ratio, of polypropylene with differing melt index in combination with polybutylene and polybutylene copolymers, and with a core layer of EVOH copolymer~ which have varying mole percent~ of ethylene in the copolymers (44~ for E105~ 48% for Gl15, and 53%
for ES-GllO). Examples 32-35 al~o show that modulus, and accordingly the softne~s of the barrier films, can be effectively controlled by changing ths me~omorphou~ polypropylene (mPP) ratio in the blend. Sp~ifically, a~ tho percent mPP i~ decreased from 80~ in Exumple~ 32-33 to 50~ in Examples 34~35~ a corre~ponding drop in th~ modulu~ of 25-28~ i8 ob~er~ed.

~A~PLE8 42-~3 Two~ three-laysred, co~xtruded barrier film~ analogou~ to the film conetruction~ illu~trated in FIG. 1 were made using a flat film proce~ by bl~nding polypropylene INo. PP3374, melt ind~x 2~5 g/10 min.; Fina Oil and Chemical Co.) and polybutylene (No. PB8340; melt index 4.0 g/l0 min.; Shell Chemical Co.) as 40 layer A, blending EVOH (No. El05; melt index 5.5 g/lO min.;
Evalca Co.) and ethylene vinyl acetatQ copolymer (EVA) ~Elvax 660; Dupont, Inc.) for layer C, and eliminating adhe~ive layer 8. The film~ were made at 12 meter~ per minute, and were WO 93tll938 PCT/US92/10082 , ~3~09 quenched on a 14C ca~ting roll to a 75 ~ thickne~s~ The proce~
co~ditions for ~ach layer of ~xamples 42 and 43 are ~hown in Table 15. The ~pecific compo~ition~ of each of the Exam~le films are given in T~ble 16~

. ~ I
Table 15 Proces~ condition~ for each layer of Example~ 42 and 43.
¦ Melt ¦ Scr-w ~emperature Speed I
Lay r ~C) (RPM) ¦
A 227 59 ......................... :
.~ 231 lO

_ . .. , ., ~,, . ~ ~ , , , . :~
Table 16 ¦
Compositions of Examples 42 and 43 films. ::
(All Example film~ were quenched at a t~mperature of 14C) ¦ Lay r A j Lay-r A ¦ L~y-r C ¦ LaY;r C
Example PP PP: PB ! EVO~:EVA ¦ EVO~:EVA
42_ 3374 50/50 ¦_E105/EVA660 49:1 ¦¦
433374 50/50 ¦ E105/EVA660 l9:1 The tsnsile propertie~ for each of the Example barrier films were obtained a~ in Example~ 1-4 and 6. Yield strain, :~
fracture ~train, yield ~tres~, fracture ~tres~ and Young' 5 modulu~ for ~xampl~ 42-43 are given in ~able 17. At least three ~ample~ for each Example barrier film were mea~ured for each valu~ report~d.

Tabl- 17 ¦ :
Yield strain, fracture ~train, yield ~tre~s, fracture stress ~nd Young's modulus for Exampl~ 42-43.
j ¦ Yi-ld ¦ Fracture ¦ Yi-ld ¦ Fracture ¦
Strain Strain Stre~s Str~a Modulus Example (~) (%) (MPa) (MPa) (MPa) . , . , _ 42 1 21 1 617 1 14 ~ 39 1 173 ~ ==~

2i23809 Example~ 42 and 43 illu~trate that thr~e~layer multllayered barrier film~ in accordance with the pre~ent invention can be formed by blending EYA copolymer along w$th ~VOH in the ga~
barrier layer of the pre~ent in~ention. When ~uch ~ gas barrier layer L~ coextruded along with the me~opolymer blends amployed in the moisture barr$er layer(~, a multilayered b rr~er film in accordance with the pre~ent invention can be formed without the - need to re30rt to optional adhesive layers.

