DE29605214U1 - Multi-layer film, in particular for bags for solutions - Google Patents
Multi-layer film, in particular for bags for solutionsInfo
- Publication number
- DE29605214U1 DE29605214U1 DE29605214U DE29605214U DE29605214U1 DE 29605214 U1 DE29605214 U1 DE 29605214U1 DE 29605214 U DE29605214 U DE 29605214U DE 29605214 U DE29605214 U DE 29605214U DE 29605214 U1 DE29605214 U1 DE 29605214U1
- Authority
- DE
- Germany
- Prior art keywords
- multilayer film
- polypropylene
- tpe
- film according
- 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.)
- Expired - Lifetime
Links
- 239000004743 Polypropylene Substances 0.000 claims description 24
- -1 polypropylene Polymers 0.000 claims description 24
- 229920001155 polypropylene Polymers 0.000 claims description 22
- 229920005629 polypropylene homopolymer Polymers 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 15
- 229920000642 polymer Polymers 0.000 claims description 13
- 229920005606 polypropylene copolymer Polymers 0.000 claims description 12
- 229920002725 thermoplastic elastomer Polymers 0.000 claims description 11
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 claims description 10
- 229920002745 polystyrene-block- poly(ethylene /butylene) Polymers 0.000 claims description 9
- 229920000346 polystyrene-polyisoprene block-polystyrene Polymers 0.000 claims description 9
- 229920002367 Polyisobutene Polymers 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 7
- 230000004888 barrier function Effects 0.000 claims description 6
- 239000003978 infusion fluid Substances 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000008155 medical solution Substances 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- 238000010791 quenching Methods 0.000 claims description 3
- 230000000171 quenching effect Effects 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229920002292 Nylon 6 Polymers 0.000 claims description 2
- 229920002302 Nylon 6,6 Polymers 0.000 claims description 2
- 229920002614 Polyether block amide Polymers 0.000 claims description 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- 239000004793 Polystyrene Substances 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 239000000155 melt Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 claims description 2
- 229920002943 EPDM rubber Polymers 0.000 claims 1
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 10
- 239000002131 composite material Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 238000009516 primary packaging Methods 0.000 description 2
- RLRINNKRRPQIGW-UHFFFAOYSA-N 1-ethenyl-2-[4-(2-ethenylphenyl)butyl]benzene Chemical compound C=CC1=CC=CC=C1CCCCC1=CC=CC=C1C=C RLRINNKRRPQIGW-UHFFFAOYSA-N 0.000 description 1
- VSKJLJHPAFKHBX-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 VSKJLJHPAFKHBX-UHFFFAOYSA-N 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- 239000004708 Very-low-density polyethylene Substances 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 244000052616 bacterial pathogen Species 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 239000003633 blood substitute Substances 0.000 description 1
- FACXGONDLDSNOE-UHFFFAOYSA-N buta-1,3-diene;styrene Chemical compound C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 FACXGONDLDSNOE-UHFFFAOYSA-N 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000000385 dialysis solution Substances 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 150000002013 dioxins Chemical class 0.000 description 1
- BXOUVIIITJXIKB-UHFFFAOYSA-N ethene;styrene Chemical group C=C.C=CC1=CC=CC=C1 BXOUVIIITJXIKB-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002742 polystyrene-block-poly(ethylene/propylene) -block-polystyrene Polymers 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 229920001866 very low density polyethylene Polymers 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion 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
- B29C48/07—Flat, e.g. panels
- B29C48/08—Flat, e.g. panels flexible, e.g. films
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion 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
- B29C48/09—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
- B29C48/10—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels flexible, e.g. blown foils
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
- B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
- B29C48/21—Articles comprising two or more components, e.g. co-extruded layers the components being layers the layers being joined at their surfaces
-
- 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
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
-
- 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
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- 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
