Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/06—Layered 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
  • B32B27/08—Layered 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
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61F—FILTERS 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
  • A61F5/00—Orthopaedic methods or devices for non-surgical treatment of bones or joints; Nursing devices ; Anti-rape devices
  • A61F5/44—Devices worn by the patient for reception of urine, faeces, catamenial or other discharge; Colostomy devices
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61F—FILTERS 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
  • A61F5/00—Orthopaedic methods or devices for non-surgical treatment of bones or joints; Nursing devices ; Anti-rape devices
  • A61F5/44—Devices worn by the patient for reception of urine, faeces, catamenial or other discharge; Colostomy devices
  • A61F5/445—Colostomy, ileostomy or urethrostomy devices
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
  • A61L28/00—Materials for colostomy devices
  • A61L28/0061—Materials for coating
  • A61L28/0069—Macromolecular materials
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B7/00—Layered 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
  • B32B7/04—Interconnection of layers
  • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/30—Properties of the layers or laminate having particular thermal properties
  • B32B2307/31—Heat sealable
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/70—Other properties
  • B32B2307/716—Degradable
  • B32B2307/7166—Water-soluble, water-dispersible
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/70—Other properties
  • B32B2307/724—Permeability to gases, adsorption
  • B32B2307/7242—Non-permeable
  • B32B2307/7244—Oxygen barrier
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/70—Other properties
  • B32B2307/724—Permeability to gases, adsorption
  • B32B2307/7242—Non-permeable
  • B32B2307/7246—Water vapor barrier
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2375/00—Polyureas; Polyurethanes
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2535/00—Medical equipment, e.g. bandage, prostheses or catheter
• • Y—GENERAL 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
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
  • Y10T428/1334—Nonself-supporting tubular film or bag [e.g., pouch, envelope, packet, etc.]
  • Y10T428/1341—Contains vapor or gas barrier, polymer derived from vinyl chloride or vinylidene chloride, or polymer containing a vinyl alcohol unit
• • Y—GENERAL 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
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
  • Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
• • Y—GENERAL 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
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
  • Y10T428/2813—Heat or solvent activated or sealable
  • Y10T428/2817—Heat sealable
  • Y10T428/2826—Synthetic resin or polymer
• • Y—GENERAL 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
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
  • Y10T428/2852—Adhesive compositions
• • Y—GENERAL 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
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
  • Y10T428/31573—Next to addition polymer of ethylenically unsaturated monomer
  • Y10T428/3158—Halide monomer type [polyvinyl chloride, etc.]

