WO2003018312A1 - A steam-sterilizable multilayer film and containers made thereof - Google Patents

A steam-sterilizable multilayer film and containers made thereof

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Publication number
WO2003018312A1
WO2003018312A1 PCT/FI2002/000688 FI0200688W WO2003018312A1 WO 2003018312 A1 WO2003018312 A1 WO 2003018312A1 FI 0200688 W FI0200688 W FI 0200688W WO 2003018312 A1 WO2003018312 A1 WO 2003018312A1
Authority
WO
Grant status
Application
Patent type
Prior art keywords
layer
film
barrier
bag
according
Prior art date
Application number
PCT/FI2002/000688
Other languages
French (fr)
Inventor
Hannu Maasola
Deva Shyam Pekka Weeraratne
Paavo Petteri Muhonen
Original Assignee
Wihuri Oy
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date

Links

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/34Layered products comprising a layer of synthetic resin comprising polyamides
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/32Layered products comprising a layer of synthetic resin comprising polyolefins
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61JCONTAINERS 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
    • A61J1/00Containers specially adapted for medical or pharmaceutical purposes
    • A61J1/05Containers specially adapted for medical or pharmaceutical purposes for collecting, storing or administering blood, plasma or medical fluids ; Infusion or perfusion containers
    • A61J1/14Details, e.g. provisions for hanging or shape retaining means; Accessories therefor, e.g. inlet or outlet ports, filters or caps
    • A61J1/1443Containers with means for dispensing liquid medicaments in a filtered or sterile way, e.g. with bacterial filters
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61JCONTAINERS 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
    • A61J1/00Containers specially adapted for medical or pharmaceutical purposes
    • A61J1/05Containers specially adapted for medical or pharmaceutical purposes for collecting, storing or administering blood, plasma or medical fluids ; Infusion or perfusion containers
    • A61J1/14Details, e.g. provisions for hanging or shape retaining means; Accessories therefor, e.g. inlet or outlet ports, filters or caps
    • A61J1/1468Containers characterised by specific material properties

Abstract

The invention relates to a steam-sterilizable, multilayer film (6). The film (6) has at least six polymer layers. The first layer (1) is a protective layer containing polyolefin based polymers, the second layer is an adhesive tie layer (2), the third layer is a barrier layer (3) made of caprolactam-free polyamide or a derivative or a copolymer thereof, the fourth layer is an adhesive tie layer (2), the fifth layer is a core layer (4), which contains polyolefin blended possibly with a thermoplastic elastomer or a derivative thereof, the sixth layer (6) is a sealing layer containing polyolefin or/and thermoplastic elastomer polymers or a derivative thereof.

Description

A steam-sterilizable multilayer film and containers made thereof

The invention relates to a steam-sterilizable multilayer film according to preamble of claim 1.

The invention also relates to the use of the steam-sterilizable multilayer film according to claim 10.

The invention also relates to the process for making of the steam-sterilizable multilayer film according to preamble of claim 11.

The use of plastic bags for packaging pharmaceutical solutions are well known in the medical field. They are used in applications where transparent and flexible packages are needed for example for infusion solutions, premixed drug solutions, dialysis solutions and blood bags. The plastic bags intended to packaging pharmaceutical solutions must be inexpensive and easy to manufacture and they must not react/interact with the components of the pharmaceutical solution, and must not migrate with any additive or component into the pharmaceutical solution. Their resistance to heat must be high, since they are subject to steam sterilization at 100-121°C. They must also be easy to seal with heat and they must withstand mechanical stresses caused by the surroundings. Their permeability to water vapor, air, oxygen and other gases must be low. One key property of plastic bags intended to be used with pharmaceutical solutions is their transparency. The co-extruded, multilayer plastic film with a barrier layer is used in containers for packaging pharmaceutical solutions.

The only known container concept that fulfils all the demands above is a container with an inner and an outer bag. Especially difficult to meet is the demand of very low permeability to water vapor and oxygen.

