CA2028393A1 - Multi-layered structure for the packaging of products sensitive to oxygen - Google Patents
Multi-layered structure for the packaging of products sensitive to oxygenInfo
- Publication number
- CA2028393A1 CA2028393A1 CA002028393A CA2028393A CA2028393A1 CA 2028393 A1 CA2028393 A1 CA 2028393A1 CA 002028393 A CA002028393 A CA 002028393A CA 2028393 A CA2028393 A CA 2028393A CA 2028393 A1 CA2028393 A1 CA 2028393A1
- Authority
- CA
- Canada
- Prior art keywords
- oxygen
- layered structure
- humidity
- barrier layer
- evoh
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 34
- 239000001301 oxygen Substances 0.000 title claims abstract description 34
- 238000004806 packaging method and process Methods 0.000 title claims abstract description 9
- 230000004888 barrier function Effects 0.000 claims abstract description 32
- 230000035699 permeability Effects 0.000 claims abstract description 7
- 239000010410 layer Substances 0.000 claims description 34
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 claims description 32
- UFRKOOWSQGXVKV-UHFFFAOYSA-N ethene;ethenol Chemical compound C=C.OC=C UFRKOOWSQGXVKV-UHFFFAOYSA-N 0.000 claims description 32
- 239000004715 ethylene vinyl alcohol Substances 0.000 claims description 32
- 239000004743 Polypropylene Substances 0.000 claims description 11
- 239000012790 adhesive layer Substances 0.000 claims description 6
- 229920000098 polyolefin Polymers 0.000 claims description 4
- -1 polypropylene Polymers 0.000 claims description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 3
- 239000005977 Ethylene Substances 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- 239000004800 polyvinyl chloride Substances 0.000 claims description 2
- 229920000915 polyvinyl chloride Polymers 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 239000000853 adhesive Substances 0.000 description 13
- 230000001070 adhesive effect Effects 0.000 description 13
- 230000001954 sterilising effect Effects 0.000 description 7
- 238000004659 sterilization and disinfection Methods 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 6
- 239000003570 air Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000012080 ambient air Substances 0.000 description 2
- 239000002274 desiccant Substances 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 229940127557 pharmaceutical product Drugs 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 2
- 229920003313 Bynel® Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 241001312297 Selar Species 0.000 description 1
- 229920003365 Selar® Polymers 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000010101 extrusion blow moulding Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000010102 injection blow moulding Methods 0.000 description 1
- 238000012432 intermediate storage Methods 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229940127554 medical product Drugs 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000825 pharmaceutical preparation Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000006748 scratching Methods 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 238000003856 thermoforming Methods 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
- 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
- B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (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
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/724—Permeability to gases, adsorption
- B32B2307/7242—Non-permeable
- B32B2307/7246—Water vapor barrier
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2323/00—Polyalkenes
- B32B2323/10—Polypropylene
-
- 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
Landscapes
- Laminated Bodies (AREA)
- Packages (AREA)
- Wrappers (AREA)
Abstract
Multi-layered structure for the packaging of products sensitive to oxygen ABSTRACT OF THE DESCRIPTIVE CONTENT OF THE INVENTION
This multi-layered structure comprises a polymeric barrier layer to humidity and a polymeric barrier layer to oxygen whose permeability to oxygen is a function of the humidity, optionally separated by a bonding layer wherein, according to the invention, the polymeric barrier layer to oxygen is on the outside of the structure.
Packaging of foodstuffs.
Fig. None.
This multi-layered structure comprises a polymeric barrier layer to humidity and a polymeric barrier layer to oxygen whose permeability to oxygen is a function of the humidity, optionally separated by a bonding layer wherein, according to the invention, the polymeric barrier layer to oxygen is on the outside of the structure.
Packaging of foodstuffs.
Fig. None.
Description
S ~
The object of the present invention is a polymeric multi-layered structure for the packaging of products sensitive to oxygen such as foodstuffs and pharmaceutical products.
The invention applies in particwlar to structures comprising 5 a polymeric barrier layer to oxygen intended to protect the product sensitive to oxygen throughout the entire life-time of the package.
In view of the fact that the polymers commonly used to maintain this barrier to oxygen, in particular the polyvinyl alcohols (PVOH) and the copolymers of vinyl alcohol and ethylene (EVOH), are sensitive to humidity, they are protected by barrier layers to humidity, in particular polyolefins or polyv~nyl chloride, usually through the intermediary of adhesive layers (GB-9-l 384 791). However, such protective layers do not completely prevent the passage of humidity in cases of intermediate storage in humid air and, above all, during sterilization, a circumstance which entails the progressive loss of the properties of the barrier layer to oxygen such as EVOH as the relative humidity increases.