- B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61J—CONTAINERS SPECIALLY ADAPTED FOR MEDICAL OR PHARMACEUTICAL PURPOSES; DEVICES OR METHODS SPECIALLY ADAPTED FOR BRINGING PHARMACEUTICAL PRODUCTS INTO PARTICULAR PHYSICAL OR ADMINISTERING FORMS; DEVICES FOR ADMINISTERING FOOD OR MEDICINES ORALLY; BABY COMFORTERS; DEVICES FOR RECEIVING SPITTLE
- A61J1/00—Containers specially adapted for medical or pharmaceutical purposes
- A61J1/05—Containers specially adapted for medical or pharmaceutical purposes for collecting, storing or administering blood, plasma or medical fluids ; Infusion or perfusion containers
- A61J1/10—Bag-type containers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion 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
- B29C48/09—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
- B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
- B29C48/22—Articles comprising two or more components, e.g. co-extruded layers the components being layers with means connecting the layers, e.g. tie layers or undercuts
-
- 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
- B32B2307/724—Permeability to gases, adsorption
- B32B2307/7242—Non-permeable
-
- 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
- B32B2309/00—Parameters for the laminating or treatment process; Apparatus details
- B32B2309/08—Dimensions, e.g. volume
- B32B2309/10—Dimensions, e.g. volume linear, e.g. length, distance, width
- B32B2309/105—Thickness
-
- 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
- B32B2439/00—Containers; Receptacles
- B32B2439/40—Closed containers
- B32B2439/46—Bags
-
- 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
- B32B2439/00—Containers; Receptacles
- B32B2439/70—Food packaging
-
- 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
- B32B2439/00—Containers; Receptacles
- B32B2439/80—Medical packaging
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Laminated Bodies (AREA)
- Medical Preparation Storing Or Oral Administration Devices (AREA)
- Packages (AREA)
- Wrappers (AREA)
Description
• ··
BeschreibungDescription
Die Erfindung betrifft eine Mehrlagenfolie, insbesondere für Beutel für Lösungen, mit Polymer-Außenschicht, - Mittelschicht und heißsiegelbarer Polymer-Innenschicht; Verfahren zur Herstellung einer coextrudierten Folie aus dem Material und deren Verwendung zur Herstellung von Beuteln für Nahrungszwecke und medizinischen Lösungen, bspw. Infusionslösungen, Dialyselösungen, Blut oder Blutersatzstoffe etc..The invention relates to a multilayer film, in particular for bags for solutions, with a polymer outer layer, middle layer and heat-sealable polymer inner layer; method for producing a coextruded film from the material and its use for producing bags for food purposes and medical solutions, e.g. infusion solutions, dialysis solutions, blood or blood substitutes, etc.
Derartige Mehrlagenfolien, die bevorzugt heißsiegelbar sind, werden bereits seit längerem zur Herstellung von flüssigkeitsdichten, insbesondere wasserdichten Beuteln eingesetzt. Sie werden insbesondere für Beutel als Primärverpackungen von medizinischen Lösungen verwendet. Sie können auch als Drainagebeutel eingesetzt werden. Dabei ist es meist ausreichend, daß sie wasserdicht sind, in speziellen Fällen, insbesondere dann, wenn sie als Primärverpackung von Sauerstoff- oder Kohlenstoffdioxidempfindlichen Materialien eingesetzt werden, kann auch eine entsprechende Gassperreigenschaft erwünscht sein. Dies ist beispielsweise für den Einsatz als Verpackung von Aminosäurelösungen der Fall.Such multilayer films, which are preferably heat-sealable, have been used for a long time to produce liquid-tight, especially waterproof bags. They are used in particular for bags as primary packaging for medical solutions. They can also be used as drainage bags. It is usually sufficient that they are waterproof; in special cases, particularly when they are used as primary packaging for oxygen or carbon dioxide-sensitive materials, a corresponding gas barrier property may also be desirable. This is the case, for example, for use as packaging for amino acid solutions.
Bisher wurden zu diesem Zweck meist Weich-PVC-Beutel eingesetzt. Diese waren hinsichtlich ihrer Flexibilität und Siegelbarkeit zufriedenstellend, hatten aber den Nachteil, daß die darin enthaltenen Weichmacher durch Migration im PVC leicht in das Beutelinnere diffundierten und so zu einer höchst unerwünschten Verunreinigung des Inhalts führen konnten. Besonders bei Infusionslösungen ist es äußerst unerwünscht, daß diese Weichmacher mit der Lösung in den Patienten gelangen.Up to now, soft PVC bags have mostly been used for this purpose. These were satisfactory in terms of their flexibility and sealability, but had the disadvantage that the plasticizers contained in them easily diffused into the inside of the bag due to migration in the PVC and could thus lead to highly undesirable contamination of the contents. Particularly with infusion solutions, it is extremely undesirable for these plasticizers to reach the patient with the solution.