~A~PL~ 44 AND COMæARISON ~SAMPI~ 45 Multilayer~d barrier film~ of sixty-fiva ~65) layer~ were made on a multilayer coextru~ion line utilizing three extruder~.
ThR 65-layered con~truction con~isted of oppo~ing, outer moiature barrier layers (here~nafter layer ~A~), each of which wa~
followed by an adheeiv~ layer (bereinafter layer ~B"), and then a gac barrier layer (hereinafter layer nC~). Thereafter, the structure alternatod layers as follow~: layer B, layer A, layer B, layer C, layer B, layer A, layer B, layer C, etc. Layer A
compri~ed polypropyl~ne No. PP3014 (melt index = 12 g/10 min.);
Exxon, Inc.). Layer B compri~ed Admerl~ QF 551A (melt index =
5.7 g/10 min.; Mitsui Pla~tic~, Inc.). While, layer C co~pr~sed an EVOH copolymer, No. EVAL F101 (melt index = 1.6 g/10 min.;
Evalca Co.).
The Example and Comparison Example barrier film~ were cast on a temparature-controlled casting roll at a t~mperature of 81C
for ComparLson Example 45, and 5C for Example 44. Wide-angle X-ray diffraction ~WAXD) mea~urements of each of the films ~howed that the Comparison Example 45 film contained undesirable crystalline polypropylene of the isotactic I structure, while the quench~d film of ~xampl~ 44 waa of mesomorphou~ polypropylene structur~. The f~lms were irradiated using electron-beam ionizing radiation and stored at room temperature for prolong~d p~riods of tim~. Th~ mechanical propertie6, including elongation to break, ~or the aging ~xample and Compar$son film~, were measured utilizing an Instronl~ ~odel 1122 machine according to ASTM D882-31, with a strain rat~ of 100% per minute. Table 18 contain~ the perc~nt elongation to break data for irradiated ~$1ms of Example 44 and Compar$con ~x~mple 45 over time.

WO 93/1193~ PCI/US92/10082 3~09 48-I ~ _ Table 18 , Percent elongation to break d~ta for irradiated ¦
5films of Exa~ple 44 and Compari~on ~xample 45. ¦
(Mon.smonth; ~=quenched; NQ=nonquenched) l i- . _ , ~ jl ~: `
~ -Beam % Elong. to Break Percent ¦
~xample Do~agz =Y=~e ~etentionl Number ~kGy) Zero One One Two Thr~e (3 Mon8.)¦
Week Week Mon. Mon. Mon.
; .. _~ ._...... j. _ ~ ' - ;i 0 393393 ___386 380 9?~
Ex. 44 50 393321 338302 340 87% ¦¦ :
(Q) 100 393317 338392 293 75%
I .
0 302302 ___363 350 116 Comp.
Ex 45 50 302268 ?0468 46 15%¦¦
100 302178 15022 17 6%
! _. _~_._ . - . -:

As the re~ult~ in Table 16 illustrate, the quenched multilayered barrier film of Example 44, which contained meso~orphou~ polypropylene, retained excellent mechanical properties (i. e., percent elongation to break)~ even at three month~ after irradiation at 100 kGy (10 Mrad) dosage~. In contra~t, the non-quench~d, cry~talline polypropylene containing film of Comparison Example 45 i8 nonfunctional three months after irradiation.

