HK1213208B - Application assembly with a medical fluid - Google Patents

Description

The present invention relates to the field of drug administration.

For the application of medicinal substances, application syringes are usually used, which can be operated either manually or using a pumping system. Conventional application syringes include a container that can be filled with a medicinal substance, as well as a piston that is slidably arranged within the container for administering the medicinal substance.

Medicinal substances that can be applied using an application syringe may be present in the form of a medicinal substance emulsion, which can fill a container of an application syringe. For oxygen-sensitive medicinal substances such as propofol, these medicinal substance emulsions are usually stored in glass containers, such as glass bottles or ampoules. Thus, the medicinal substance can be stored in an oxygen-tight manner until just before use, and then transferred into an application syringe with a container if needed, and subsequently administered. However, such storage of medicinal substances is complicated and therefore expensive. Moreover, contamination of the medicinal substance may occur due to the separate transfer process.

Therefore, the printed publication WO 94/25089 proposed using application syringes with glass containers to store the oxygen-sensitive propofol directly therein. However, application syringes with glass containers are not shatterproof. As a result, inserting such glass containers into pump injection systems is problematic.

In the document JP 2008 067989 A, a storage container for a pre-filled syringe is described. The syringe body is made of polypropylene or a cyclic polyolefin. The syringe and a plunger rod are placed in the storage container. The storage container is sealed with a removable film.

In the patent application US 2012/0143144 A1, an auto-injector is described which comprises a syringe body containing a medicinal substance and an oxygen absorber. An oxygen-impermeable container encloses the medicinal substance and the oxygen-absorbing material within the auto-injector.

In the document US 2006/0275336 A1, a kit for an osteoinductive agent is described. Two syringes are placed in a container filled with an oxygen-free gas.

Therefore, the object of the present invention is to create an efficient concept for storing oxygen-sensitive pharmaceuticals in containers of application syringes.

This task is solved by the features of the independent claims. Advantageous further developments are the subject of the dependent claims, the description, and the drawings.

The present invention is based on the insight that the above object can be solved by using a plastic container of an application syringe pre-filled with an oxygen-sensitive medicament, which is hermetically enclosed by an oxygen-tight casing. In this way, it becomes possible to store oxygen-sensitive medicaments in pre-filled and oxygen-permeable plastic containers of application syringes over a longer period of time.

The oxygen-dense casing can, for example, accommodate the application syringe with the pre-filled plastic container as secondary packaging or blister pack, and protect against oxygen ingress.

According to one aspect, the invention relates to an application arrangement comprising an application syringe with a plastic container, wherein the plastic container is filled with an oxygen-sensitive medicament fluid, and an oxygen-tight casing that hermetically encloses the application syringe, preferably wherein at least partially the inner side of the plastic container is silicone-coated. Due to this silicone coating, in particular the sliding ability of a piston within the plastic container can be increased and the medicament fluid can be additionally protected.

According to another aspect, the invention relates to an application arrangement comprising an application syringe including a plastic container filled with an oxygen-sensitive medicinal fluid; and an oxygen-tight casing enclosing the application syringe in an oxygen-tight manner, wherein the oxygen-sensitive medicinal fluid is a medicinal emulsion containing propofol, and the plastic container is made of plastic comprising at least one cyclo-olefin copolymer, and wherein at least partially, the inner side of the plastic container is silicone-coated. Such a plastic container is particularly resistant to propofol, which acts as a solvent. At the same time, the propofol is effectively protected especially against oxygen present in the environment.

The oxygen-dense enclosure preferably surrounds the application syringe with the filled plastic container, thereby also protecting the medicinal product stored in the plastic container against oxygen, even when using oxygen-permeable plastics. The inner space enclosed by the sleeve, in which the application syringe is arranged, can additionally be evacuated to reduce the oxygen density. However, the inner space enclosed by the sleeve can also be filled with a fluid, such as a gas or liquid, that is low in oxygen or binds oxygen.

The oxygen-dense layer has an oxygen permeability of less than or equal to 10 cm³/m²·d·bar, preferably less than or equal to 5 cm³/m²·d·bar, particularly preferably less than or equal to 2 cm³/m²·d·bar. The oxygen permeability or oxygen tightness is determined according to the specifications in the standard DIN 53380.