In order to remedy this disadvantage according to EP-A-O
059 274 it has been suggested that a desiccating agent be introduced into the multi-layered structure, in particular into the adhesive layers surrounding the oxygen barrier. However, during sterilization (usually at about 121 C in the case of foodstuffs) the passage of oxygen through the multi-layered structure is quite considerable since, on the one hand, the permeability of the EVOH is not only a function of the humidity but also of the temperature and, on the other, the passage of water vapour may lead to the saturation of the desiccating agent which thus becomes ineffective. In addition, the more impermeable the external wall of the structure to water, the slower is the removal of the water retained by the EVOH layer after sterilization.
The present invention enables the effect of this loss of impermeability to oxygen during the life-time of the packaging to be reduced by placing the humidity-sensitive layer in a manner such that it is at the lowest possible level of relative humidity and which is the fastest possible to evaporate once the package has been formed.
The solution according to the invention consists of placing the oxygen barrier layer on the outside of the multi-layered structure, in particular on the external wall of the packaging in the case where the packaged product contains water.
Thus, the object of the invention is a multi-layered structure for the packa~ing of products sensitive to oxygen, in particular foodstuffs, comprising a polymeric barrier layer to humidity and a polymeric barrier layer to oxygen whose permeabiiity to oxygen is a function of the humidity, sald layers being optionally bound together by an adhesive layer, wherein the polymeric barrier layer bo oxygen is located at the outside of the structure.
The invention is part;cularly useful in the case in which the "oxygen barrier layer" com~rises EVOH or consists of EVOH.
The "humidity barrier layer" may in particular be a poly-olefin or any other polymer usually used for packaging foodstuffs or pharmaceutical or medical products, and be in particular a coextrudable polymer.
In accordance with an alternative, the multi-layered structure according to the invention may comprise two or more than two successive barrier layers to oxygen, in particular EVOH, optionally bound by adhesive layers.
Thus, whereas the structures according to the state of the art are of the type :
A/adhesive/EVOH/adhesive/B
in which A, B and the adhesives are barrier polymers to humidity for the protection of the EVOH from humidity, the invention consists of having the structure :
A/adhesive/EVOH
A being the polymeric barrier to humidity, in particular a polyolefin, for example polypropylene, which is in contact with the packaged product when the latter contains water, which is in particular the case for most foodstuffs (their relative humidity varying from 60 to 100 %).
In this case the EVOH is in contact with the ambient air which is at a lower level of humidity.
The invention may be explained as follows.
In the case of a package sealed according to the~state of the art the situation is the following :
Foodstuff/A/adhesive/EVOH/adhesive/B/outside air In such a structure at equilibrium the humidity of the EVOH -hence its efficiency as oxygen barrier - is such that it lies between ~r~
the humidity of the foodstuff and the humidity of the ambient air, but is always higher than the humidity of the air.
By placing the EVOH layer on the outside according to the invention , its humidity is equal to the humidity of the air, hence the lowest possible humidity in the place where the package is stored and, consequently, the EVOH exhibits maximal capacity with respect to its efficiency as oxygen barrier.
The multi-layered s-tructure according to the invention may be constructed in a known manner, in particular by coextrusion of the polymers forming each of the layers (e.g. by flat sheet die), by extrusion - blow moulding, by injection - blow moulding, etc.
The following example illustrates the invention.
EXAMPLE
A multi-layered structure PP/adhesive/EVOH is produced by extrusion in the form of a rigid sheet 1.2 mm thick and having the following composition :
thickness of layer PP (Transparent homopolymer from the Amoco company) ..................... 4 % 48 lum PP (idem., with +5 % of white TiO2 pigment) .......................... 90.5 % 1086 lum Grafted PP homopolymer adhesive (Bynel from the Dupont de Nemours company)................................ 2.5 % 30 lum EVOH (Selar from the DuPont de Nemours company) ............................... 3 % 36 ~m Trays (138 mm x 138 mm x 33 mm, about 20 g weight) are made from this sheet by thermoforming by means of a RDM37.10 machine of the ILLIG company.