The first main object of the invention is to provide a film and a plastic container made thereof which would be steam sterilizable and suitable for use in two bag concepts as an inner bag and as an outer bag and also in one bag concept without outer wrapping. Requirements for inner bag are softness, transparency, and collapsibility. An inner bag should own some water barrier properties and it should be steam- sterilizable. Outer bag should be steam-sterilizable and it should have enough oxygen barrier properties for the use mentioned bag is intended for. A film suitable for one bag concept should have properties of an inner bag and an outer bag. In one bag concept there is no need of the outer bag. Therefore the film for one bag concept should not be too brittle, hard or inflexible but soft and collapsable. It should have required water and oxyxen permeability properties and be transparent. There should be no migration of the container material into the solution in said container. The protection of the film against oxygen and water vapor is important since oxygen may react with active pharmaceutical substances and effect the performance of the drug. Diffusion of water vapor will effect the drug concentration. Influx of gases in the container will effect the volume readings on the container and can, if larger amounts of gas influx to the container, give causes to gases to flow in the blood stream.

The second main object of the invention is to provide a film and a container made thereof suitable for medical and pharmaceutical solutions requiring a medium oxygen barrier. Medium oxygen barrier has oxygen transmission rates in a unit range of 10 to 500, preferably 201-100. Such medical and pharmaceutical solutions are typically aqueous solutions for intravenous infusion.

The third objective of the invention is to provide a film and a container made thereof which have low manufacturing costs.

In this context container with one bag concept means a container used to contain pharmaceutical or physiological solutions with one film bulkhead.

In the following is reviewed prior art dealing inner bag solutions and outer bag solutions and the possibility of using these known plastic materials in the one bag concept.

The inner bag plastic material has since the beginning been soft polyvinyl chloride, i.e. PVC (for example US Patent 4,507,123). It has been observed that a patient who has been treated long periods with an infusion solution, packed in a PNC bag, has absorbed a few grams of softener from the bag, which may result in a permanent hazard to the patient's health. PNC has therefore too high permeability to water vapor and oxygen to be used in the one bag concept.

During recent years has an inner bag plastic material of multilayer polypropene, i.e. PP been started to get used (for example US Patent 4,910,085, US Patent 5,783,269, US Patent 5,993,949, EP 0,216,639). These polypropylene based materials have a better water vapor barrier (approximately 2 times) and a worse oxygen barrier (approximately 2 times) properties compared to PNC. As to the environmental and migration aspects they perform better than PVC. Their drawback compared to PVC is however their higher cost per kilogram of multilayer PP film materials. The multilayer polypropylene or polyolefin based plastic materials are usually co-extruded 3-layer films of which at least two layers are polypropylene/polyolefin based. The third layer can contain polyester, polycarbonate or polyamide (for example EP 0,216,639, US Patent 4,910,085). Polypropylen based inner bag cannot normally be used in one bag solutions, since they do not own enough oxygen barrier.

US Patent 4910085 discloses a multiple layer film useful in packaging and packages made therefrom. A first layer of the film is a material containing an ester group, a polycarbonate or a polyether block amide copolymer. A second layer of the film is a sealant, preferably polypropylene polymer blend with an elastomeric styrene-ethylene-butylene-styrene copolymer. A third functionally adhesive layer is between the first and second layers. The composition of the third adhesive layer is typically either a polypropylene modified with a carboxy group such as an organic acid or anhydride or a styrene ethylene butylene styrene copolymer. The permeability properties of the film against oxygen, air, and water vapors are not good enough and therefore it is needed a secondary film containing a barrier layer for water vapors and oxygen.

US Patent 5,783,269 describes a non-PVC multilayer film containing an outer layer, a supporting layer together with at least one interposed central layer, characterized in that the outer and supporting layers contain polymers having Vicat softening temperatures of above approximately 121°C and that at least one central layer contains polymers having softening temperatures of below 70°C. The non-PVC multi-layer film is particularly suitable for the production of medical bags. This patent describes films that can be used as an inner bag or an outer bag but not in one bag concept due to too high permeability to oxygen, air and water vapor.

