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AU642917B2 - Multi-layered structure for the packaging of products sensitive to oxygen - Google Patents
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AU642917B2 - Multi-layered structure for the packaging of products sensitive to oxygen - Google Patents

Multi-layered structure for the packaging of products sensitive to oxygen Download PDF

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Publication number
AU642917B2
AU642917B2 AU64794/90A AU6479490A AU642917B2 AU 642917 B2 AU642917 B2 AU 642917B2 AU 64794/90 A AU64794/90 A AU 64794/90A AU 6479490 A AU6479490 A AU 6479490A AU 642917 B2 AU642917 B2 AU 642917B2
Authority
AU
Australia
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.)
Withdrawn - After Issue
Application number
AU64794/90A
Other versions
AU6479490A (en
Inventor
Jean-Louis Flork
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ONO
Original Assignee
ONO
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
Application filed by ONO filed Critical ONO
Publication of AU6479490A publication Critical patent/AU6479490A/en
Application granted granted Critical
Publication of AU642917B2 publication Critical patent/AU642917B2/en
Anticipated expiration legal-status Critical
Withdrawn - After Issue legal-status Critical Current

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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
    • B32B27/06Layered 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
    • B32B27/08Layered 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
    • 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
    • B32B27/30Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/306Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
    • 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
    • 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
    • B32B7/00Layered 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
    • B32B7/04Interconnection of layers
    • B32B7/12Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • 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
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/70Other properties
    • B32B2307/724Permeability to gases, adsorption
    • B32B2307/7242Non-permeable
    • B32B2307/7246Water vapor barrier
    • 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
    • B32B2323/00Polyalkenes
    • B32B2323/10Polypropylene
    • 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
    • B32B2439/00Containers; Receptacles
    • B32B2439/70Food packaging

Landscapes

  • Laminated Bodies (AREA)
  • Packages (AREA)
  • Wrappers (AREA)

Description

6429 7 COMMONWEALTH OF AUSTRALIA PATENTS ACT 1952 COMPLETE SPECIFICATION NAME ADDRESS OF APPLICANT:
ONO
B.P. 7 Auneau 28700 France NAME(S) OF INVENTOR(S): Jean-Louis FLORK ADDRESS FOR SERVICE: O DAVIES 'COLLISON Patent Attorneys 1 Little Collins Street, Melbourne, 3000.
COMPLETE SPECIFICATION FOR THE INVENTION ENTITLED: Multi-layered structure for the packaging of products sensitive to oxygen The following statement is a full description of this invention, including the best method of performing it known to me/us:r la -The object of the present invention is a polymeric multilayered structure for the packaging of products sensitive to oxygen such as foodstuffs and pharmaceutical products.
The invention applies in particular to structures comprising 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 polyvnyl chloride, usually through the intermediary of adhesive layers (GB-A-1 384 791). 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-0 059 274 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 1210 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 1 oss 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 -2the packaged product contains water.
According to the present invention, there is provided a multilayered structure for the packaging of products sensitive to oxygen and which contain water, in particular foodstuffs, comprising a polymeric barrier layer to humidity and at least one polymeric barrier layer to oxygen consisting of EVOH and whose permeability to oxygen is a function of the humidity, said layers being optionally bound by adhesive layers, wherein, in use of the multi-layered structure, the polymeric barrier layer to humidity is in contact with the packaged product and the polymeric barrier layer to oxygen is on the outside of the structure and in contact with the ambient air.
The "humidity barrier layer" may in particular be a polyolefin 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 25 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 .o.0 35 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 93P..,q:\oper\nS,6 4 795-p.o 2 3 5,2 3 -3 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 structure according to the invention may be constructed in a known manner, in particular by coextrusion of the polymers forming each of the layers 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 2 PP (Transparent homopolymer from the Amoco company) 4 48 pm PP (idem., with +5 of white TiO 2 pigment) 90.5 1086 mr Grafted PP homopolymer adhesive 25 (Bynel R from the Dupont de Nemours 2.5 30 um EVOH (SelarR from the DuPont de Nemours company) 3 36 rm Sq '30 Trays (138 mm x 138 mm x 33 mm, about 20 g weight) are made
S
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 2200 C for 2s at 6 bars (0.6 MPa). The trays are placed in an autoclave and maintained there at 1210 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. Subsequently they are stored at 230 C and 50 relative humidity (RH).
4 The trays are opened after a lapse of time of from 1 to 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 300 C and 3 65-70 RH. As an example, a permeability of 0.022 cm 02/24 h was 3 3 measured after 1 day, 0.023 cm /24 h after 7 days and 0.018 cm 3 02/24 h after 28 days.
For comparison, the same tests were performed on the multilayered 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 layer of:the same thickness as the structures just mentioned. The results of the measurements are reported f:5 on the appended graph. Permeability with the EVOH on the inside in Scontact with the water was measured to be 0.038 cm 3 0/24 h after 7 days; 0.19 cm 02/24 h after 14 days; 0.19 cm 0 /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 although the EVOH layer *9 is separated from the water by a barrier layer to humidity 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 the EVOH layer in contact with the water absorbs water during the sterilization SO (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...
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 result 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 o of various recipients such as trays, cartons, tubes, and in particular 5 sealable containers of this type.
o *0 0 o* 0 6 Se 0 Seoo 0000 0 So..
p