The trays are filled with cold water and then fitted with non-strippable covers (made of aluminium/lacquer) and sealed at 220 C
for 2s at 6 bars (0.6 MPa). The trays are placed in an autoclave and maintained there at 121 C for 30 mn with a counter pressure of 2 bars (0.2 MPa),then they are cooled by injection of cold water into the autoclave. S~bsequently they are stored at 23 C and 50 % relative humidity (RH).
, ri r~ r~ ,~ r J
The trays are opened after a lapse of time of from 1 to 30 days after the sterilization step and the permeability is measured each time a tray is opened.
The permeability to oxygen is measured by means of an apparatus of the Oxtran type according to the ASTM D 3985 standard at 30 C and 65-70 % RH. As an example, a permeability of 0.022 cm 02/24 h was measured after 1 day, 0.023 cm /24 h after 7 days and 0.018 cm 02/24 h after 28 days.
For comparison, the same tests were performed on the multi-layered structures just mentioned but turned inside out (EVOH on the inside of the tray in contact with the water) and on a commercially available multi-layered structure : PP/adhesive/EVOH/adhesive/PP having the same total thickness and a EVOH iayer of the same thickness as the structures just mentioned. The results of the measurements are reported on the appended graph. ( Permeability with the EVOH on the inside in contact with-the water was measured to be 0.038 cm 02/24 h after 7 days;
0.19 cm 02/24 h after 14 days; 0.19 cm 02/24 h after 28 days).
It is observed that :
- for the structure according to the invention (curve 1), although the EVOH layer was loaded with water at the start of the sterilization, it loses it as soon as the air becomes dry and this effect is magnified after removal from the autoclave;
- for the known structure (curve 2), although the EVOH layer is separated from the water by a barrier layer to humidity (PP), it is loaded with water which remains, as it were, trapped in the structure for several days after sterilization, a circumstance which leads to the loss of its barrier capacity to oxygen; and - in the case of the inside out structure (curve 3), the EVOH
layer in contact with the water absorbs water during the sterilization (without being saturated) and afterwards it continues to take up water, thus losing its barrier effect to oxygen.
The invention applies to multi-layered structures comprising at least one EVOH layer or any other similar product acting as a barrier to oxygen and sensitive to humidity, and at least one layer of another extrudable polymer such as polyethylene, polypropylene, polystyrene, ethylene polyterephthalate (EPT), polyvinyl chloride (PVC), polycarbonate ~PC), etc -- 5 -- j~ ,~ "
The barrier effectiveness to oxygen of the EVOH placed as the outside layer may be reinforced or guaranteed by one or more additiOnal layers of EVOH, for example by a structure of the type :
PP/adhesive/EVOH/adhesive/EVOH.
It should be noted that the EVOH in the outside position offers the following additional advantages :
- an antistatic effect - a glossy appearance - an easier check of its presence (its absence as a possible resul-t of scratching may be revealed by staining the adhesive).
The multi-layer structure according to the invention, in a rigid or semi-rigid form, may be advantageously used for the manufacture of various recipients such as trays, cartons, tubes, and in particular sealable containers of this type.
The object of the present invention is a polymeric multi-layered structure for the packaging of products sensitive to oxygen such as foodstuffs and pharmaceutical products.
The invention applies in particwlar to structures comprising 5 a polymeric barrier layer to oxygen intended to protect the product sensitive to oxygen throughout the entire life-time of the package.
In view of the fact that the polymers commonly used to maintain this barrier to oxygen, in particular the polyvinyl alcohols (PVOH) and the copolymers of vinyl alcohol and ethylene (EVOH), are sensitive to humidity, they are protected by barrier layers to humidity, in particular polyolefins or polyv~nyl chloride, usually through the intermediary of adhesive layers (GB-9-l 384 791). However, such protective layers do not completely prevent the passage of humidity in cases of intermediate storage in humid air and, above all, during sterilization, a circumstance which entails the progressive loss of the properties of the barrier layer to oxygen such as EVOH as the relative humidity increases.
In order to remedy this disadvantage according to EP-A-O
059 274 it has been suggested that a desiccating agent be introduced into the multi-layered structure, in particular into the adhesive layers surrounding the oxygen barrier. However, during sterilization (usually at about 121 C in the case of foodstuffs) the passage of oxygen through the multi-layered structure is quite considerable since, on the one hand, the permeability of the EVOH is not only a function of the humidity but also of the temperature and, on the other, the passage of water vapour may lead to the saturation of the desiccating agent which thus becomes ineffective. In addition, the more impermeable the external wall of the structure to water, the slower is the removal of the water retained by the EVOH layer after sterilization.