~2AMPL~S ~6-50, AND
CO~PARISON E~A~PLES 51-55 Multilayer barrier films corre~ponding in con~truction to Example~ 1-4 and 6, and Comparative ~xample~ 5, and 7-10 (Example films 1-4 and 6 were u~ed for Examples 46-50; Compari~on Example film~ 5 and 7-10 were ueed for Comparison Example~ 51-55) were electron beum irradiatsd at a do~age of 50 kGy (5 Mrads) and then immediately placed in liguid n~trogen. Electron paramagnetic resonance (EPR) analy~is was performed by fir~t warming the films to room temperature, cutt~ng them to 1.3 cm x 7.6 cm in size, weigh~ng, and then mounting the film ~trips in tub~s. This technique allows reproducible ~ample po~tioning in the EPR
cavity. Radical peak height~ were rocorded for each sample as a function of elapsed time from the initial measurement uoing a VarianI~ model 4502 spectrometer with a 23 cm magnet operat~ng in the ~X~-band. Fremy's ~alt was u~ed as the magnetic field reference. Peak he$ght represent8 radical concentration as mea~ured in ~pin~/gram. Initial run8 were used to e~timate W O 93/1193X PCT/USg2~10082 - ' radical concentration, and the declining numbers are proportional to the initial number. Since different instrument setting~ were u~ed for ~om~ ~amples, all number~ were normalized. Spin concentration was calibrat~d Again~t the National Bureau of Standard~ No. 261 Ruby Standard.
Normaliz~d radical p~ak height in spin~/gram i~ ~hown in Table 19 a~ a funct~on of elap~ed tLme (bour~) for ~xamples 46-50- and Compari00n Examples 51-55. In all ca~e~, radial deeay occurs in the quanched fil~ (Examples 46-50) at a much faster ratQ than in th~ eomparison nongu~nch~d film~ (Comparison ~xamples 51-55).
This is more cl~arly demonstrated in FIGS. 18-20 wher~ normalized radical peak height iB plotted against ~lapsed time. For example, a~ FIG. 18 illu0trat~, radical decay oc~urs at consist~ntly fa~ter rate for the quenched f$1m of ~xample 46 (line A) in comparison to the nonquenched film of Comparison Example 52 (lin~ B). Likewi~e, analogous result~ are ~hown with the quenched film of Example 47 (line A~ and Compari~on Ex3mple 53 (line B) in FIG. 19. Furthermore, excellent reproducibility of the data is d~mon~trated in FIG. 20 where value3 for guenched film Examples 48 and 50 (l~ne A) fall on the same general curve as for the nongu~nched film- of CompariAon Examples 54 (line B~
and 55 ~line C). Thus, the guench~d film~ containing meaomorphou~ polypropylene are expscted to maintain their integrity and propertie~ to a greater extent than thsir nonguenched counterpart~ since the radicals available for degradætion are reduced mora rapidly in the quenched films than in the nonquenched filma.

WO 93/1193$ PCI'~US92/100~7 E ~c¦ ~ 'o~ ;E 3 a ID OD ~D ~ c e u~ ~ ~ ~D _ ~r a~ ~ :

m ~ ~ E ~ v f~ o o ~ ~D ~ ~ ~ ~ ¦

1~ " v UE~ Z rl 1~ O 0 1 -------- ¦ ~

r lC X ~ O~ ~ ~D r1 r ul ~r N O
XLI~:: . _ _ __ _ _ _ _ ¦ ~ ~ ol ~ ~

~A~PL~8 56-71 ~ND
COMPARS~O~ X~AMPL~S 72-8 Sixteen, five-layerad coextruded barrier films ~ere made using a flat ~iLm proc~s as de~sribed in ~xample8 1-4 and 6 and, thirteen, five-layered coextruded barrier film~ were made a~
de~cribed for Comparison Example~ 5 and 7-10. The barrier films were generally coextrud~d at a film thickness of abou~ 75 ~, with each moi~ture b~rrier layer (hereinafter lsyer ~A~) being about 31 ~ thick, each adhe~ive layer (hereinafter layer ~B"I
being about 4 ~ thick, and th~ g~ barrier layer (hereinafter layer "C~) being ~bout 8 ~ thick. The construction of the five-lay~r barrier films of Example~ 56-?1 and Co~parison Example~ 72-84 corre~ponded to the multilayered construction~
~llu~trated in FIG. 2 herein.
Layer A compri~ed mixtures by weight of polypropylene resin ~PP) (PP3576; melt index ~ 9 g/10 min; Fina Oil and Chemical Co.) with ethylene vinyl acetate copolymer resin (EVA)(No. UE656; melt index = 5.4 g/10 min.; 12~ vinyl acetate content; Quantum Chemical Corp.), or with ethylene acrylic acid copolymer resin (EAA)(Pri~acor 3340; melt index = 9 g/10 min.; 6.5~ acrylic acid comonomer content; Dow Chemical Co.), or with both polybutylene re~in (PB)(P W00; melt index = 20 g/10 min.; Shell Chemical Co.) and EVA, or with both PB and EAA. Layer B comprised a polypropylene based adhe~ive layer of Admerl~ QF551A resin (melt index = 5.7 g/10 min.); Mitsui Plastics, Inc.). Layer C was ma~e of an ethylene vinyl alcohol copolymer (EV~H~E105A, melt index = 5.5 g/10 min.; ~valca Co.).
The blended mixtures were dry blended before being melted and coextruded. The films for Examples 56-71 and Comparison Example~ 72-84 were extruded at a melt temperature of 221C for layer A, and 232C for layers B and C. Table 20 li~ts specific constructions for Examples 56-71 and Comparison Examples 72-84.
Temperature for the quench roll for Examples 56-71 was maintained at 19C in order to control the mesomorphous structure of the polypropylene in the mesopolymer blend, while ~ quench temperature of 66C was utilized with Comparison Examples 72-84, thereby re~ult~ng in crystalline polypropylene being pre~ent ~n the polymer blonds. Adheoive and gas barrier layer conotructions were ~ept conHtant acros~ all the Examples and Comparison Ex~mpleo.

