WO2005108065A1 - Lamine en plastique pour emballage faisant barriere contre les gaz - Google Patents

Lamine en plastique pour emballage faisant barriere contre les gaz Download PDF

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Publication number
WO2005108065A1
WO2005108065A1 PCT/SE2005/000538 SE2005000538W WO2005108065A1 WO 2005108065 A1 WO2005108065 A1 WO 2005108065A1 SE 2005000538 W SE2005000538 W SE 2005000538W WO 2005108065 A1 WO2005108065 A1 WO 2005108065A1
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WO
WIPO (PCT)
Prior art keywords
layer
gas barrier
polymer
packaging laminate
web
Prior art date
Application number
PCT/SE2005/000538
Other languages
English (en)
Inventor
Torsten Olofsson
Monika BÜRKI
Original Assignee
Tetra Laval Holdings & Finance S.A.
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 Tetra Laval Holdings & Finance S.A. filed Critical Tetra Laval Holdings & Finance S.A.
Priority to EP05722324A priority Critical patent/EP1747096A1/fr
Priority to JP2007513100A priority patent/JP2007536140A/ja
Publication of WO2005108065A1 publication Critical patent/WO2005108065A1/fr

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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
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B32B27/322—Layered products comprising a layer of synthetic resin comprising polyolefins comprising halogenated polyolefins, e.g. PTFE
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • 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
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • 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
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/0008—Electrical discharge treatment, e.g. corona, plasma treatment; wave energy or particle radiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • B65D65/40—Applications of laminates for particular packaging purposes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D75/00—Packages comprising articles or materials partially or wholly enclosed in strips, sheets, blanks, tubes, or webs of flexible sheet material, e.g. in folded wrappers
    • B65D75/008—Standing pouches, i.e. "Standbeutel"
    • 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
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/412—Transparent
    • 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
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/546—Flexural strength; Flexion stiffness
    • 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
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/552—Fatigue strength
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2310/00—Treatment by energy or chemical effects
    • B32B2310/14—Corona, ionisation, electrical discharge, plasma treatment
    • 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
    • B32B2323/04—Polyethylene
    • B32B2323/043—HDPE, i.e. high density polyethylene
    • 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
    • B32B2323/04—Polyethylene
    • B32B2323/046—LDPE, i.e. low density polyethylene
    • 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
    • B32B2367/00—Polyesters, e.g. PET, i.e. polyethylene terephthalate
    • 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
    • B32B2377/00—Polyamides
    • 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