The present invention enables the effect of this loss of impermeability to oxygen during the life-time of the packaging to be reduced by placing the humidity-sensitive layer in a manner such that it is at the lowest possible level of relative humidity and which is the fastest possible to evaporate once the package has been formed.
The solution according to the invention consists of placing the oxygen barrier layer on the outside of the multi-layered structure, in particular on the external wall of the packaging in the case where the packaged product contains water.
Thus, the object of the invention is a multi-layered structure for the packa~ing of products sensitive to oxygen, in particular foodstuffs, comprising a polymeric barrier layer to humidity and a polymeric barrier layer to oxygen whose permeabiiity to oxygen is a function of the humidity, sald layers being optionally bound together by an adhesive layer, wherein the polymeric barrier layer bo oxygen is located at the outside of the structure.
The invention is part;cularly useful in the case in which the "oxygen barrier layer" com~rises EVOH or consists of EVOH.
The "humidity barrier layer" may in particular be a poly-olefin or any other polymer usually used for packaging foodstuffs or pharmaceutical or medical products, and be in particular a coextrudable polymer.
In accordance with an alternative, the multi-layered structure according to the invention may comprise two or more than two successive barrier layers to oxygen, in particular EVOH, optionally bound by adhesive layers.
Thus, whereas the structures according to the state of the art are of the type :
A/adhesive/EVOH/adhesive/B
in which A, B and the adhesives are barrier polymers to humidity for the protection of the EVOH from humidity, the invention consists of having the structure :
A/adhesive/EVOH
A being the polymeric barrier to humidity, in particular a polyolefin, for example polypropylene, which is in contact with the packaged product when the latter contains water, which is in particular the case for most foodstuffs (their relative humidity varying from 60 to 100 %).
In this case the EVOH is in contact with the ambient air which is at a lower level of humidity.
The invention may be explained as follows.
In the case of a package sealed according to the~state of the art the situation is the following :
Foodstuff/A/adhesive/EVOH/adhesive/B/outside air In such a structure at equilibrium the humidity of the EVOH -hence its efficiency as oxygen barrier - is such that it lies between ~r~
the humidity of the foodstuff and the humidity of the ambient air, but is always higher than the humidity of the air.
By placing the EVOH layer on the outside according to the invention , its humidity is equal to the humidity of the air, hence the lowest possible humidity in the place where the package is stored and, consequently, the EVOH exhibits maximal capacity with respect to its efficiency as oxygen barrier.
The multi-layered s-tructure according to the invention may be constructed in a known manner, in particular by coextrusion of the polymers forming each of the layers (e.g. by flat sheet die), by extrusion - blow moulding, by injection - blow moulding, etc.
The following example illustrates the invention.
EXAMPLE
A multi-layered structure PP/adhesive/EVOH is produced by extrusion in the form of a rigid sheet 1.2 mm thick and having the following composition :
thickness of layer PP (Transparent homopolymer from the Amoco company) ..................... 4 % 48 lum PP (idem., with +5 % of white TiO2 pigment) .......................... 90.5 % 1086 lum Grafted PP homopolymer adhesive (Bynel from the Dupont de Nemours company)................................ 2.5 % 30 lum EVOH (Selar from the DuPont de Nemours company) ............................... 3 % 36 ~m Trays (138 mm x 138 mm x 33 mm, about 20 g weight) are made from this sheet by thermoforming by means of a RDM37.10 machine of the ILLIG company.
The trays are filled with cold water and then fitted with non-strippable covers (made of aluminium/lacquer) and sealed at 220 C
for 2s at 6 bars (0.6 MPa). The trays are placed in an autoclave and maintained there at 121 C for 30 mn with a counter pressure of 2 bars (0.2 MPa),then they are cooled by injection of cold water into the autoclave. S~bsequently they are stored at 23 C and 50 % relative humidity (RH).
, ri r~ r~ ,~ r J
The trays are opened after a lapse of time of from 1 to 30 days after the sterilization step and the permeability is measured each time a tray is opened.
The permeability to oxygen is measured by means of an apparatus of the Oxtran type according to the ASTM D 3985 standard at 30 C and 65-70 % RH. As an example, a permeability of 0.022 cm 02/24 h was measured after 1 day, 0.023 cm /24 h after 7 days and 0.018 cm 02/24 h after 28 days.