Ein weiterer Nachteil der Weich-PVC-Beutel besteht darin, daß diese aufgrund der bei der Verbrennung auftretenden Chlorverbindungen und Dioxine Schwierigkeiten bei der Abfallbeseitigung hervorrufen. Es wurde bereits vorgeschlagen, anstelle von PVC Polyethylenbeutel einzusetzen. DiesesAnother disadvantage of soft PVC bags is that they cause difficulties in waste disposal due to the chlorine compounds and dioxins that are produced during combustion. It has already been suggested that polyethylene bags should be used instead of PVC. This
Material hat jedoch den Nachteil, daß es maximal bei einer Temperatur von 121°C autoklavierbar ist (Wasserdampfsterilisation) . Ferner fehlte es den PE-Alternativen häufig an der erwünschten Transparenz und Flexibilität.However, the material has the disadvantage that it can only be autoclaved at a maximum temperature of 121°C (steam sterilization). Furthermore, the PE alternatives often lack the desired transparency and flexibility.
Aus der DE 44 10 876 ist bereits eine coextrudierte Mehrschichtfolie mit einem Polypropylen-TPS-Compound als bei einer Temperatur von 115 - 150°C heißsiegelbare Innenschicht und einer Polypropylen-Homopolymerschicht als Außenschicht sowie einer Polypropylen/VLDPE-Schicht als Verbindungsschicht beschrieben. Diese bekannte Mehrschichtfolie ist jedoch sowohl hinsichtlich ihrer Transparenz als auch hinsichtlich ihrer Flexibilität als auch hinsichtlich der Aneinanderhaftung der den Mehrlagenfolie bildenden Schichten aneinander verbesserungsfähig. Aufgrund der Einstellung der Innenschicht auf eine Siegeltemperatur von maximal 150°C ist es problematisch, derartige Folien zu autoklavieren.DE 44 10 876 already describes a coextruded multilayer film with a polypropylene TPS compound as an inner layer that can be heat-sealed at a temperature of 115 - 150°C and a polypropylene homopolymer layer as an outer layer and a polypropylene/VLDPE layer as a connecting layer. However, this known multilayer film can be improved both in terms of its transparency and its flexibility as well as in terms of the adhesion of the layers forming the multilayer film to one another. Due to the setting of the inner layer to a maximum sealing temperature of 150°C, it is problematic to autoclave such films.
Die grundlegenden Anforderungen an Mehrschichtfolien zum Einsatz als Verpackung von wäßrigen Lösungen, insbesondere Infusionslösungen od. dgl. sind also, daß dieseThe basic requirements for multilayer films used as packaging for aqueous solutions, in particular infusion solutions or the like, are that they
- hohe Flexibilität- high flexibility
- sehr gute Transparenz- very good transparency
- physiologische Unbedenklichkeit aufweisen,- are physiologically safe,
- siegelbar mit dauerbeheizten Werkzeugen oder impulsschweißbar und- sealable with permanently heated tools or impulse weldable and
- autoklavierbar auch oberhalb von 121°C sind und- are autoclavable even above 121°C and
- gute Wasserdampf-Barrieren sind.- are good water vapor barriers.
Es ist also Aufgabe der Erfindung, eine schweißbare, d.h. impulsschweißbare oder heißsiegelbare Mehrschichtfolie zu schaffen, die eine Alternative zum bisher verwendeten Weich-PVC ist.It is therefore the object of the invention to create a weldable, i.e. impulse-weldable or heat-sealable multilayer film, which is an alternative to the soft PVC used to date.
Die Aufgabe wird erfindungsgemäß durch eine Mehrschichtfolie gelöst die eine Außenschicht aus einem Polymeren,The object is achieved according to the invention by a multilayer film which has an outer layer made of a polymer,
I··I··
mindestens eine Verbindungsschicht aus einem Polypropylen-Compound aus einem Polypropylen-Homo- oder Copolymerisat und mindestens einem TPE oder Polyisobuten und eine Innenschicht aus einem Polypropylen-Compound mit mindestens einem TPE.at least one connecting layer made of a polypropylene compound made of a polypropylene homo- or copolymer and at least one TPE or polyisobutene and an inner layer made of a polypropylene compound with at least one TPE.
Bevorzugt weist die Innenschicht eine niedrigere Siegeltemperatur als die Außenschicht auf, wodurch dann das Heißsiegeln mit dauerbeheizten Werkzeugen möglich ist. Es ist aber auch möglich, Mehrlagenfolien ohne ein derartiges Schmelzpunktgefälle der Folien vorzusehen - diese müssen dann bspw. impulsgeschweißt werden.Preferably, the inner layer has a lower sealing temperature than the outer layer, which then enables heat sealing with permanently heated tools. However, it is also possible to provide multi-layer films without such a melting point gradient of the films - these must then be impulse welded, for example.