WO 93/11938 PCI/U~92/1()082 2 ~ ~ 3 8 9 - 52 Table 20 Film constructions a~d Young's ~odulue value~ ~MPa) for Exampl~ 56-71 and Compari~on Example~ 72-84.
j ~ _ _ Young'o ~x.No./ Quench Modulu~ ¦
Comp. Ex. Blend Rat$o Temp. Ex./Comp. Ex.¦
No.Composition (Wt %) (C) ~ ;r = ~ ~ ~. .. _~_ i~
56/72 mPPs~VA 100/0 10/66 386/497 ._~ . .. _ -. _ ~ . 11 lo - 57!73 mPP:EVA _ 75/25 10/66 337/405 58/74 ~PP:~VA 50/50 10/66 268/304 l . ~_ ... .. ___ . ._ . Il 59/75 ~PP:EVA 25/75 10/66 189/254 ~. ~ _ . - . . 11 60¦-- mPP:~VA 0/100 10~66_ 178/---61l76 mPP:PB:EVA 50/50/0 10/66 241/309 62/77 mPPsPB:~VA37.5/37.5/25 10/66 230/263 63/78 mPP:PBsEVA 25~25/50 10/66 173/227 64/?9 . mPPsPB EVA12.5/12.5/75 10/66 1581205_ 65/80 mPPsE~A 75/25 10/66 331/414 66/81 mPPsEAA 50/50 10/66 289/347 . .. _ . -67/82 mPP:EAA 25/75 10/66 231/274 68/-- mPP:EAA 0/100 10/66 176/---~_ .__ .
69/83 mPP:PB EAA37.5/37.5/~5 10/66 240/291 .
70/84 mPP-.PB:EAA 25/25/50 10/66 71/-- mPP:P8:EAA12.5/12.5/75 10/66 192/---, _ - - ~
T~n~ile properties were performed on an Instron ~ model 1122 machine according to the Bam~ procedure~ as disclosed in ~xamples 1-4 and 6, and Co~par$~on Example~ 5 and 7-10 herein.
30In ~ach ca~e, at lea~t thre~ ~amples of each Exumple and Compari~on Exa~ple w~re m~asured for each value reported.
The effect of the amount of me~omorphou~ polypropylene ~-:
(mPP) in the mo$~ture ~arrier laysr ~layer A) on the modulu~
(Young'~ modulu~) for the mult~layered barri.er f$1ms of Example~
3555-71 (in co~par$~on to th~ effQct of cry~talline polypropylene $n Comp~iri~on Ex~mple~ 72-84 i8 ~hown in Table 20. In all ca~es, the modulus for the quenched f$Lm~ of Example~ 56-71 i8 6.5%-41%
lower than for the nonquenched film~ of Compari~on Examples 72-84. A mor~ det~ d analy~i~ for th~ effect of mPP on barrier 40film modulu~ for Exumple~ 56-60 i~ hown in FIG. 15. For mPP
concentration~ of le~e than about 70~ (or EVA concentrations in the me~opolymer blend of greater than 30~) the multilayered barrier filme bQcums l~e~ Cti.~r (i.a. softer). As can b~ Heen in FIG. 15, modulu~ values for ~ multilayer~d barrier films with mosopolymer blend concentrations in this range (line ~) (i.e.~
1Q~ than 70~ mPP) are lower than would be exp~ctod from the Rule of Mixture~ (line B), as that term is definad her~in. Similar effects on modulus ar~ shown ln Figure 16 for the multilayered barrier filme of ~x~mples 60-64 with mPP:PB:EVA mesopolymer blend concentratione of l~ee than about 70% of mPP and PB (or EVA
conc~ntrations in the me~opolymer blend greater than 30%). As w~th ~xample~ 56-60, modulus ~alues for the multilayered barrier films with mesopolymer blend concentratione in this range ~line A) (L.e., lee8 than 70~ mPP:PB) are lower than would b~ expected from the Rule of Mixture- ~line ~). Thus, adding EVA to mPP or mPP:PB rc~ins forming the moi~tur~ barri~r layer of the multilayered barrier film~ ~ynergi~tically results in multilayered barrier ~ilm8 whLch are less stiff than would be expected for ~PP or mPP:PB me~opolymer blends in the concentration range of about 0~ to 70~.
Synergy in fracture strain, as shown in Figure 17, wae aleo observed for Exumples 61 and 68-71, wh~re the moi~ture barrier, layer of the multilayered barrier film~ comprised a me~opolymer blend of mPP:PB:EAA. That is, fracture strains were greater than would be ex~eçted (line A) than under the Rule of Mixtures ~line B), ae that term is defined herein. Thus, u~ing mPP:PB:EAA
mesopolymer blende in the moisture barrier layers of the multilayered barrier filme rosults in filme which are surprieingly tougher ~i.e. dieplay a greater etain to fracture) than would be expected.
Oxygen transmieeion rate ~TR) data wae collected for the films of Examples 58, 63, 66 and 70 according to the same procedures and utili~ing the same equipment ae deecribed for Exampl~s l-4 and 6 h~rein. The r~-ults were normalized to a 25 thick film, and reported in cc/~2/day-atmosphere at 25C and 0~
relative humidity a~ per Example~ 1-4 and 6. The 02~R data for Examples 58, 63, 66 and 70 are reported in Table 21. The results indicate that meeopolym~r blends of me~Gmorphous polypropylene (~PP) and ethylene vinyl c-tate (EVA) and ethylene acryl$c acid (EAA), e$ther alone or in comb$nat$on with polybutylene (PB), d~mon~trate comparable ~TR values to the mPP:PB compositions reported in Table 6 here$n.