A multiple layer structure comprising a skin layer, a barrier layer, a radio frequency layer, susceptible layer having a first polyolefin in the range of 30- 60% by weight, a second polyolefin in an amount within the range of 25-50% by weight, a radio frequency susceptible polymer in an amount within the range 3- 40% by weight, a styrene and hydrocarbon block copolymer in an amount within the range of 5-40% by weight of the sealant layer is described in US Patent 5,993,949. This film and packages made thereof have too high permeability towards oxygen air and water vapor to be used in the one bag concept. The cost of these films is usually higher than the cost of the films described above.

In the patent document EP 0,686,091 is described an autoclavable, transparent multilayer film with oxygen barrier capacity. The film is assembled in sequential layers A-B-C-D-C-B'-A' wherein A and A' are layers substantially resistant for water vapor, B and B' are layers providing adhesive bonding between layers A and A' with C. Layer C consists of a moisture absorbing polymer substantially impermeable to oxygen and it contains an aromatic polyamide or derivative or copolymer thereof. D is a layer consisting of polyethylene vinyl alcohol (EVOH). Films made according to this patent are useful as an outer bag. However, they give too stiff films to be used in one bag applications. Stiffness is partly due to the structure of D containing EVOH that has good oxygen permeability properties but which makes the film more inflexible. The properties of the film according to the patent EP 0,686,091 is compared later to the structure of the film according to the invention in a comparison test.

The invention relates to a steam-sterilizable multilayer film according to claim 1.

The invention relates also the use of the steam-sterilizable, multilayer film for making containers according to claim 10.

The invention relates also process for making a steam-sterilizable multilayer film according to claim 11.

A steam-sterilizable, multilayer film according to the invention has six polymer layers. The mentioned layers are following: the first layer is a protective layer, the second layer is an adhesive tie layer, the third layer is a barrier layer made of caprolactam free polyamide or a derivate or a copolymer thereof, the fourth layer is an adhesive tie layer, the fifth layer is a core layer, which contains polyolefin blended possible with a thermoplastic elastomer or a derivate thereof and the sixth layer is a sealing layer containing polyolefin or/and thermoplastic elastomer polymers or a derivate thereof.

The steam-sterilizable, multilayer film according to the invention is preferably made by co-extruding the film layers in clean room conditions.

The basic idea behind the invention is to form a film in which the oxygen barrier layer is formed by polyamide based polymers where polyamides are caprolactam free. Preferably the polyamides are aromatic polyamides. The softness and flexibility of the film and container made thereof is secured by a polyolefin based core layer.

It is well known that polyamides give good protection against oxygen but some polyamides like nylon, PA 6, cause problems with caprolactam migration. The co-extrusion properties vary for different polyamides. For example PA 66 is not appropriate in many applications. The selection of polyamides used in this patent application is therefore of great importance.

As mentioned before the function of the core layer is to give more flexibility to overall structure of the container. It should also stand for steam sterilization temperatures. The core layer should be transparent and preferably water vapor impermeable. The structure of the core layer can be based on polyesters, polyuretans or polyolefins. Preferably core layer is composed of a polyolefin based polymer blended with thermoplastic elastomers. Preferably core layer consists of a polypropylene or polypropylene copolymers blended with compounds giving elasticity such as thermoplastic elastomers as those based on SEBS block copolymers, sold by Shell Chemical Company under product designation of KRATON. Elastomer can also be based on LMDH, ethylene vinyl acetate and ethylene acrylic acid copolymers and other elastomers known from prior art. Propylene copolymer can be for example heterophasic ethylene- propylene copolymer with moderate ethylene content.

The innermost heat sealing layer of the film according to the invention should tolerate steam-sterilization temperature and it should have good heat-sealing properties. It should also be transparent and compatible with liquids stored in a container. Preferably the heat sealing layer has also some water vapor barrier properties. Preferably the heat sealing layer contains polyolefins as for example polypropylen. Polypropylen can be polypropylen homopolymer or polypropylene based copolymers, propylene-ethylene copolymers with 2-8% ethylene. More preferably the sealant layer contains polypropylen or polypropylene copolymer blended with elastomer(s). Elastomer is preferably a thermoplastic elastomer as styrene-hydrocarbon block polymers such as styrene-ethylene-butylene-styrene (SEBS) block polymers. The inner sealing layer is connected to the mentioned core layer.