Vorteilhafterweise ist das mindestens eine TPE zur Compoundierung mit Polypropylen ausgewählt ist aus der Gruppe bestehend aus SSBS, SIS, SEBS, SEB, Polyetherestern (TPE-E), Polyurethan (TPE-U), Polyetheramid (TPE-A) und EPDM/PP-Blend .Advantageously, at least one TPE for compounding with polypropylene is selected from the group consisting of SSBS, SIS, SEBS, SEB, polyether esters (TPE-E), polyurethane (TPE-U), polyether amide (TPE-A) and EPDM/PP blend.
TPE ist hier die allgemein übliche Abkürzung für thermoplastisches Elastomer.TPE is the commonly used abbreviation for thermoplastic elastomer.
Unter SEBS wird hier Styrol/Ethylen/Butylen-Styrol Triblock-Polymer; unter SEB ein Styprol/Ethylen/Butylen-Diblock-Polymer unter SEPS sein Styrol-Ethylen/Propylen-Styrol-Triblock-Polymer, unter SBS ein Styrol-Butadien-Styrol-Triblock-Polymer (SBS) und unter SIS ein Styrol-Isopren-Styrol-Tripollock-Plymer verstanden.SEBS is understood here to mean styrene/ethylene/butylene-styrene triblock polymer; SEB is understood to mean styrene/ethylene/butylene diblock polymer; SEPS is understood to mean styrene-ethylene/propylene-styrene triblock polymer; SBS is understood to mean styrene-butadiene-styrene triblock polymer (SBS) and SIS is understood to mean styrene-isoprene-styrene tripollock polymer.
Unter EPDM wird ein Terpolymer aus Ethylen, Propylen und einem nichtkonjugierten Dien (EPDM) und/oder Ethylen-Alpha-Olefin-Copolymer verstanden.EPDM is a terpolymer of ethylene, propylene and a non-conjugated diene (EPDM) and/or ethylene-alpha-olefin copolymer.
Es kann aber auch mit Polyisobuten, das eine hohe Flexibilität und einen niedrigen Schmelzpunkt aufweist, compoundiert werden.However, it can also be compounded with polyisobutene, which has high flexibility and a low melting point.
Es ist besonders bevorzugt, daß die mindestens eine Zwischenschicht einen höheren Anteil an TPE aufweist, daIt is particularly preferred that the at least one intermediate layer has a higher proportion of TPE, since
dadurch ein geringerer melt flow index und damit eine höhere Flexibilität erzielt wird. Es kann aber auch sinnvoll sein, als Zwischenschicht Polyisobuten einzusetzen.This results in a lower melt flow index and thus greater flexibility. However, it can also be useful to use polyisobutene as an intermediate layer.
Es kann erforderlich sein, daß die Außenschicht eine Barriere gegen Sauerstoff - oder Kohlenstoffzutritt ist.It may be necessary for the outer layer to be a barrier against oxygen or carbon access.
Dies kann bspw. dadurch erzielt werden, daß die Außenschicht ausgewählt ist aus der Gruppe bestehend aus Polyamid 6, Polyamid 66, Polystyrol, Polyacrylnitril. Derartige Sperrschichten müssen aber zumeist mittels eines Haftvermittlers an den Schichtverbund beferstigt werden und können als dritte, vierte od. weitere Außenschicht vorgesehen sein.This can be achieved, for example, by selecting the outer layer from the group consisting of polyamide 6, polyamide 66, polystyrene, polyacrylonitrile. However, such barrier layers usually have to be attached to the layer composite using an adhesion promoter and can be provided as a third, fourth or further outer layer.
Es kann auch sinnvoll sein, falls keine Sauerstoff-Sperreigenschaften nötig sind, daß die Außenschicht ein Polypropylen-Homopolymerisat oder aber auch ein Polypropylen-Copolymerisat ist. Diese Schicht eignet sich insbesondere im Verbund mit einer Verbindungsschicht die ein Polypropylen-Compound aus einem Polypropylen - Hompolymerisat, einem Polypropylen-Copolymersiat und einem TPE-S ist und einer heißsiegelbaren Innenschicht aus einem Polypropylen-Compound bestehend aus einenm Polypropylen-Homopolymerisat, einem Polypropylen-Copolymerisat und einem TPE.It can also be useful, if no oxygen barrier properties are required, for the outer layer to be a polypropylene homopolymer or a polypropylene copolymer. This layer is particularly suitable in combination with a connecting layer which is a polypropylene compound made of a polypropylene homopolymer, a polypropylene copolymer and a TPE-S and a heat-sealable inner layer made of a polypropylene compound consisting of a polypropylene homopolymer, a polypropylene copolymer and a TPE.