WO 93/11938 PCI`/US92/10082 2~23~09 _ ~4 _ T~ble 21 Oxygen tran~mieoion rates ~TR), a~ expr~s~ed in c'c/m2/d-. atm, ~or ~xample~ 58, 63, 66, and 70.

Ex. No. Compo~ition Ratio ~wt ~) ~c/m~/d-atm) l . _ . - . jl 58 mPP:EV~ 50/50 3.3 , . - . .
63 mPP.PB:EVA 25/25/50 3.4 66 mPPsEAA 50(50 3.0 ¦
mPP:PB:EAA 25/25/50 3.0 ~a~l~s 85-9~
~ive multilayer~d tube~ and five multilayered pouches were ~ormed from the multilayer barrier films of Exu~ples 3, 58, 63, 66 and 70. To make the tube~, the film~ were curvQd into a cylinder and h~at sealed on on~ edge using a heat sealer (Sentinell~, Inc.). The ~ouches were m~de by either folding the Example film over on itself, and then heat ~ealing two-sides, or ::
by using two films, placing one on top of thQ other, and then heat ~ealing three of th~ side~. The tube and pouch dimen~ions, along with compositions of the moisture barrier layers of the film~, ar~ shown in Table 22 for the tube~ of Examples 85-89, and in Table 23 for the pouches of Examples 90-94.
~ . -' Table 22 :-overall tube dimension~ and ~ompo~ition of the ::
moi~ture barrier layers of the multilayered :~
tubings of Ex~mples 85-89.
. , . , ... ,~ . ,._, .
Original Mo~sture Tube Tub~ Wall Exampl~ Exampl~ Barrier Layer Radium Thicknes~
Numb-rNu ber CompositLon (cm) ~micron~) 3 PP:PB 1.9 102 _, (50~) . ~
86 58 PP:2VA ~0/50) 1.3 74 _ _ .87 63 PP:PB:EVA 1.1 64 .. 525/25/50) 88 66 PP:EAA ~50/50) 1.4 89 89 70 PP:PBP:~AA 1.3 76 (25/25/50) .~ ......... ~ ~ e W O 93~11938 2 ~ 2 3 ~ 0 9 PCT/US92/10082 - 55 - `