Claims (7)

1. Multi-layered structure for the packaging of products sensitive to oxygen and which contain water, in particular foodstuffs, comprising a polymeric barrier layer to humidity and at least one polymeric barrier layer to oxygen consisting of EVOH and whose permeability to oxygen is a function of the humidity, said layers being optionally bound by adhesive layers, wherein, in use of the multi- layered structure, the polymeric barrier layer to humidity is in contact with the packaged product and the polymeric barrier layer to oxygen is on the outside of the structure and in contact with the ambient air.
2. Multi-layered structure according to claim 1, comprising two or more than two successive barrier layers to oxygen; optionally bound together by adhesive layers.
3. Multi-layered structure according to any one of claims 1 or 2, wherein the barrier layer to humidity is a polyolefin.
4. Multi-layered structure according to claim 3, wherein the polyolefin is polypropylene.
5. Multi-layered structure according to any one of claims 1 or 2, wherein the barrier layer to humidity is an ethylene polyterphthalate or a polyvinyl chloride.
6. Packaging comprising a wall with a multi-layered structure according to any one of claims 1 to •e
7. A multi-layered structure according to claim 1, substantially as hereinbefore described with reference to the examples. Dated this 23rd day of August, 1993 ONO By Its Patent Attorneys SDAVIES COLLISON CAVE 930823,q:\oper\ms,64795-o.235,6 'NT 0g 930823,q:\oper\jns,64795-po.235,6 I
AU64794/90A 1989-10-31 1990-10-16 Multi-layered structure for the packaging of products sensitive to oxygen Withdrawn - After Issue AU642917B2 (en)

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 (2)

Publication Number Publication Date
AU6479490A AU6479490A (en) 1991-05-09
AU642917B2 true AU642917B2 (en) 1993-11-04

Family

ID=9386977

Family Applications (1)

Application Number Title Priority Date Filing Date
AU64794/90A Withdrawn - After Issue AU642917B2 (en) 1989-10-31 1990-10-16 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)

* Cited by examiner, † Cited by third party
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

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4561920A (en) * 1984-02-08 1985-12-31 Norchem, Inc. Formerly Northern Petrochemical Company Biaxially oriented oxygen and moisture barrier film

Family Cites Families (11)

* Cited by examiner, † Cited by third party
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
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

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4561920A (en) * 1984-02-08 1985-12-31 Norchem, Inc. Formerly Northern Petrochemical Company Biaxially oriented oxygen and moisture barrier film

Also Published As

Publication number Publication date
HU906969D0 (en) 1991-05-28
AU6479490A (en) 1991-05-09
EP0426522A1 (en) 1991-05-08
FR2653756A1 (en) 1991-05-03
HUT61928A (en) 1993-03-29
CS535590A3 (en) 1992-02-19
PL287575A1 (en) 1991-07-15
CA2028393A1 (en) 1991-05-01
FR2653756B1 (en) 1992-05-15
JPH03183544A (en) 1991-08-09
YU203690A (en) 1992-12-21
NZ235866A (en) 1992-12-23
BR9005508A (en) 1991-09-17

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