Als Außenschicht kann auch ein Polyisobuten/Polypropylen-Polymeres eingesetzt werden - in diesem Fall ist die Mehrlagenfolie dann aufgrund der Schmelzeigenschaften des Polyisobutens mittels Impulsschweißen verbindbar.A polyisobutene/polypropylene polymer can also be used as the outer layer - in this case, the multilayer film can be joined by impulse welding due to the melting properties of the polyisobutene.
Die mindestens eine Verbindungsschicht im Folienverbund sorgt nicht nur für die Haftung der Außen- und Innenschicht aneinander, sondern sorgt auch für die Flexibilität der Mehrlagenfolie. Somit wird das Verbindungsschichtmaterial danach ausgewählt, daß es hoch-flexibel ist und auch eine gute Kontakttransparenz der Mehrlagenfolie bietet.The at least one connecting layer in the film composite not only ensures that the outer and inner layers adhere to one another, but also ensures the flexibility of the multilayer film. The connecting layer material is therefore selected so that it is highly flexible and also offers good contact transparency of the multilayer film.
Ein derartiger Verbund haftet durch die Coextrusion problemlos aneinander und gewährleistet dennoch eine gute Siegelbarkeit dern Innenfolie sowie ein Temperaturgefälle der Siegeltemperaturen von außen nach innen.Such a composite adheres to one another without any problems due to coextrusion and still ensures good sealability of the inner film as well as a temperature gradient of the sealing temperatures from the outside to the inside.
Es kann aber auch eine Mehrlagenfolie ohne Temperaturgefälle ausgebildet werden, wobei diese dann bspw. nach dem Impulsverfahren verschweißbar ist.However, a multi-layer film can also be formed without a temperature gradient, which can then be welded using the impulse process, for example.
Eine typische Gesamt-Foliendicke liegt bspw. im Bereich von 150 bis 350 um.A typical total film thickness is, for example, in the range of 150 to 350 µm.
Es ist besonders bevorzugt, daß daß die Schichten coextrudiert sind, wodurch das Vorsehen von Adhasionsverbesserern oder aber auch Klebstoffen vermieden werden kann und die Herstellung der Mehrschichtfolie in einem einzigen Herstellungsschritt erfolgen kann.It is particularly preferred that the layers are coextruded, whereby the provision of adhesion improvers or adhesives can be avoided and the production of the multilayer film can take place in a single production step.
Die Erfindung betrifft auch ein Verfahren zur Herstellung einer coextrudierten Folie aus dem Material nach einem der vorangehenden Ansprühce, dadurch gekennzeichnet, daß die Schichten von oben nach unten coextrudiert und sodann abgeschreckt werden. Bevorzugt erfolgt das Abschrecken durch Extrusion in ein Wasserbad. Durch dieses Abschrecken wird der amorphe Zustand des Polymeren aus der Schmelze erhalten und die Flexibilität sowie Transparenz derselben gegenüber nicht abgeschreckten Folien erheblich verbessert.The invention also relates to a method for producing a coextruded film from the material according to one of the preceding claims, characterized in that the layers are coextruded from top to bottom and then quenched. Preferably, quenching is carried out by extrusion into a water bath. This quenching preserves the amorphous state of the polymer from the melt and significantly improves the flexibility and transparency of the same compared to non-quenched films.
Es ist insbesondere für die Verwendung der Mehrschichtfolie zur Herstellung von Beuteln günstig, wenn das Material als Schlauch extrudiert wird. Dadurch wird eine Kontamination der Innenseiten des Beutels durch Keime vermieden.It is particularly advantageous for the use of multilayer film to make bags if the material is extruded as a tube. This prevents contamination of the inside of the bag by germs.
Es ist besonders bevorzugt, die erfindungslgmeäßen Mehrlagenfolei zur Herstellung von Beuteln für Nahrungszwecke und medizinischen Lösungen, bspw. Infusionslösungen einzusetzen.It is particularly preferred to use the multilayer film according to the invention for producing bags for food purposes and medical solutions, for example infusion solutions.
Nachfolgend wird die Erfindung anhand von Ausführungsbeispielen,/die deir Schutzunfang keineswegs a«£. e beschränkt ist, näher erläutert.The invention is explained in more detail below using embodiments, the scope of which is in no way limited.