Furthermore, the oxygen barrier layer also acts as a barrier to water vapor. The oxygen barrier layer has a water vapor permeability of less than or equal to 10 g/m²·d, preferably less than or equal to 5 g/m²·d, particularly preferably less than or equal to 3 g/m²·d. The water vapor permeability is determined according to the specifications in the standard DIN 53122.

The plastic container can be completely or only partially filled with the medicinal fluid.

The application syringe can be formed solely by the filled plastic container. According to one embodiment, the application syringe may include a plastic piston rod. The plastic piston rod can be a component of the application arrangement. According to one embodiment, however, the plastic piston rod is not a component of the application arrangement.

According to an embodiment, the oxygen-sensitive pharmaceutical fluid is a pharmaceutical emulsion.

According to an embodiment, the drug fluid comprises a drug with poor water solubility, requiring at least 30 ml of water to dissolve 1 g of the drug. Thus, by using the oxygen-tight casing, an entire group of oxygen-sensitive drugs can be stored permanently.

According to an embodiment, the active pharmaceutical ingredient fluid is or comprises propofol, particularly a propofol emulsion. Propofol is described by the chemical name 2,6-diisopropylphenol (IUPAC),

The plastic container is formed from a plastic material that includes one of the following polymers: cyclo-olefin copolymer, cyclo-olefin polymer, or crystal clear polymer. Such a plastic container is resistant to solvents. In particular, such a plastic container can be used for storing propofol, which acts as a solvent.

According to an embodiment, the application arrangement or application syringe further comprises a plastic piston rod that is displaceably stored in the plastic container, and the plastic piston rod is particularly arranged next to the plastic container and hermetically covered by the oxygen-tight sheath.

According to one embodiment, the application syringe may essentially include only the filled plastic container, which is hermetically sealed against oxygen. The plastic piston rod can then be provided separately. According to this embodiment, an oxygen-tight covering is not necessary for packaging the plastic piston rod.

According to an embodiment, the plastic piston rod is formed from a plastic material comprising one of the following polymers: cyclo-olefin copolymer, cyclo-olefin polymer, or crystal clear polymer, or it is formed from polypropylene.

In a further embodiment of the invention, the plastic container and/or the plastic piston rod are at least axially displaceably mounted within the oxygen-tight housing. This allows the plastic container and/or the plastic piston rod to perform a compensating movement in case of a lateral, for example axial, impact, such as in the direction of the opposite side, particularly without damaging themselves and/or without damaging the housing. In one embodiment of the invention, the plastic container and/or the plastic piston rod and the housing are designed such that the two end faces of the plastic container and/or the two end faces of the plastic piston rod can each be positioned at a distance of approximately 0.5 cm to approximately 2 cm from the inner surface of the housing. This provides sufficient space to enable an axial compensating movement.

In a further embodiment of the invention, the plastic container and the plastic piston rod are at least partially separated from each other by at least one flexible, preferably elastic, spacer. This allows shocks in a direction perpendicular to the longitudinal axis of the plastic container and/or the plastic piston rod to be cushioned. In one embodiment, the at least one spacer has a width of approximately 0.3 cm to about 1.5 cm.

According to an embodiment, the oxygen-tight sheath comprises an ethylene-vinyl alcohol copolymer barrier, particularly an ethylene-vinyl alcohol copolymer layer. By providing the ethylene-vinyl alcohol copolymer barrier, the sheath is made oxygen-tight. The ethylene-vinyl alcohol copolymer barrier can, for example, be designed in the form of an ethylene-vinyl alcohol copolymer layer with which the sheath is sealed. However, the ethylene-vinyl alcohol copolymer barrier can also be directly provided in plastic from which the oxygen-tight sheath can be manufactured.

According to an embodiment, the oxygen barrier layer can be made of a multi-layer plastic. The plastic layers can, for example, include a polyethylene terephthalate film with an ethylene-vinyl alcohol copolymer barrier or a polyester with an ethylene-vinyl alcohol copolymer barrier. The multi-layer plastic can further include a peelable polyethylene film, particularly sealed with an oxygen-tight ethylene-vinyl alcohol copolymer barrier.

According to an embodiment, the oxygen-dense casing comprises a shell formed from thermoplastic plastic, in particular deep-drawn. The shell can, for example, be deep-drawn to accommodate the application syringe.