The main purpose of the outer protective layer is to protect the container from mechanical stress. It should consist of a transparent, mechanical durable, flexible polymer(s). It may also form a barrier layer for water vapors. The outer layer can consist of one of those known in the prior art; it can for example comprise polyolefin or polyester copolymers but preferable the outer layer comprises polyolefins as isobutylen or polypropylen or polyolefin based crosslinked structures. More preferably the outer layer comprises homopolymer or copolymer polyolefins as polypropylene homo- or copolymers. Polypropylene copolymer is preferably polypropylene-ethylene copolymer with moderate ethylene content.

The main purpose of the adhesive tie layer is on the first hand between the outer layer and the barrier layer and on the second hand between the barrier layer and the sealant layer to form a firm linkage layer between two layers composed of different polymers. The adhesive layer can be composed of those polymers known in the prior art. The adhesive layer can be composed of modified polyolefins and propylene and ethylene copolymers such as those sold by Mitsui Petrochemicals as the Admer product series. Suitable is for example QF-551, which is composed of carboxy modified polypropylene. The selection of the adhesive layer is however not limited in these examples but all polymers that fulfil functional requirement of transparency and good adhesive properties after heating to the sealing layer and the barrier layer and the barrier layer and the outer layer can be used. Preferably the adhesive layer strengthens the overall structure of the container.

The first main advantage of the film and the container made thereof according to the invention over prior art is, that the water vapor and oxygen barrier properties of the film/container are superior compared to PVC and the most known multilayer polypropylene films/containers. Therefore the container according to the invention is suitable for medical or pharmaceutical solutions, requiring medium oxygen barrier and it is formed of the steam-sterilizable, multilayer film.

The second main advantage of the film according to the invention is that containers made thereof can be used as an inner bag or as an outer bag or as one bag concept. Containers are soft and flexible enough to be used as an inner bag or in one bag concept. They are however stiff enough and they have good oxygen barrier properties to be used as outer packages for containers medical or pharmaceutical solutions.

Another very important advantage of the containers according to the invention over the prior art containers with two bags concept is, that containers do not need any secondary packages acting as water/moisture and/or oxygen barrier. This lowers significantly manufacturing costs.

Other advantages of the films and containers made thereof are following:

The container according to the invention is made by co-extrusion process with capability of extruding at least six layers. The process is performed in clean room conditions, required for pharmaceutical packages, which gives possibility to optimize the properties of the film and to achieve lower production costs.

The invention is described in greater detail below with reference to the accompanying Figure 1.

Figure 1 is a schematic view of a film in a preferred embodiment according to the invention with six layers. The layer 1 is an outer layer, which acts as a protective layer against mechanical stress and heat during the manufacturing process. The protective first layer 1 is made of heat-resistant polypropylene copolymer but also other polyolefin based polymers known in the prior art, which stand for steam sterilization conditions up to temperature 100-121°C and mechanical stress can be used. The second layer 2; 22 and fourth layer 2; 21 are adhesive tie layers. The third layer 3 is a barrier layer for oxygen and water vapors. The barrier layer 3 typically consists of a lactam free polyamide based polymer(s). The sixth layer 5 is for sealing. The sealing layer 5 consist of a polyolefin based layer such as polypropylene copolymer with an elastomer. Between an inner adhesive layer 2; 21 and the sealing layer 5 is the core layer 4 consisting of a polypropylene based heterophasic copolymer with or without an elastomer.