Mehrlagenfolie auf Polypropylenbasis:Multilayer film based on polypropylene:
Außenlage: Polypropylen-Homopolymerisat (DAPLEN KF 201, erhältlich von der PCT/LINZ)) mit einer Dicke von 15 ^im Verbindungsschicht: CAWITON MED PR 3530 (erhältlich von der Fa WITTENBURG/Bissum/Niederlande) 95 &mgr;&igr;&agr;. Outer layer: polypropylene homopolymer (DAPLEN KF 201, available from PCT/LINZ)) with a thickness of 15 μm. Bonding layer: CAWITON MED PR 3530 (available from WITTENBURG/Bissum/Netherlands) 95 μm.
ein Polypropylen-Compound bestehend ausa polypropylene compound consisting of
a) Polypropylen-Homopolymerisata) Polypropylene homopolymer
b) Polypropylen-Copolymerisatb) Polypropylene copolymer
c) TPE-S (SBS, SIS, SEBS oder SEB) Innenschicht: CAWITON MED PR 3663 40^m (erhältlich von der Fa WITTENBURG/Bissum/Niederlande) 95 pm c) TPE-S (SBS, SIS, SEBS or SEB) Inner layer: CAWITON MED PR 3663 40^m (available from WITTENBURG/Bissum/Netherlands) 95 pm
ein Polypropylen-Compound bestehend ausa polypropylene compound consisting of
a) Polypropylen-Homopolymerisata) Polypropylene homopolymer
b) Polypropylen-Copolymerisatb) Polypropylene copolymer
c) TPE-S (SBS, SIS, SEBS oder SEB)c) TPE-S (SBS, SIS, SEBS or SEB)
Die Gesamtdicke der in ein Wasserbad extrudierten Mehrlagenverbundfolie betrug etwa 150um.The total thickness of the multilayer composite film extruded in a water bath was about 150 μm.
Außenlage: Polypropylen-Homopolymerisat (DAPLEN KF 201, erhältlich von der PCT/LINZ)) mit einer Dicke von 20 um Verbindungsschicht: CAWITON MED PR 3530 (erhältlich von der Fa WITTENBURG/Bissum/Niederlande) 125 umOuter layer: polypropylene homopolymer (DAPLEN KF 201, available from PCT/LINZ)) with a thickness of 20 µm Bonding layer: CAWITON MED PR 3530 (available from WITTENBURG/Bissum/Netherlands) 125 µm
ein Polypropylen-Compound bestehend ausa polypropylene compound consisting of
a) Polypropylen-Homopolymerisata) Polypropylene homopolymer
b) Polypropylen-Copolymerisatb) Polypropylene copolymer
c) TPE-S (SBS, SIS, SEBS oder SEB) Innenschicht: CAWITON MED PR 3663 55 ^m (erhältlich von der Fa WITTENBURG/Bissum/Niederlande) 95 umc) TPE-S (SBS, SIS, SEBS or SEB) Inner layer: CAWITON MED PR 3663 55 ^m (available from WITTENBURG/Bissum/Netherlands) 95 um
ein Polypropylen-Compound bestehend ausa polypropylene compound consisting of
a) Polypropylen-Homopolymerisata) Polypropylene homopolymer
b) Polypropylen-Copolymerisatb) Polypropylene copolymer
c) TPE-S (SBS, SIS, SEBS oder SEB)c) TPE-S (SBS, SIS, SEBS or SEB)
Die Gesamtdicke der in ein Wasserbad extrudierten Mehrlagenverbundfolie betrug etwa 200um.The total thickness of the multilayer composite film extruded in a water bath was about 200 μm.
Außenlage: Polypropylen-Homopolymerisat (DAPLEN KF 201, erhältlich von der PCT/LINZ)) mit einer Dicke von 25 um Verbindungsschicht: CAWITON MED PR 3530 (erhältlich von der Fa WITTENBURG/Bissum/Niederlande) 155 yimOuter layer: polypropylene homopolymer (DAPLEN KF 201, available from PCT/LINZ)) with a thickness of 25 µm Bonding layer: CAWITON MED PR 3530 (available from WITTENBURG/Bissum/Netherlands) 155 yim
ein Polypropylen-Compound bestehend ausa polypropylene compound consisting of
a) Polypropylen-Homopolymerisata) Polypropylene homopolymer
b) Polypropylen-Copolymerisatb) Polypropylene copolymer
c) TPE-S (SBS, SIS, SEBS oder SEB) Innenschicht: CAWITON MED PR 3663 70 um (erhältlich von der Fa WITTENBURG/Bissum/Niederlande) 95 umc) TPE-S (SBS, SIS, SEBS or SEB) Inner layer: CAWITON MED PR 3663 70 um (available from WITTENBURG/Bissum/Netherlands) 95 um
ein Polypropylen-Compound bestehend ausa polypropylene compound consisting of
a) Polypropylen-Homopolymerisata) Polypropylene homopolymer
b) Polypropylen-Copolymerisatb) Polypropylene copolymer