Table 23 Ovsr~ll pouch dimzn~ one and compo~ition of the mo~Hture lbarrier layar~ of the multilayered pouches l :
1of Ex~mples 90-94.
.. ~ .. , ,~,_... ~ ~ .......... ~ ~ ~ - il Moif~ture Orlgin~l Barrier ¦ Pcuch Pouch Pouch ~xample Example Layer ¦ ~ength Width Thickne6~ ¦
Number Number Compo~ition i (cm) (cm) (micron~
~ ~ ~ , ... ~ . .I.. I I .-_~ ~ .1.. _ ¦ 90 3 PP:PB ~50/50) 8 14 102 . . _ . r _. . .
91 58 pp-~VA 7 12 74 92 63 PP:PB:EVA 6 ll 64 (25/25/50) 93 66 PP:EAA 8 ll 8g -~ (50/50) _ 94 70 PP:PB:EAA 7 ll 76 l (25/25/S0) - _ ;
SlW~5S g5--102, AND
COKPARISON ~SAMPL~S 103-ll0 To determine noice generated by a fiLm during wrinkling, an apparatu~ capable of flexing a film sample in a cyclic and repeatable manner wa~ csn~tructed in accordance with the teaching of U.S. Patent No. 4,376,799, the di~closure of which i~ herein incorporated by reference. Sa~ples of Example film~ were cut to 8.~ cm by 8.8 cm in size. One end of the film was wrapped around a stationary cylinder of 2.5 cm diameter and the other end to a second, rot~table cylinder displaced 5 om parallel from the ~tationary cylinder. Thus, the film formed a cylinder which connected the atationary cylinder to the rotatable cylinder.
Noise wa~ generated by the film when the motor wa~ engaged and the rotatable cylinder and attached film were rotated 15 in a forward direction and then 15 in the rever~e direction at a frequency of 1.2 cycles per ~econd. A microphone inserted in the stationary cylinder wae u~ed to pick up noi~e and generate an electrical eignal which was used for further analysis. The signal from th~ microphone wa~ proce~ced through a preamplifier wh~ch measured sound level in decibels over a rangs of 0 to 20 XHz. Th~ ~ignal wa~ then routed to a fre~uency analyzer which meaeured the inteneity of generated sound Ln volte ae a function of it~ frequency. Theee valuee were then recorded and ueed for noi~e data analy-i~. Background noi-e, that i~, noi~Q in the room ns wRll ~ noi-e generat~d by the operating apparatu~
without an attached f$1m, wae eubtracted from the film noiee WO 93/1~938 PCr/US92/10~2 3~9 ~pectrum to produ Q a ~p~ctrum characteristi~ of the film only.
All t~ats w~re p*rforMed in an ~necho~c chamber.
Noi~s can ba mea~ur~d both in t~rm0 of it~ frequency and inten~ity. In gencral, sounda of hlgh inten~ity and frequency ~eem louder to the human ear than sound~ of lower inten~ity and frsquency. Thu~, a ~qu~te~ film ~hould exh~bit a low frequency, l~w intenuity hOiB~ ~psctruM.
Noi~o 0p~ctra for qu~nched and nonquenched multilayer b~rrier film~ of Example~ 95-102 and Compari~on Examples 103-110 wer~ genkrated. Noi~e data for both qu~nched film~ and the corresponding nonquench~d filma are ~hown in FIGS. 21-36. Table 24 correl~tes the FIG. number with th~ Example and Compari~on Example number, ca~ting roll tempsratur~ and film composition.