For comparison, the same tests were performed on the multi-layered structures just mentioned but turned inside out (EVOH on the inside of the tray in contact with the water) and on a commercially available multi-layered structure : PP/adhesive/EVOH/adhesive/PP having the same total thickness and a EVOH iayer of the same thickness as the structures just mentioned. The results of the measurements are reported on the appended graph. ( Permeability with the EVOH on the inside in contact with-the water was measured to be 0.038 cm 02/24 h after 7 days;
0.19 cm 02/24 h after 14 days; 0.19 cm 02/24 h after 28 days).
It is observed that :
- for the structure according to the invention (curve 1), although the EVOH layer was loaded with water at the start of the sterilization, it loses it as soon as the air becomes dry and this effect is magnified after removal from the autoclave;
- for the known structure (curve 2), although the EVOH layer is separated from the water by a barrier layer to humidity (PP), it is loaded with water which remains, as it were, trapped in the structure for several days after sterilization, a circumstance which leads to the loss of its barrier capacity to oxygen; and - in the case of the inside out structure (curve 3), the EVOH
layer in contact with the water absorbs water during the sterilization (without being saturated) and afterwards it continues to take up water, thus losing its barrier effect to oxygen.
The invention applies to multi-layered structures comprising at least one EVOH layer or any other similar product acting as a barrier to oxygen and sensitive to humidity, and at least one layer of another extrudable polymer such as polyethylene, polypropylene, polystyrene, ethylene polyterephthalate (EPT), polyvinyl chloride (PVC), polycarbonate ~PC), etc -- 5 -- j~ ,~ "
The barrier effectiveness to oxygen of the EVOH placed as the outside layer may be reinforced or guaranteed by one or more additiOnal layers of EVOH, for example by a structure of the type :
PP/adhesive/EVOH/adhesive/EVOH.
It should be noted that the EVOH in the outside position offers the following additional advantages :
- an antistatic effect - a glossy appearance - an easier check of its presence (its absence as a possible resul-t of scratching may be revealed by staining the adhesive).
The multi-layer structure according to the invention, in a rigid or semi-rigid form, may be advantageously used for the manufacture of various recipients such as trays, cartons, tubes, and in particular sealable containers of this type.
Claims (8)
1. Multi-layered structure for the packaging of products sensitive to oxygen, in particular foodstuffs, comprising a polymeric barrier layer to humidity and at least one polymeric barrier layer to oxygen whose permeability to oxygen is a function of the humidity, said layers being optionally bound by adhesive layers, wherein the polymeric barrier layer to oxygen is on the outside of the structure.
2. Multi-layered structure according to Claim 1, wherein the polymeric barrier layer to oxygen comprises EVOH.
3. Multi-layered structure according to Claim 2, wherein the polymeric barrier layer to oxygen consists of EVOH.
4. Multi-layered structure according to any one of the Claims 1 to 3, comprising two or more than two successive barrier layers to oxygen, optionally bound together by adhesive layers.
5. Multi-layered structure according to any one of the Claims 1 to 4, wherein the barrier layer to humidity is a polyolefin.
6. Multi-layered structure according to Claim 5, wherein the polyolefin is polypropylene.
7. Multi-layered structure according to any one of the Claims 1 to 4, wherein the barrier layer to humidity is an ethylene poly-terphthalate or a polyvinyl chloride.