C) TPE-S (SBS, SIS, SEBS oder SEB) Die Gesamtdicke der in ein Wasserbad extrudierten Mehrlagenverbundfolie betrug etwa 250 p.m. C) TPE-S (SBS, SIS, SEBS or SEB) The total thickness of the multilayer composite film extruded in a water bath was about 250 pm
Außenlage: Polypropylen-Homopolymerisat (DAPLEN KF 201, erhältlich von der PCT/LINZ)) mit einer Dicke von 25 umOuter layer: polypropylene homopolymer (DAPLEN KF 201, available from PCT/LINZ)) with a thickness of 25 µm
Verbindungsschicht: Polyisobuten-Homopolymerisat - mit einer Dicke von 100 ^mBonding layer: Polyisobutene homopolymer - with a thickness of 100 ^m
Innenschicht: CAWITON MED PR 3663 70 um (erhältlich von der Fa WITTENBURG/Bissum/Niederlande) 95 umInner layer: CAWITON MED PR 3663 70 um (available from WITTENBURG/Bissum/Netherlands) 95 um
ein Polypropylen-Compound bestehend ausa polypropylene compound consisting of
a) Polypropylen-Homopolymerisata) Polypropylene homopolymer
b) Polypropylen-Copolymerisatb) Polypropylene copolymer
c) TPE-S (SBS, SIS, SEBS oder SEB)c) TPE-S (SBS, SIS, SEBS or SEB)
Die Gesamtdicke der in ein Wasserbad extrudierten Mehrlagenverbundfölie betrug etwa 250 um.The total thickness of the multilayer composite film extruded in a water bath was about 250 µm.
Diese Mehrlagenfolien bzw. daraus hergestellte Beutel sollen insbesondere für medizinische Zwecke bevorzugt heißsterilisierbar sein und auch keine Inhaltsstoffe der Folien an das Beutelinnere abgeben.These multilayer films or bags made from them should preferably be heat-sterilizable, especially for medical purposes, and should not release any of the film’s ingredients into the bag’s interior.
Claims (1)
Priority Applications (15)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE29605214U DE29605214U1 (en) | 1996-03-21 | 1996-03-21 | Multi-layer film, in particular for bags for solutions |
| DE19640038A DE19640038C2 (en) | 1996-03-21 | 1996-09-29 | Multi-layer film based on polypropylene, process for its production and its use |
| EP19960945824 EP0892830B1 (en) | 1996-03-21 | 1996-10-23 | Multilayered sheet, process for the production thereof and use thereof |
| HU9901061A HU229658B1 (en) | 1996-03-21 | 1996-10-23 | Transparent multilayered sheet, process for the production thereof and use thereof |
| ES96945824T ES2205074T3 (en) | 1996-03-21 | 1996-10-23 | MULTI-PATH FILM AND PROCEDURE FOR ITS PRODUCTION, AND ITS USE. |
| JP53301297A JP2000506462A (en) | 1996-03-21 | 1996-10-23 | Multilayer film, method of manufacturing the same, and method of using the same |
| KR19980707051A KR100439410B1 (en) | 1996-03-21 | 1996-10-23 | Multilayer foil, its manufacturing method and use |
| US09/142,975 US6127043A (en) | 1996-03-21 | 1996-10-23 | Multilayered sheet, process for the production thereof and use thereof |
| AT96945824T ATE247152T1 (en) | 1996-03-21 | 1996-10-23 | MULTI-LAYER FILM, METHOD FOR THE PRODUCTION THEREOF AND USE THEREOF |
| RU98119079/04A RU2193973C2 (en) | 1996-03-21 | 1996-10-23 | Transparent multilayer film and method of its production |
| PCT/DE1996/002012 WO1997034951A1 (en) | 1996-03-21 | 1996-10-23 | Multilayered sheet, process for the production thereof and use thereof |
| BR9612569A BR9612569A (en) | 1996-03-21 | 1996-10-23 | Multilayered sheet, process for its preparation and application |
| DE59610666T DE59610666D1 (en) | 1996-03-21 | 1996-10-23 | MULTIPLE FILM, METHOD FOR THEIR PRODUCTION AND THEIR USE |
| AU17166/97A AU1716697A (en) | 1996-03-21 | 1996-10-23 | Multilayered sheet, process for the production thereof and use thereof |
| CNB961802243A CN1161406C (en) | 1996-03-21 | 1996-10-23 | Multilayered sheet, process for prodn. thereof and use thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE29605214U DE29605214U1 (en) | 1996-03-21 | 1996-03-21 | Multi-layer film, in particular for bags for solutions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE29605214U1 true DE29605214U1 (en) | 1997-07-24 |
Family
ID=8021418