According to one embodiment, the shell forms or creates a shaping part for the positive engagement reception of the application syringe. In this way, the application syringe is positively held within the shell. The shaping part forming the shell can further include a positive engagement receiving portion for the piston rod. Each positive engagement receiving portion can be realized by a depression in a shell base. The shell can also be shaped such that locking of the application syringe is possible therein. For example, the shell formed as a shaping part can include latching projections on its side, which are elastic and are initially displaced when inserting the plastic container and/or the plastic piston rod, and then return to their original position, thereby enabling the application syringe to be locked. In one design, the shell has a wall thickness in a range of 50 µm to 5000 µm, preferably from 10 µm to 1000 µm. The measurement is performed according to DIN 53370.

According to an embodiment, the thermoplastic plastic comprises an amorphous polyethylene terephthalate film with an ethylene-vinyl alcohol copolymer barrier or biaxially oriented polyester with an ethylene-vinyl alcohol copolymer barrier. In one configuration, the thermoplastic plastic, which forms the shell, has a surface weight in a range of 50 g/m² to 5000 g/m², preferably from 300 g/m² to 1000 g/m². The measurement is carried out according to ISO 2286-2.

According to an embodiment, the shell is sealed with a peelable film or polyethylene film or a polyethylene film with an ethylene-vinyl alcohol copolymer barrier layer, which is oxygen-tight. In one design, the peelable film has a thickness in a range of 10 µm to 2000 µm, preferably from 50 µm to 300 µm. The measurement is carried out according to DIN 53370. In another design, the peelable film has a grammage in a range of 10 g/m² to 1000 g/m², preferably from 50 g/m² to 200 g/m². The measurement is performed according to ISO 2286-2.

According to an embodiment, the oxygen-impermeable casing comprises another shell formed from thermoplastic plastic, particularly a shell formed from thermoplastic plastic, wherein the further shell includes an ethylene-vinyl alcohol copolymer barrier, and wherein the further shell is connected to the shell in an oxygen-impermeable manner, particularly welded or glued. The further shell can, for example, also form a molded part for the positive-locking reception of the application syringe. Thus, the application syringe is held by one hand by a shell forming a lower part and by a lid or by an upper part formed by the further shell. The shell and the further shell are, for example, connected in an oxygen-impermeable manner along a joining seam, which can be realized by welding or gluing. The connected shells thus form a stable casing that can safely accommodate the pre-filled plastic container. The further shell can also be made of plastic and have the same material structure as the shell.

According to an embodiment, the plastic container is fluid-tightly closed at both the distal and proximal ends by respective removable closures. The removable closures can, for example, be designed as plugs, stoppers, pistons, or screw caps. This prevents the medicinal fluid from leaking out. The distal closure of the plastic container can be formed by a piston, into which a plastic piston rod can be inserted or screwed.

According to an embodiment, the application arrangement may include an oxygen absorber, which may, for example, comprise iron powder. The oxygen absorber may be insertable into the shell of the housing or may be connected to the shell.

The inner side of the plastic container and/or the outer side of the piston and/or the outer side of the closure is at least partially, preferably entirely, silicone-coated, in particular with silicone. This increases their sliding properties. Furthermore, this provides additional protection for the medicinal product.

According to another aspect, the invention relates to a method for producing the application arrangement according to the invention. The method comprises the steps of providing an application syringe with a plastic container, filling the plastic container with an oxygen-sensitive pharmaceutical fluid, in particular with propofol, and hermetically enclosing the application syringe with the filled plastic container by means of a hermetic cover.

Further features of the manufacturing process arise directly from the structure of the inventive application arrangement and the production steps, in particular, necessary for the manufacture of the aforementioned plastics.

Further embodiments will be explained in more detail with reference to the accompanying drawings. They show: Fig. 1, a schematic view of an application arrangement; Fig. 2a, b, schematic side views of an application arrangement; and Fig. 3, a flowchart of a manufacturing method for producing an application arrangement.

Fig. 1 shows schematically an application arrangement according to an embodiment. The application arrangement comprises an application syringe 100 with a plastic container 101 and a plastic plunger rod 103. The plunger rod 103 has an insert 105 at its distal end, which can be inserted into a piston 113. The plastic plunger rod 103 is stored, for example, outside the plastic container 101 here.

The plastic container 101, as indicated in Fig. 1, is filled with a medicinal fluid 107, preferably with propofol. The plastic container 101 has, on the proximal side, a nozzle 109, which is closed with a closure 111, for example, a plastic cap. The nozzle 109 has, preferably, a male Luer connection or a Luer-Lock connection.