In all CaB~s~ tha qu~nchod mult$1ay~r barri~r films are quieter than the nonqu~nched film~ of the ~ame, but nonquenched, co~po~ition. .~
, . , . . I .
Table 24 -.
Film con~truction~ and correlation to FIG. No. for film~
of Examples 95-102 and Comparison Example~ 103-110 (EN=Example NumbRir; OEN-Comparison ~xample Number;
ONsOriginal ~xample Numbeir; OCN=Original Compari~on Exumple Number). I m . _, . ., _ . .. ~ . I
Casting Roll Moi~ture Component FIG. Temp. Layer Weight EN/CEN ON/OCN No. (C) Comp. Ratio 95/103 1/7 21J2210J66 PP:PB 100:0_ 96/104 2/3 23/2410/66 PP~PB 80:20 I :
I .
¦ 97/1056/9 25/25 10/66PP:PB 50 50 ¦ 98/10657/7327/28 10/66PP:EVA 75:25 .
¦- 99/10763/78 ~ 10166PP:PB:EYA25:25:50 ¦ 100~108 64/79 31/3210~66 PP:PB:EVA 12.5:12.5:75 ~:
3S 1 101/109 66t~1 33/3410/66 _PP:EAA 50:50 ::
102/11069/8435/36 10/66!pB EAA37.5:37.5.25 CooDarat~v~ mDl~ 112 and ~u~pl-~ 113-114 Sample~ of the multilayer~d barrier film of Example 3 were coated with acrylic acid (AA) ~onomer (Example 113) or dimethylacryla~id~ (DMA) monomer (Example 114). The~e coated films wer~ th-n irradiated u~ing an lectron beam at a do~age of 50 kGy ~5 Mrad~) in an inert nitrogein atmosphere, resulting in W 0 93/11938 PCr/~s92/l0082 ,.,",, 2123~og the grafting of th~se monomers to the surfaces of the coated film~. In addition, two control films were produced. The first control film compri~ed an uncoated and nonradiated ~amp~e of the Example 3 film (comparative Example 111~. Th~ s~cond control film compri~ed an uncoated film irr~di~t~d at ~ do~age of 50 kGy ~Compar~tive Exlmple 112) according to the ~ame procedure a~ for Examp~ :3 113 and 114r - To a~ s the strength of th~ grafted layer, 180 peel adhesion m~acurement~ wer~ perfor~ed according to the following 10proc~dure. A 2.5 cm wide, 20.3 cm long ~trip of pressure-eensitive adhesive tape (Scotchl~ brand tape no. 8411; 3M
Company) wa~ adher~d to a 10.1 cm wide, 15.2 cm long ~heet of each of tho Exa~ple and Comparat~ve ~xample films, with a fres end of the tape ext~nding beyond the end of each film. The ~ample f ilmB were then roll~d twice with a 1.35 kg hard rubber roller to ensure contact between the adhesive and the aample films. The sample~ were then aged at room temperature (22C) for 24 houra, after which the free end of the tape was removed from th~ sample~ at a rate of 15.2 cm/m~n using a 01ip/peel testing machine (Instrumentors, Inc., Strong~vil~e, 0~). The graft monomers employed, electron beam radiation dosage employed, and the peak peel adhesion force mea~ured in gr~ms/2.5 cm for the ~ample films of Comparative Exam21es 111 and 112, and Example~
113 and 114 are ~hown in Table 25.