Definitions

  • the present invention relates to a gas barrier packaging laminate having durability to stress crack formation and yet a bending stiffness and good integrity between the laminate layers, comprising outside layers of heat- sealable olefin polymer, a first gas barrier layer of SiOx, coated onto a first polymer carrier layer and a second gas barrier layer of SiOx, coated onto a second polymer carrier layer, and an intermediate polymer layer laminated between the first and the second gas barrier coated polymer carrier layers.
  • the invention also relates to a method of manufacturing the packaging laminate and to packaging containers produced from the packaging laminate.
  • packages for beverage and liquid food of the type that are single-use disposable plastic pouches, preferably at least partly, at some portion of the package, transparent to display the contents to the consumer when exposed on the shelf, e.g. in the food store.
  • Most commonly such packages are provided with a straw for direct drinking or a pull-tab for opening and pouring of the contents.
  • Such packages do not have the advantage of having the dimension and grip stability of the more common paperboard packaging laminate drink packages of the Tetra Brik® - type.
  • they have the image of a more positive environmental profile in many countries, with the argument that the amount of used packaging material as well as the volume of the emptied package is very small and because it may be recyclable with other similar flexible plastic items.
  • the traditional Tetra Brik-type packages have an oxygen barrier layer of aluminium foil, which in some countries is less desirable and which also makes a transparent package impossible.
  • a web of the packaging laminate is continuously formed into a tube, filled with contents and sealed off to pillow-shaped packaging containers by a simultaneous heat sealing and cutting operation.
  • the pillow-shaped packaging container is then normally fold-formed into a parallellepipedic packaging container.
  • the main advantage of this continuous tube-forming, filling and sealing packaging process concept is that the web may be sterilised continuously just before tube-forming, thus providing for the possibility of an aseptic packaging process, i.e. a process wherein the liquid content to be filled as well as the packaging material itself are reduced from bacteria and the filled packaging container is produced under clean circumstances such that the filled package may be stored for a long time even at ambient temperature, without the risk of growth of microorganisms in the filled product.
  • SiOx gas barrier layer compared to other gas barrier materials are firstly that it has a positive environmental profile, secondly, that it is not affected, i.e. the barrier properties remain intact, when in contact with surrounding moisture or liquid, it is transparent and since it is applied in very thin layers, also flexible and resistant to cracking when bent or folded.
  • the cost-efficiency of the material itself will be reduced with increasing thickness.
  • the packages fold-formed from the packaging laminate must have durability to stress crack formation in order to withstand handling at transport etc., which is a prerequisite that is difficult to combine with the requirements on stiffness.
  • the pouch-type drink packages available today on the market often have a laminated structure including a single gas barrier layer of, for example, an ethylene vinyl alcohol polymer (EVOH), and do not have the requirements on stiffness properties according to the present invention. It is therefore an object of the present invention to provide a packaging laminate that alleviates the above discussed disadvantages and problems.
  • EVOH ethylene vinyl alcohol polymer
  • the invention is also directed to a packaging container filled with beverage or liquid food produced from the packaging laminate of the invention as well as to a method of manufacturing of the laminated packaging material of the invention.
  • the above-mentioned object is achieved by means of an intermediate polymer layer laminated between the first and the second gas barrier coated polymer carrier layers.
  • the intermediate polymer layer includes at least first and second part-layers, whereof said first part-layer has a higher stiffness than said second part-layer and said second part-layer has higher elastomeric properties than said first part-layer.
  • the facings of a sandwich panel act similarly to the flanges of an I-beam, resisting the bending loads and increasing the bending stiffness of the structure, by being distancedjrom each other by an intermediate layer.
  • the lower density core in addition gives continuous support to the flanges or facings. It has been observed, that the elastomeric property of the second part-layer of the intermediate layer increases the resistance of the package to crack formation during cyclic loading, i.e. exposure to repeated stresses or vibrations such as might be the case during transport, by absorbing the mechanical stresses with elastic, reversible deformations.
  • the stiffness property of the first part- layer of the intermediate layer gives an extra contribution, in addition to the sandwich effect, to the stiffness properties of the packaging laminate as a whole. It has furthermore been observed, as a comparison, that if the intermediate layer is constituted by a single layer of a polymer of high stiffness, such as the polymer of the first part-layer of the present invention, there is an increased risk of stress crack formation at mechanical stresses. However, it has also been observed, for the comparison, that if a single layer of a polymer of high elastomeric properties constitutes the intermediate layer, the stability of the laminate during sealing might be impaired because the polymer of high elastomeric properties has a tendency to melt too much and escape the sealing area, i.e.
  • the sealing window is narrowed.
  • the required thickness of such an intermediate layer adds to the costs of the laminate in an undesirable way.
  • tests have been performed in which the intermediate layer is constituted by a blend of a high stiffness polymer and a polymer of high elastomeric properties (ratios 25/75, 40/60 and 60/40).
  • the results showed similar failure frequencies (50 to 90 %) in transport test simulations, due to stress crack formation, as in the case of an intermediate layer constituted by a single layer of a polymer of high stiffness.
  • the solution to the above mentioned problem and need is thus to provide a thin, packaging laminate with good gas barrier properties by means of laminating the two polymer carrier layer films, coated with the SiOx gas barrier layers, into a construction with an intermediate, distancing layer including at least first and second part-layers, whereof said first part-layer has a higher stiffness than said second part-layer and said second part-layer has higher elastomeric properties than said first part-layer, the laminate further having outer heat sealable layers of thermoplastic polymer.