The plastic container 101 is closed on the distal side by a piston 113, into which the insert 105 can be inserted, for example, screwed in. In this way, the plastic piston rod 103 can be completed with the piston 113. Thus, the piston 113 also serves simultaneously as a distal closure of the plastic container 101. According to one embodiment, the plastic piston rod 103 may already have a piston instead of the insert 105. In this case, the piston container 101 is provided on the distal side with another closure.

Furthermore, the plastic container 101 includes lateral flaps 115, 117, which allow not only manual application but also the use of the applicator syringe in a pumping system.

The application arrangement further includes an oxygen-tight casing 119, which can be formed, for example, as a blister or as secondary packaging, and which completely and oxygen-tightly encloses the application syringe 100.

The oxygen-impermeable sheath 119 comprises an oxygen-impermeable shell 121 and an oxygen-impermeable film 123, which seals the shell 121 in an oxygen-impermeable manner along an edge 125 of the shell 121.

For this purpose, the container 121 can be formed from a transparent deep-drawing film based on an APET film with an EVOH barrier (EVOH: ethylene-vinyl alcohol) and a peelable sealing layer made of polyethylene. Thus, the container 121 is a good oxygen barrier and has high stiffness as well as good deep-drawing properties, which allows the container 121 to be designed as a shaped part. The container 121 can have at least one of the following technical properties: Total thickness 500 µm DIN 53370, surface weight 646 g/m2 ISO 2286-2, oxygen permeability < 1 cm3/m2 d bar 23°C / 35% r.F. DIN 53380, water vapor permeability < 1 g/m2 d 23°C / 85% r.F. DIN 53122.

Film 123 can, for example, be a polyethylene film with an EVOH barrier, and thus also be oxygen-tight. Film 123 can also be made based on an APET film (APET: amorphous polyethylene terephthalate), thereby achieving increased rigidity. Film 123 is, for example, oxygen-tight along the edge 125 connected to the shell 121, for example by welding or gluing.

The housing 121 can be provided as a form-fitting component for the form-coupled reception of the plastic container 101 and the piston 113. For this purpose, the housing 121 can include a receiving recess 127 for receiving the plastic container 101 and a receiving recess 129 for receiving the plastic piston rod 103.

For holding the plastic container 101, the receiving trough 127 can include clamping protrusions 131. The receiving trough 129 can include clamping protrusions 133 for holding the plastic piston rod 103. The clamping protrusions 131, 133 are elastic and thus can be pressed when the plastic container 101 or the plastic piston rod 103 is mounted. Due to the elasticity of the clamping protrusions 131, 133, these exert, for example, a radially directed force on the plastic container 101 or on the plastic piston rod 103, thereby allowing these elements to be fixed. In one embodiment, the elements 101 and/or 103 can be fixed in such a way that they cannot fall out of the holder, but at the same time remain axially movable. Thus, the plastic container 101 and/or the plastic piston rod 103 can perform an axial compensating movement, for example, during an axial impact, especially without being damaged themselves and/or without damaging the housing 121.

The receiving recesses 127 for receiving the plastic container 101 and the receiving recesses 129 for receiving the plastic piston rod 103 are arranged separately from each other by at least one spacer 130. In the illustrated embodiment, they are separated from each other by two spacers 130. The aforementioned clamping projections 131, 133 are arranged on the spacers 130. The spacers 130 are flexible, preferably elastic. This allows shocks to be cushioned in a direction perpendicular to the longitudinal axis of the plastic container 101 and/or the plastic piston rod 103. Each of the two spacers 130 is provided by means of a type of wall or section of a wall.

The container 121 and/or the film 123 is made of a plastic composite consisting of biaxially oriented polyester with a co-extruded sealing barrier layer made of polyethylene, EVOH, and polyethylene. Such a plastic composite is characterized by good transparency. In addition, a wide sealing area as well as a good oxygen barrier can be achieved. A film 123 formed in this way can be used particularly as a lid film for sealing deep-drawn containers, for example the container 121. The film 123 can have at least one of the following technical properties: Total thickness 100 µm DIN 53370, surface weight 107.5 g/m2 ISO 2286-2, tensile strength - longitudinal 40 - 60 N/mm2 ISO 527-3, tensile strength - transverse 35 - 55 N/mm2 ISO 527-3, elongation at break - longitudinal 40 - 120 % ISO 527-3, elongation at break - transverse 40 - 120 % ISO 527-3, oxygen permeability 1 cm3/m2 d bar 23°C / 35% r.F. DIN 53380, CO2 permeability < 4 cm3/m2 d bar 23°C / 35% r.F. DIN 53380, N2 permeability < 1 cm3/m2 d bar 23°C / 35% r.F. DIN 53380.