Family Applications (3)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE29605214U Expired - Lifetime DE29605214U1 (en) | 1996-03-21 | 1996-03-21 | Multi-layer film, in particular for bags for solutions |
| DE19640038A Expired - Fee Related DE19640038C2 (en) | 1996-03-21 | 1996-09-29 | Multi-layer film based on polypropylene, process for its production and its use |
| DE59610666T Expired - Lifetime DE59610666D1 (en) | 1996-03-21 | 1996-10-23 | MULTIPLE FILM, METHOD FOR THEIR PRODUCTION AND THEIR USE |
Family Applications After (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE19640038A Expired - Fee Related DE19640038C2 (en) | 1996-03-21 | 1996-09-29 | Multi-layer film based on polypropylene, process for its production and its use |
| DE59610666T Expired - Lifetime DE59610666D1 (en) | 1996-03-21 | 1996-10-23 | MULTIPLE FILM, METHOD FOR THEIR PRODUCTION AND THEIR USE |
Country Status (2)
| Country | Link |
|---|---|
| DE (3) | DE29605214U1 (en) |
| RU (1) | RU2193973C2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001001775A1 (en) * | 1999-07-07 | 2001-01-11 | Biopure Corporation | Preserving a hemoglobin blood substitute with a transparent overwrap |
| US6610832B1 (en) | 1995-03-23 | 2003-08-26 | Biopure Corporation | Preserving a hemoglobin blood substitute with a transparent overwrap |
| WO2005116128A1 (en) * | 2004-05-25 | 2005-12-08 | E.I. Dupont De Nemours And Company | Copolyetherester composition and multilayer structure thereof |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6127009A (en) * | 1996-05-08 | 2000-10-03 | Pactiv Corporation | Dispenser unit, process for manufacturing the same and its use |
| DE10361851B4 (en) | 2003-12-23 | 2018-08-02 | Polycine Gmbh | Heat sterilizable multilayer film and use thereof |
| AU2005304335B2 (en) * | 2004-11-10 | 2009-09-17 | Avery Dennison Corporation | In-mold labels and uses thereof |
| RU2474598C2 (en) * | 2005-06-23 | 2013-02-10 | Эвери Деннисон Копэрейшн | Hot-melt pressure-sensitive adhesive composition and adhesive article |
| DE102007003327A1 (en) * | 2007-01-17 | 2008-07-24 | Evonik Degussa Gmbh | Multilayer film and composite part made therefrom |
| KR101039270B1 (en) * | 2007-12-24 | 2011-06-07 | 제이더블유생명과학 주식회사 | Multilayer Film For Medical Solution Container And A Container Comprising The Same |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2063868C (en) * | 1991-03-25 | 2002-11-12 | Walter Berndt Mueller | Nylon copolymer medical film |
| AT403583B (en) * | 1993-07-26 | 1998-03-25 | Danubia Petrochem Polymere | Graft-modified elastomeric polypropylene@ - useful as compatibility promoters and coupling agents in polyolefin/non-polyolefin blends and polyolefin/metal composites |
| JP2997831B2 (en) * | 1993-09-06 | 2000-01-11 | グンゼ株式会社 | Laminate |
| DE4447626C5 (en) * | 1994-03-29 | 2007-01-25 | Fresenius Ag | Medical multi-chamber bag |
-
1996
- 1996-03-21 DE DE29605214U patent/DE29605214U1/en not_active Expired - Lifetime
- 1996-09-29 DE DE19640038A patent/DE19640038C2/en not_active Expired - Fee Related
- 1996-10-23 DE DE59610666T patent/DE59610666D1/en not_active Expired - Lifetime
- 1996-10-23 RU RU98119079/04A patent/RU2193973C2/en not_active IP Right Cessation
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6610832B1 (en) | 1995-03-23 | 2003-08-26 | Biopure Corporation | Preserving a hemoglobin blood substitute with a transparent overwrap |
| WO2001001775A1 (en) * | 1999-07-07 | 2001-01-11 | Biopure Corporation | Preserving a hemoglobin blood substitute with a transparent overwrap |
| WO2005116128A1 (en) * | 2004-05-25 | 2005-12-08 | E.I. Dupont De Nemours And Company | Copolyetherester composition and multilayer structure thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| DE19640038A1 (en) | 1997-09-25 |
| RU2193973C2 (en) | 2002-12-10 |
| DE59610666D1 (en) | 2003-09-18 |
| DE19640038C2 (en) | 2001-11-29 |
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