The films according to Figure 1 and containers made thereof have following characteristics: they are steam-sterilizable, processed in a clean room conditions with a co-extrusion process. A co-extruded multilayer barrier film and a container made thereof are used with pharmaceutical solutions as one bag concept. The containers have following characteristics: they are highly transparent, there is no migration, they have high barrier against oxygen, air, and water vapor, they are steam-sterilizable, they have high flexibility and low manufacturing cost.

Example 1

According to the preferred embodiment of the invention, a six layer film 6 according to the figure 1 was made by co-extruding. The outer layer 1 is made of heat-resistant polypropylen copolymer, melting point 150°C and the thickness 20 μm.

The both adhesive tie layers 2;21 and 2;22 are made from carboxy modified polypropylene, thicknesses 5-10 μm.

The barrier layer 3 is a caprolactam free polyamid (70%) with low crystallinity and excellent tranparency blended with an amorphous thermoplastic semi- aromatic copolyamid , thickness 20 μm.

The core layer 4 is a random heterophasic polypropylene copolymer, thickness 100 μm.

The sealing layer 5 is a mixture of polypropylene copolymer (80%) and thermoplastic elastomer (SEBS-block polymer)(20%).

Experiment

The following experiment was carried out on a aforementioned film according to the invention in order to test its 02 permeability.

Table 1

A film according to the invention (Infu Medium Barrier film):

Layer Thickn

1. Polypropylene copolymer protective layer 20

2. Adhesive tie layer 10

3. Barrier layer (polyamide based) 20

4. Adhesive tie layer 10

5. Core layer 80

6. Sealing layer 40

Oxygen permeability (ccm/d/m2) of this film at 23°C was 50% RH 40.

Example 2

The oxygen permeability of the following two films according to the prior art was tested. The films have the following structure presented in Table 2 and 3. Table 2

The first film according to the prior art:

Polypropylene copolymer protective layer (outer layer) Propylene copolymer + elastomer Propylene copolymer + elastomer (sealing layer).

The oxygen permeability of this film (ccm/d/m2) at 23°C was 50% RH 400.

Table 3

A second film according to the prior art:

PVC

The oxygen permeability (ccm/d/m2) of PVC-film at 23°C was 50% RH 190.

Comparison test

In a comparison test was compared three different films: Infu Low Barrier, Infu Medium Barrier and Infu High Barrier films. Infu Low Barrier film is a polyolefin based multilayer film according to the prior art. Polyolefins used are either copolymers or homopolymers or thermoplastic elastomers or rubbers. Infu Medium Barrier film is a film according to the invention from example 1. Infu High Barrier film is a film according to the EP-patent 686091, film number 5. Low barrier films are those with OTR>500, medium barrier film has 10<OTR<500 and high barrier films has OTR≤IO.

Table 4

Infu Low Barrier Infu Medium Barrier Infu High Barrier

OTR 757 52 0,5

Punct. Force [N] 25 23 22

Punct energy [N/mm] 214 163 86

Elongation MD [%] 614 531 405

Elongation TD [%] 600 499 382

Elasticity MD [N/mm] 343 425 1120

Elasticity TD [N/mm] 286 374 1085 From the comparison test above it can be seen that puncture resistance, presented as an energy value needed to penetrate the film, is reduced from low to high barrier film. Infu High Barrier film is more brittle and stiff.

A significant reduction of the elongation values indicates, that the Infu High Barrier film is not as soft as the low and medium barrier versions. Breakage of the film occur earlier, that is, at lower tension.

The elastic behavior, that is, the tendency of a material to return its shape after the tension (mechanical load, stress) has been taken away, correspondently is most pronounced for the harder Infu High Barrier film.

Conclusions: Containers made of Infu High Barrier film are more brittle and suffer and therefore not so suitable for inner packages as containers made of Infu Medium Barrier film.

The Infu High Barrier film is not as soft as the low and medium barrier versions and it has a pronounce tendency to keep its shape and therefore it is not so suitable for inner packages as containers made from Infu Low Barrier and from Infu Medium Barrier films. The Infu Medium Barrier film is soft enough and collapsible to be used as an inner package. It has also enough water and oxygen barrier to be used as an outer package or in one bag concept.