The plastic container 101 is shaped according to an embodiment from cyclic polymer. Cyclic polymers have a high purity and resistance, ensuring a longer storage of pharmaceuticals. However, cyclic polymers are permeable to oxygen. This oxygen permeability is not only disadvantageous for oxygen-sensitive products, such as oil-in-water emulsions, but also for oxygen-sensitive pharmaceuticals, such as propofol.

To compensate for the oxygen permeability of the plastic container 101 according to one embodiment, the housing 119 is provided, which can be made of a plastic blister and may have an oxygen barrier layer.

The plastic container 101 is shaped according to an embodiment from COC (Cyclic Olefin Copolymer), COP (Cyclic Olefin Polymer) or CCP (Crystal Clear Polymer). These prove to be resistant to propofol, which acts as a solvent. The piston 113 and/or the cap 111 is made, for example, of rubber, particularly bromobutyl. The plastic piston rod 103 can, for example, be formed from polypropylene.

The plastic container 101 is formed from a transparent plastic belonging to the group of cyclo-olefin copolymers or cyclo-olefin polymers. The housing 119 forms an oxygen-impermeable packaging that encloses the plastic container 101 filled with the medicinal fluid 107.

The inside of the plastic container 101 is silicone-treated or coated with silicone. This increases their lubricity. In addition, the medicinal product is thereby additionally protected.

According to another embodiment, piston 113 is at least partially siliconized. According to one embodiment, the closure 11 is also at least partially siliconized.

Figures 2a and 2b show different side views of the application arrangement shown in Figure 1. According to one embodiment, the application arrangement can include a non-fluid oxygen absorber 135, which may for example comprise iron dust. The oxygen absorber 135 is arranged, for example, at the bottom of the shell 121.

In Fig. 3, a diagram of a method for producing an application arrangement is shown. The method 300 includes the step 301 of providing an application syringe with a plastic container, the step 303 of filling the plastic container with an oxygen-sensitive pharmaceutical fluid, for example, with propofol or a propofol fluid, particularly a propofol emulsion, and the oxygen-tight enclosing 305 of the application syringe with the filled plastic container by an oxygen-tight cover. The method further includes the step of positioning the pre-filled plastic container 101 and the plastic piston rod 103 in the deep-drawn cup 121, as well as the oxygen-tight closing of the cup 121 with the lid film 123, for example, by welding or bonding.

One advantage of the application arrangement, according to an embodiment, is its easy application without the need for transferring the medicinal product into additional containers. Furthermore, the application syringe can be directly taken and used without requiring further assembly steps. The plastic container 101, for example, has a capacity of 50 ml, thereby enabling automatic detection of the plastic container by conventional pumping systems. By using the plastic container, a higher impact resistance compared to glass is achieved. In addition, waste can be reduced while saving time by eliminating application preparation steps, which are, for example, caused by the transfer of the medicinal product.

Reference list

100 Application syringe 101 Plastic container 103 Plastic piston rod 105 Insert 107 Medicinal fluid 109 Nozzle 111 Cap 113 Plastic piston 115 Side wings 117 Side wings 119 Oxygen tight casing 121 Shell 123 Film 125 Rim 127 Receiving groove for the application syringe 129 Receiving groove for the piston rod 130 Spacer or wall section between the receiving groove for the application syringe and the receiving groove for the piston rod 131 Clamp projection 133 Clamp projection 135 Oxygen absorber 300 Method 301 Step of preparation 303 Step of filling 305 Oxygen tight wrapping

Claims (13)

1. An application assembly comprising:

   - an applicator syringe (100) comprising a plastic receptacle (101) made of a transparent plastic from the group of cyclic olefin copolymers or cyclic olefin polymers, wherein the plastic receptacle (101) is filled with an oxygen-sensitive active pharmaceutical ingredient fluid (107); and