Definitions

• the present invention relates to an oxygen and moisture impermeable coextruded or coate ⁇ multilayer barrier film, and to articles produced therefrom including ostomy bags and heat sealable bags for packaging a variety of materials.
• Plastic film laminates having oxygen and moisture vapor barrier properties were desirable for current packaging requirements, as well as for use in medical applications such as the fabrication of ostomy bags. Such films have been provided through the use of multi-ply film laminates where at least one of the plies was oxygen and moisture vapor impermeable.
• the films comprise chlorinated polyethylene films or plasticized polyvinyl chloride films, polyvinylidene chloride copolymer films, or multilayered structures such as ethylene vinyl acetate - polyvinylidene chioride/ethylene vinyl acetate combination films.
• Such constructions adequately meet the needs of oxygen and moisture barrier properties, but in use were often difficult to dispose of in a manner convenient to the user, such as by flushing the bag down a 5 toilet.
• Martini et al U.S. Patent No. 4,906,495, relate to a laminated film used for ostomy applications.
• the barrier and water soluble layers must be glued together using an additional adhesive layer.
• Such additional layers not only add to materials and manufacturing costs, but also result in a thicker film laminate having greater stiffness. 0 Both Brooks et al, U.S. Patent No. 4,772,279, and Coombes, U.S. Patent No.
• the present invention meets that need by providing an oxygen and moisture impermeable multilayer barrier film which may be produced by coextrusion or coating 5 techniques without the need for separate adhesive layers to secure the other layers together.
• the film provides excellent adhesion between layers, odor barrier characteristics, and a heat sealable surface for fabrication of bags.
• an oxygen and moisture impermeable multilayer barrier film having a heat seal strength of at least 1 0 lb/men of film width, ana DreferaDly greater than 1.5 lb/inch of film width was provi ⁇ ed.
• oxygen impermeable it was meant that the film has an oxygen transmission rate of equal to or less than 90 cc/m2/day atm.
• moisture impermeable it was meant that the film has a water vapor transmission rate of equal to or less than 5 gm/m ⁇ /day.
• the film comprises a barrier layer of a homopolymer or copolymer of vinylidene chloride which was coextruded with or coated onto a water soluble film layer.
• the water soluble layer preferably comprises a blend of a water soluble polymer such as polyvinyl alcohol, polycaprolactone, or polyethyloxozaline and a thermoplastic polyurethane.
• the water soluble layer was thicker than the barrier layer and comprises from I to 50- by weight of the thermoplastic polyurethane, and more preferably from 10 to 25 " by weight of the thermoplastic polyurethane.
• the water soluble film may be a monolayer or may include two or more layers with the first layer comprising the water soluble polymer and thermoplastic polyurethane blend and the second layer comprising the same or different water soluble polymer to enhance the water sol u bi I ity of the f i I m .
• the adhesion between the water soluble and barrier layers may be enhanced by a number of means. These include coating or coextruding a thermoplastic polyurethane layer to the water soluble layer or blending an adhesion-enhancing amount of a thermoplastic polyurethane with the barrier layer.
• the resulting film has an oxygen transmission rate of less than 90 cc/m2/day atm.
• the barrier layer was formulated to heat seal to itself to form a disposable bag with the barrier film facing inward.
• the barrier film may further comprise an optional heat sealable skin layer of a suitable adhesive resin including such as a thermoplastic polyurethane on the side opposite the water soluble layer.
• a suitable adhesive resin including such as a thermoplastic polyurethane
• Such a layer provides enhanced heat seal properties to the film.
• the multilayer barrier films of the present invention have a sufficient bond between the layers to permit coextrusion or coating without the use of additional adhesive layers and without the need for a lamination of the layers. Further, the resulting barrier film possesses properties which render the film suitable for use as disposable or reusable ostomy pouches, as well as packages for agricultural chemicals, detergents, and other household chemicals.
• Fig. 1 was a schematic cross-section of one embodiment of the multilayer barrier film of the present invention useful as a disposable ostomy pouch including a water soluble layer;
• Fig. 2 was a front elevational view of an ostomy bag or pouch formed from the multilayer barrier film of Fig. 1 of the present invention.
• the multilayer barrier film of the present invention provides greater adhesion between layers than prior art laminated films without the need for separate adhesive or glue layers and the attendant cost associated with the extra manufacturing step involved with lamination. This allows the films to be produced by a coating process in which the barrier film material was coated onto a water soluble film layer.
• the resulting multilayer films possess low oxygen and moisture vapor transmission rates, as well as having the odor barrier properties needed for ostomy applications.
• the practice of the present invention makes it possible to achieve these properties without the use of additional adhesive layers through the proper selection and blending of the components of each layer of the film.
• multilayer film 10- comprises a barrier layer 14 of a homopolymer or copolymer of vinylidene chloride with vinyl chloride or methyl methacrylate which was coextruded with or coated onto a water soluble film layer 12.
• the water soluble layer 12 preferably comprises a blend of a water soluble polymer such as, for example, polyvinyl alcohol, polycaprolactone, or polyethyloxozaline and a thermoplastic polyurethane.
• water soluble layer II comprises from I to 50- by weight of the thermoplastic polyurethane, and more preferably from 10 to 25- by weight of the thermoplastic polyurethane.
• additional thermoplastic polyurethane may be added to the blend to enhance the adhesion of the coating to the barrier layer.
• caution must be used as the water solubility of the film was adversely affected as the amount of thermoplastic polyurethane was increased.
• the water soluble film may comprise a single monolayer of the blend, it was also possible to coextrude this blend with another water soluble polymer resin to produce a bi-layer film having enhanced water solubility.
• a suitable barrier material includes a copolymer of vinyl chloride (15-20 percent by weight) and vinylidene chloride (80-85 percent by weight) commercially available from The Dow Chemical Company under the trademark Saran ® F279.