8. Packaging comprising a wall with a multi-layered structure according to any one of the Claims 1 to 7.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8914296 | 1989-10-31 | ||
| FR8914296A FR2653756B1 (en) | 1989-10-31 | 1989-10-31 | MULTILAYER STRUCTURE FOR PACKAGING OXYGEN SENSITIVE PRODUCTS. |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2028393A1 true CA2028393A1 (en) | 1991-05-01 |
Family
ID=9386977
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002028393A Abandoned CA2028393A1 (en) | 1989-10-31 | 1990-10-24 | Multi-layered structure for the packaging of products sensitive to oxygen |
Country Status (11)
| Country | Link |
|---|---|
| EP (1) | EP0426522A1 (en) |
| JP (1) | JPH03183544A (en) |
| AU (1) | AU642917B2 (en) |
| BR (1) | BR9005508A (en) |
| CA (1) | CA2028393A1 (en) |
| CS (1) | CS535590A3 (en) |
| FR (1) | FR2653756B1 (en) |
| HU (1) | HUT61928A (en) |
| NZ (1) | NZ235866A (en) |
| PL (1) | PL287575A1 (en) |
| YU (1) | YU203690A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2685678A1 (en) * | 1991-12-27 | 1993-07-02 | Cmb Flexible | COMPLEX FILM, PARTICULARLY FOR PACKAGING FOOD PRODUCTS AND METHOD OF MANUFACTURE. |
| JPH0853162A (en) * | 1994-08-11 | 1996-02-27 | Kurita Seizosho:Kk | Packing material for ion-exchange resin |
| FR2745788B1 (en) * | 1996-03-11 | 1998-04-10 | Oreal | PACKAGING PROTECTED BY BARRIER MEDIA |
| CZ2010472A3 (en) * | 2010-06-15 | 2011-08-10 | Ústav anorganické chemie AV CR, v.v.i. | Polymer-based compound material containing nanoparticles and process for preparing thereof |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1384791A (en) * | 1972-04-28 | 1975-02-19 | Grace W R & Co | Laminates |
| GB1489635A (en) * | 1975-03-03 | 1977-10-26 | Toyo Seikan Kaisha Ltd | Packaging materials |
| US4182457A (en) * | 1976-08-10 | 1980-01-08 | Toyo Seikan Kaisha Limited | Multilayer container |
| JPS5677143A (en) * | 1979-11-30 | 1981-06-25 | Yoshino Kogyosho Co Ltd | Polyethylene terephthalate resin product |
| JPS57199657A (en) * | 1981-06-03 | 1982-12-07 | Toyo Seikan Kaisha Ltd | Plastic vessel, oxygen barrier property thereof is improved |
| JPS59213731A (en) * | 1983-05-18 | 1984-12-03 | Yoshino Kogyosho Co Ltd | Method for treating container made of thermoplastic polyester |
| JPS602361A (en) * | 1983-06-21 | 1985-01-08 | 株式会社クラレ | Spare shape with gas impermeable coating and biaxial oriented composite hollow body |
| JPS60122148A (en) * | 1983-12-05 | 1985-06-29 | 東レ株式会社 | Laminate |
| US4561920A (en) * | 1984-02-08 | 1985-12-31 | Norchem, Inc. Formerly Northern Petrochemical Company | Biaxially oriented oxygen and moisture barrier film |
| JPS6211644A (en) * | 1985-06-26 | 1987-01-20 | 株式会社クラレ | Laminate having excellent gas permeability resistance |
| US4952628A (en) * | 1987-08-24 | 1990-08-28 | E. I. Du Pont De Nemours And Company | Barrier blends based on amorphous polyamide and ethylene/vinyl alcohol, unaffected by humidity |
| CA1335424C (en) * | 1987-12-29 | 1995-05-02 | Tohei Moritani | Multilayered packaging materials having high gas barrier property |
-
1989
- 1989-10-31 FR FR8914296A patent/FR2653756B1/en not_active Expired - Lifetime
-
1990
- 1990-10-16 EP EP90402902A patent/EP0426522A1/en not_active Withdrawn
- 1990-10-16 AU AU64794/90A patent/AU642917B2/en not_active Withdrawn - After Issue
- 1990-10-24 CA CA002028393A patent/CA2028393A1/en not_active Abandoned
- 1990-10-26 JP JP2290586A patent/JPH03183544A/en active Pending
- 1990-10-29 NZ NZ235866A patent/NZ235866A/en unknown
- 1990-10-29 YU YU203690A patent/YU203690A/en unknown
- 1990-10-30 BR BR909005508A patent/BR9005508A/en not_active Application Discontinuation
- 1990-10-30 PL PL28757590A patent/PL287575A1/en unknown
- 1990-10-31 HU HU906969A patent/HUT61928A/en unknown
- 1990-10-31 CS CS905355A patent/CS535590A3/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| NZ235866A (en) | 1992-12-23 |
| YU203690A (en) | 1992-12-21 |
| AU642917B2 (en) | 1993-11-04 |
| FR2653756A1 (en) | 1991-05-03 |
| AU6479490A (en) | 1991-05-09 |
| JPH03183544A (en) | 1991-08-09 |
| EP0426522A1 (en) | 1991-05-08 |
| HU906969D0 (en) | 1991-05-28 |
| FR2653756B1 (en) | 1992-05-15 |
| HUT61928A (en) | 1993-03-29 |
| CS535590A3 (en) | 1992-02-19 |
| BR9005508A (en) | 1991-09-17 |
| PL287575A1 (en) | 1991-07-15 |
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Legal Events
| Date | Code | Title | Description |
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| FZDE | Dead |