   - an oxygen-tight envelope (119) which envelopes the applicator syringe (100) in an oxygen-tight manner, wherein the oxygen-tight envelope (119) comprises an oxygen-tight shell (121) and an oxygen-tight film (123), characterized in that the shell (121) is formed from a transparent deep-drawn film based on APET film with an EVOH barrier and a peelable sealing layer made of polyethylene and/or in that the film (123) is formed from a transparent plastic composite of biaxially oriented polyester comprising a co-extruded sealing block layer made of polyethylene, EVOH, polyethylene, wherein an interior enclosed by the envelope (119) is filled with a fluid which is low in oxygen or binds oxygen; and

   - an oxygen absorber (135) in the envelope (119), wherein an inside of the plastic receptacle (101) is siliconized at least in sections.
2. The application assembly according to claim 1, wherein the oxygen-sensitive active pharmaceutical ingredient fluid (107) is an active pharmaceutical ingredient emulsion.
3. The application assembly according to claim 1 or 2, wherein the active pharmaceutical ingredient fluid (107) comprises an active pharmaceutical ingredient having a water solubility in which at least 30 ml of water are required to dissolve 1 g of active pharmaceutical ingredient.
4. The application assembly according to any of the preceding claims, wherein the active pharmaceutical ingredient fluid (107) comprises propofol.
5. The application assembly according to any of the preceding claims, wherein the plastic receptacle (101) is formed from plastic comprising Crystal Clear Polymer.
6. The application assembly according to any of the preceding claims, wherein the applicator syringe (100) comprises a plastic plunger rod (103) storable in a shiftable manner in the plastic receptacle (101), in particular a plastic plunger rod (103) which is storable in a shiftable manner in the plastic receptacle (101) and arranged beside the plastic receptacle (101) and which is enveloped in an oxygen-tight manner by means of the oxygen-tight envelope (119).
7. The application assembly according to claim 6, wherein the plastic plunger rod (103) is formed from plastic comprising at least one of the following polymers: cyclic olefin copolymer, cyclic olefin polymer or Crystal Clear Polymer, or is formed from polypropylene.
8. The application assembly according to any of the preceding claims, wherein the plastic receptacle (101) is stored in an at least axially shiftable manner in the oxygen-tight envelope (119) and/or wherein the plastic plunger rod (103) is stored in an at least axially shiftable manner in the oxygen-tight envelope (119).
9. The application assembly according to any of the preceding claims, wherein the plastic receptacle (101) and the plastic plunger rod (103) are stored at least separately by means of at least one flexible spacer (130).
10. The application assembly according to any of the preceding claims, wherein the shell (121) is deep-drawn.
11. The application assembly according to claim 10, wherein the shell (121) forms a molding for the formfitting accommodation of the applicator syringe (100).
12. The application assembly according to any of claims 10 to 11, wherein the oxygen-tight envelope (119) comprises a further shell formed from thermoplastic, in particular a shell formed from thermoplastic, wherein the further shell comprises an ethylene-vinyl alcohol copolymer barrier, and wherein the further shell is joined, in particular welded or adhesively bonded, to the shell (121) in an oxygen-tight manner.
13. A method for producing the application assembly according to any one of claims 1 to 12, comprising:

    Providing (301) an applicator syringe comprising a plastic receptacle (101) made of a transparent plastic from the group of cyclic olefin copolymers or cyclic olefin polymers;

    Siliconizing at least one section of an inside of the plastic receptacle (101);

    Filling (303) the plastic receptacle with an oxygen-sensitive active pharmaceutical ingredient fluid, in particular with propofol; and

    Enveloping (305), in an oxygen-tight manner, the applicator syringe with the filled plastic receptacle by means of an oxygen-tight envelope (119), wherein the oxygen-tight envelope (119) comprises an oxygen-tight shell (121) and an oxygen-tight film (123), characterized in that

    the shell (121) is formed from a transparent deep-drawn film based on APET film with an EVOH barrier and a peelable sealing layer made of polyethylene and/or in that the film (123) is formed from a transparent plastic composite of biaxially oriented polyester comprising a co-extruded sealing block layer made of polyethylene, EVOH, polyethylene,

    wherein an interior enclosed by the envelope (119) is filled with a fluid which is low in oxygen or binds oxygen and an oxygen absorber (135) is laid into the envelope (119).