• a water soluble polyvinyl alcohol resin such as Vinex ® 5030 resin, commercially available from Air Products and Chemicals, Inc. may be used.
• other water soluble polyvinyl alcohol resins such as Vinex ® 2144 may be used. The two or more layers may be coextruded.
• the relative thickness of he two layers may be controlled, giving the advantage of being able to control the water solubility characteristics of the film.
• the unmodified water soluble polymer resin layer may comprise up to 75 percent or more of the bi-layer film to provide enhanced water solubility.
• a thermoplastic polyurethane may be blended with the polyvinyl alcohol or other water soluble poiymer layer.
• Suitable thermoplastic poiyurethanes include those based on the reaction of a polyisocyanate (aromatic or aliphatic) with polyester, polyether, or polycaprolactone polyols. Chain extenders such as diols and diamines may aiso be used in the reaction.
• thermoplastic poiyurethanes were commercially available from the B.F. Goodrich Co. under the trademark Estane ® and from The Dow Chemical Company under the trademark Pellethane ® .
• a preferred thermoplastic o polyurethane composition was Pellethane ® 2355-95AE.
• an optional thermoplastic polyurethane skin 16 may be coextruded with or coated on the surface of water soluble layer 12. Skin layer 16, and/or the thermoplastic polyurethane blended into water soluble layer 12, acts as to enhance the adhesion of barrier layer 14 to water soluble layer 12.
• the resulting film should have an oxygen transmission rate 5 of less than 90 cc/m2/dayatm (6 cc/100 in2/dayatm). This higher oxygen transmission rate was acceptable for a barrier film which was designed to be disposable.
• the multilayer film may include an optional skin layer 18 of a heat sealable material such as, for example, a thermoplastic polyurethane or other suitable adhesive resin on the side of the film opposite water soluble layer 12 to provide enhanced heat seal properties for the film when folded to form a bag or pouch.
• a heat sealable material such as, for example, a thermoplastic polyurethane or other suitable adhesive resin
• Fig. 2 illustrates a typical disposable ostomy bag 20 including an opening 22 formed from the multilayer barrier film of Fig. 1.
• the bag may be formed by folding and heat sealing the edges of multilayer film 10.
• the film was preferably folded and sealed such that the barrier and heat sealable skin layers provide the inner surfaces of the bag or pouch 20.
• the barrier film of the present invention provides an easily disposable ostomy pouch with the moisture resistance and odor and oxygen barrier properties needed.
• the barrier films ofthe present invention may also find use in other packaging applications where moisture and oxygen barrier properties were required.
• the multilayer film of the present invention may be produced using conventional extrusion or coating techniques.
• the configuration of the extrusion die can be varied and can be such as to reduce the thickness and dimensions of each individual layer.
• the thickness of the multilayer film may be controlled.
• Suitable coating devices include rotogravure coaters.
• the water soluble polyvinyl alcohol layer the thicker layer, comprising 75 percent or more of the overall film thickness.
• the water soluble layer wiii be between 1 to 3 mils thick, while the barrier iayer wiil have a thickness of between 0.1 to 0.2 mils.
• the film may comprise a first layer of the water soluble poiymer/thermopiastic polyurethane blend, a second layer of a thermoplastic polyurethane, and a barrier iayer comprising a vinylidene chloride homopolymer or copolymer.
• Another possible combination comprises the water soluble polymer/thermoplastic polyurethane blend and a barrier Iayer comprising a vinylidene chloride/ thermoplastic polyurethane blend.
• Still another combination was a coextruded three Iayer film comprising the water soluble o poiymer/thermopiastic polyurethane blend and a Iayer of thermoplastic polyurethane, and a third Iayer comprising the polyvinylidene chloride/thermoplastic polyurethane blend.
• Still another possible combination includes a first Iayer comprising the water soluble polymer/thermoplastic polyurethane blend, a second Iayer comprising thermoplastic polyurethane, a third Iayer of a vinylidene chloride homopolymer or copolymer, and a fourth 5 Iayer of the thermoplastic polyurethane.
• Example 1 0 A multilayer film was produced in accordance with the present invention by first dissolving 5- by weight of a thermoplastic polyurethane (Pellethane ® 2354-80A5) in tetrahydrofuran at 45-50°C.
• a thermoplastic polyurethane Pellethane ® 2354-80A5
• the coating was applied to the surface of an extruded 2.0 mil thick polyvinyl alcohol film (Vinex ® 5030 from Air Products and Chemicals, Inc.) containing 10 percent by weight thermoplastic polyurethane (Pellethane ® 2355-95AE) at a coating weight of 5 2 gm/m2, to yield a thickness of 0.05 mil.
• the coated film was then placed in an oven to dry for 1 1/2 minutes at 120°C.
• a coating of the barrier material was then prepared by dissolving Saran ® F279 resin in a mixture comprising 65 percent by weight tetrahydrofuran and 35 percent by weight toluene.
• the final lacquer contained approximately 18 percent by weight Saran ® .
• the coating 0 was applied to the surface of the coated water soluble film at a coating weight of 4 gm/m2 (approximately 0.1 mil thick) and dried at 1 10°C for two minutes to drive off the solvents and to crystalize the coating.
• the resulting multilayer barrier film had a heat seal strength of 7.7 N (1.73 lb) at 300°F, 30 psi, 1 sec dwell, and an oxygen transmission rate of 13.9 cc/m2/dayatm.
• Example 2 5 A multilayer film was prepared as in Example 1 except that the water soluble film comprised 85 percent Vinex ® 5030 and 15 percent Pellethane ® 2355-95AE. The resulting film had a heat seal strength of 9.9 N (2.22 lb) at 300°F, 30 psi, 1 sec dwell, and an oxygen transmission rate of 8.4 cc/m 2 dayatm.
• Example 3
• a multilayer film was produced in accordance with the present invention by first dissolving 5 percent by weight thermoplastic polyurethane (Pellethane 3 2354-80AI) in tetrahydrofuran at 45-50°C. The lacquer was applied to the surface of an extruded 2.0 mil thick
• a coating of the barrier material was prepared by dissolving Saran ® F279 resin and Pellethane ® 2354-80AI in a mixture comprising 65 percent by weight tetrahydrofuran and
• the coating was applied to the surface of the coated water soluble film at a coating weight of 4 gm/m 2 (approximately 0.1 mil thick) and dried at 1 10°C for two minutes to drive off the solvents and crystalize the coating.
• the resulting film had a heat seal strength of 96.3 N (1.41 lb) at 300°F, 30 psi, 1 sec dwell, and an oxygen