Claims

Claims
1. A steam-sterilizable, multilayer film (6), characterized in that the film has at least following polymer layers:
- the first layer is a protective layer (1) containing polyolefin based polymers, - the second layer is an adhesive tie layer (2; 22),
- the third layer is a barrier layer (3) made of caprolactam free polyamide or a derivative or a copolymer thereof,
- the fourth layer is an adhesive tie layer (2; 21),
- the fifth layer is a core layer (4), which contains polyolefin blended possibly with a thermoplastic elastomer or a derivative thereof,
- the sixth layer is a sealing layer (5) containing polyolefin or/and thermoplastic elastomer polymers or a derivative thereof.
2. The steam-sterilizable, multilayer film (6) according to Claim 1, characterized in that the core layer (4) comprises at least a polypropylene based heterophasic copolymer with or without an elastomer.
3. The steam-sterilizable, multilayer film (6) according to Claim 2, characterized in that the core layer (4) is a random heterophasic polypropylene copolymer.
4. The steam-sterilizable, multilayer film (6) according to any of the preceding claims, characterized in that the barrier layer (3) is formed of a caprolactam-free polyamid blended with an amorphous thermoplastic semi-aromatic copolyamid.
5. The steam-sterilizable, multilayer film (6) according to any of the preceding claims, characterized in that the protective layer (1) contains polypropylene.
6. The steam-sterilizable, multilayer film (6) according to Claim 5, characterized in that the protective layer (1) is made of homopolymer polypropylene or copolymer propylene or a derivative thereof.
7. The steam-sterilizable, multilayer film (6) film according to any of the preceding claims, characterized in that the sealing layer (5) contains polypropylene as polypropylene copolymer like random copolymer propylene or heterophasic copolymer propylene or a derivative thereof.
8. The steam-sterilizable, multilayer film (6) film according to Claim 7, characterized in that the sealing layer (5) contains a mixture of polypropylene copolymer like a random copolymer or a heterophasic copolymer propylene or derivative thereof blended with an elastomer.
9. The steam-sterilizable, multilayer film (6) according to any of the preceding claims, characterized in that the oxygen transmission rate (OTR) of the film is 10 to 500 preferably 20-100.
10. The use of the film according to Claims 1-9 for manufacturing container with medium oxygen barrier in one bag concept for medical or pharmaceutical solutions.
11. A process for making the steam-sterilizable, multilayer film (6) according to any of claim 1-9, characterized in that the film layers are co-extruded together in clean room conditions.
PCT/FI2002/000688 2001-08-22 2002-08-22 A steam-sterilizable multilayer film and containers made thereof WO2003018312A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
FI20011686 2001-08-22
FI20011686A FI20011686A0 (en) 2001-08-22 2001-08-22 Hörysterilisoitava multi-layer film as well as on the manufactured storage containers

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR20047002672A KR20040041154A (en) 2001-08-22 2002-08-22 A steam-sterilizable multilayer film and containers made thereof
EP20020753109 EP1423277A1 (en) 2001-08-22 2002-08-22 A steam-sterilizable multilayer film and containers made thereof

Publications (1)

Publication Number Publication Date
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Country Status (4)

Country Link
EP (1) EP1423277A1 (en)
KR (1) KR20040041154A (en)
FI (1) FI20011686A0 (en)
WO (1) WO2003018312A1 (en)

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US8465819B2 (en) 2005-04-28 2013-06-18 Otsuka Pharmaceutical Factory, Inc. Drug solution container package and method for manufacturing the same
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US9662867B2 (en) 2006-06-14 2017-05-30 Avery Dennison Corporation Conformable and die-cuttable machine direction oriented labelstocks and labels, and process for preparing
US9636895B2 (en) 2006-06-20 2017-05-02 Avery Dennison Corporation Multilayered polymeric film for hot melt adhesive labeling and label stock and label thereof
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KR20040041154A (en) 2004-05-14 application
FI20011686A0 (en) 2001-08-22 application
EP1423277A1 (en) 2004-06-02 application

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