I : ; : ..................... =_ -Table 25 Graft monomers u~ed, electron beam radiation do~age employed, and peak peel adhesion measured in grams/2.5 30cm for the ~ample films of Comparative 2xamples 111 and 112, and ~xample~ 113 and 114.
. j . . ; .
GraftE-beam Dose Peak Peel Force Ex. No. NonGmer (kGy) ~g!25 cm) 35 Compi none O 5.9 _ __ Comp. none 50 7.8 Ex. 112 _ _ Ex. 113 AA 50 12.1 . . ---. .. ... .
Ex. 114 DMA 50 14.5 ~ ~ _ ~ Th~ data of Table 25 ~how that barrier film~ of the pre~ent inv~ntion with an additional mcnomer l~y-r grafted thereto have higher peel ~trength th~n th~ ~mB film~ lacking in the additional monomer layer, and when not xpo~ed to electron beam WO 93/11938 PCl`/US92/10082 .

2~ 9 - 58 -radiation in an inert atmosphere. Thu~, adhe~ion promoting layer~, as well as other làyers, can be added to the barrier films of the preeent invention ut$1izing the above te~hnique~.
While in accordanc~ with the patent statutes, de~cription of the prefarred weight fractions, proceseing conditions, and product u~ages ha~e been provid~d, the ~cope of the invention i~
not to be limited thereto or thereby. YariouH modification~ and alter~tions of the present invention will be appar~nt to tho~e ~killed in the art without departing from the 8cope and ~pirit of the present invention. The examples de~cribed in this application are ~llustrative of the po~ibilitie~ of varying the amounts and types of polymeric materials in the multilayered barrier structure~ to achieve properties for specific purpooes.
Con~equently, for an under~tanding o~ the ~cope of the pre~ent invention, reference i~ made to the following claim~.

Claims (10)

What is Claimed is:
1. A multilayered structure comprising:
(a) a gas barrier layer having opposing sides, and comprising a non-chlorine containing organic polymer which is substantially impermeable to oxygen gas; and (b) at least one moisture barrier layer comprising a mesophase proplylene-based material contacting at least one of the sides of the gas barrier layer.
2. A multilayered structure according to claim 1, wherein the non-chlorine containing organic polymer is selected from the group consisting of a vinyl-alcohol-containing polymer, polyacrylonitrile, polystyrene, polyester, nylon, and combinations thereof.
3. A 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.
4. A multilayered structure according to claim 3, wherein the mesopolymer blend comprises a blend of mesomorphous polypropylene and at least a discernable amount of a second polymer.
5. A multilayered structure according to claim 3, wherein the mesocopolymer comprises a propylene-based material with a discernable amount of at least one moiety.
6. A multilayered structure according to claim 1, wherein the multilayered structure further comprises one or more adhesive layers disposed between the gas barrier layer and moisture barrier layer.
7. A multilayered structure according to claim 1, wherein the [coextruded] multilayered structure is [-] and comprises a film, a tube, a fiber, a microfiber, an ostomy pouch, a transdermal drug delivery patch, a tape, or a packaging material.
8. A multilayered structure according to claim 1, wherein the multilayered structure further comprises a fabric backing selected from the group consisting of a woven material, a nonwoven material, and combinations thereof affixed to at least a portion of the multilayered structure.
9. A method for forming a multilayered structure comprising:
(a) coextruding a propylene-based material along with a nonchlorine containing organic polymer which is substantially impermeable to oxygen gas to form a multilayered extrudate; and (b) quenching the multilayered extrudate immediately after extruding to provide a multilayered structure with a core layer of the non-chlorine containing organic polymer and at least one layer of a mesophase propylene-based material proximate the core layer.
10. A radiation resistant article formed from a multilayered structure comprising:
(a) a gas barrier layer having opposing sides, and comprising a non-chlorine containing organic polymer which is substantially impermeable to oxygen gas; and (b) at least one moisture barrier layer comprising a mesophase propylene-based material contacting at least one of the sides of the gas barrier layer, wherein the article is quenched immediately after being melt extruded.
CA 2123809 1991-12-18 1992-11-18 Multilayered barrier structures Abandoned CA2123809A1 (en)

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US81000191A 1991-12-18 1991-12-18
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US5407713A (en) 1995-04-18
EP0617665A1 (en) 1994-10-05
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WO1993011938A1 (en) 1993-06-24
DE69228827D1 (en) 1999-05-06

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