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• Health & Medical Sciences (AREA)
• Veterinary Medicine (AREA)
• Public Health (AREA)
• Epidemiology (AREA)
• Life Sciences & Earth Sciences (AREA)
• Animal Behavior & Ethology (AREA)
• General Health & Medical Sciences (AREA)
• Nursing (AREA)
• Heart & Thoracic Surgery (AREA)
• Biomedical Technology (AREA)
• Engineering & Computer Science (AREA)
• Vascular Medicine (AREA)
• Orthopedic Medicine & Surgery (AREA)
• Materials For Medical Uses (AREA)
• Orthopedics, Nursing, And Contraception (AREA)
• Laminated Bodies (AREA)
• Extrusion Moulding Of Plastics Or The Like (AREA)

Priority Applications (6)

Applications Claiming Priority (2)

Publications (1)

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Family Applications (1)

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Cited By (5)

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Citations (8)

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• 1993
  • 1993-09-20 US US08/123,270 patent/US5468526A/en not_active Expired - Fee Related
• 1994
  • 1994-08-26 WO PCT/US1994/009682 patent/WO1995008440A1/en not_active Ceased
  • 1994-08-26 DK DK94926612T patent/DK0720531T3/da active
  • 1994-08-26 JP JP50977395A patent/JPH09506300A/ja active Pending
  • 1994-08-26 ES ES94926612T patent/ES2102247T3/es not_active Expired - Lifetime
  • 1994-08-26 AT AT94926612T patent/ATE153597T1/de active
  • 1994-08-26 AU AU76397/94A patent/AU681906B2/en not_active Ceased
  • 1994-08-26 DE DE69403487T patent/DE69403487T2/de not_active Expired - Fee Related
  • 1994-08-26 KR KR1019960701427A patent/KR960704709A/ko not_active Abandoned
  • 1994-08-26 EP EP19940926612 patent/EP0720531B1/en not_active Expired - Lifetime
  • 1994-08-26 CA CA 2172138 patent/CA2172138A1/en not_active Abandoned
  • 1994-09-17 TW TW83108625A patent/TW322454B/zh active

Patent Citations (8)

Non-Patent Citations (1)

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