  • the intermediate layer is comprised of three part-layers, wherein the third part-layer is identical either to the first or the second part-layer and the three part-layers are arranged symmetrically in the intermediate layer, i.e.
  • the best mode embodiment of the intermediate layer is that the third part-layer is identical to the second part-layer and that they are arranged on either side of the first part-layer, all three layers preferably being of essentially the same thickness.
  • at least 50 %, preferably at least 60 % by weight of said intermediate layer is constituted by layer(s) of high elastomeric properties.
  • Embodiments may however be conceived in which the third part-layer is identical to the first part-layer and arranged such that the second part-layer is positioned between said first part-layer and said third part-layer, all three layers preferably being of essentially the same thickness.
  • each part-layer of the intermediate layer has a thickness of 5-30 ⁇ m, preferably 10-25 rn and most preferred 10-20 ⁇ m.
  • the polymer carrier layers comprise polyester, polyamide or polypropylene materials and therefore have a certain degree of inherent stiffness, however, other relatively stiff polymers may also be employed for the carrier layers according to the invention. More preferably, they are oriented films and thus have a higher degree of crystallinity than non-oriented polymer films.
  • the structural sandwich construction of two relatively stiff carrier layers laminated to each side of such an intermediate polymer layer comprising a thermoplastic polymer with high elastomeric properties provides for a laminate having good resistance to cracking during repeated mechanical_stress and surprisingly good bending stiffness in relation to its thickness.
  • the arrangement of the two PECVD-deposited SiOx-layers has proved to result in a much more than two-fold increased gas barrier, compared to a laminate or film containing merely one SiOx-layer.
  • the construction having a distancing intermediate layer also acting as a "buffer" for penetration of gas, in particular oxygen gas provides for surprisingly improved gas barrier properties, which prove a synergistic effect resulting from this particular construction.
  • the laminate has excellent gas barrier properties and is both economical and easy to handle in a high speed, continuous packaging process.
  • the total thickness of the intermediate layer is from 30 to 55%, preferably from 35 to 50% of a total thickness of the packaging laminate.
  • the intermediate layer composed of at least a first and a second part-layer, is the thickest individual layer of the laminate.
  • the thickness of the carrier layers constitutes from about 5 to about 20, more preferably from about 5 to about 16 % of the total packaging laminate.
  • the carrier layers do not contribute to the total bending stiffness of the packaging laminate only by their mere thickness, but also by their interaction with the relatively thicker distancing intermediate layer.
  • the carrier layer of oriented polymer is a premanufactured film of polyester, polyamide (PA) or polypropylene (PP), such as a cast or co- extrusion cast film or more preferably a mono- or biaxially oriented polyethyleneterephtalate (PET), polyethylenenaphtenate (PEN), polyamide (PA), polypropylene (PP) polymer film or a multilayer film comprising a substrate surface layer of such a polymer or a multilayer film comprising at least one such mono- or biaxially oriented layer .
  • PET polyethyleneterephtalate
  • PEN polyethylenenaphtenate
  • PA polypropylene
  • PP polypropylene
  • premanufactured oriented polymer films as the carrier layers, it is ensured that they have some inherent bending stiffness relative to other layers in the laminate that are extrusion or coextrusion laminated, also at lower thicknesses.
  • a polymer of high stiffness for the first part-layer is suitably selected from the group consisting of high density polyethylene (HDPE) and polypropylene (PP).
  • HDPE high density polyethylene
  • PP polypropylene
  • thermoplastic polymer with high elastomeric properties for the second part-layer is suitably selected from the group consisting of very low density polyethylene (VLDPE), ultra low density polyethylene (ULDPE), ethylene-based co-polymer or terpolymer and polyolef in-based elastomer or plastomer. More preferably, the polymer of the second part-layer layer is a polyethylene copolymer or is VLDPE or ULDPE.
  • a particularly well functioning example of a shock absorbing polymer is "Attane ®" VLDPE from Dow. Other examples are “Exxco012" from Exxon and "Clearflex CLBO” from Polimeri.
  • the polymer of the second part-layer is a thermoplastic polymer with high elastomeric properties, which imparts to the pouch or walls of the packaging laminate flexibility enough to absorb and dampen energy of impacts, without leading to ruptures and leaking along sealing areas, e.g., the transversal top sealing of a wedge-like pouch, and the polymer of the carrier layer is an oriented polypropylene, or preferably, an oriented polyester or polyamide.
  • the gas barrier layers of SiOx are positioned in the laminate such that they are facing each other, with the intermediate polymer layer between them. In this way, optimal gas barrier layers may be obtained and the layers of SiOx will be protected in the best way.
  • the SiOx layers are facing outwards in the laminate structure are conceivable.
  • PECVD technique a method of depositing inorganic layers, such as SiOx, onto polymer films, which however, generally result in thicker and less flexible layers of the SiOx. This in turn, due to the formation of cracks in the SiOx layer, generally results in laminates of lower quality with regard to oxygen barrier properties.
  • the SiOx gas barrier layers are applied by means of the continuous method of plasma enhanced chemical vapour deposition, PECVD, of SiOx from a plasma of an organic silicon compound, such as hexadimethylsiloxane (HDMSO).
  • PECVD plasma enhanced chemical vapour deposition
  • the thickness of the carrier polymer layer is from about 7 to about 30 microns ( ⁇ m), more preferably from about 8 to about 20, most preferably from about 8 to about 15 ⁇ m, and according to a preferred embodiment, the two carrier polymer films have about the same or exactly the same thickness. It is known that the PECVD process works optimally with the above thickness of the carrier layer, which is also preferred from the economical point of view.
  • carrier layers i.e. the outer layers of the sandwich construction, that have about the same or exactly the same thickness, although it may be possible for certain desired properties to use carrier layers of different thickness or bending stiffness.
  • the total thickness of the intermediate layer is from about
  • the packaging laminate is from about 100 to about 80 ⁇ m, most preferably from about 100 to about 150 ⁇ .
  • the thickness of the intermediate layer should be from about 40 to about 65 ⁇ m, when the second part-layer comprises a polymer such as for example VLDPE or ULDPE.
  • the second part-layer comprises a polymer such as for example VLDPE or ULDPE.
  • thicker intermediate layers such as up to 90 ⁇ m, in particular if the total thickness of the packaging laminate is desired to be from about above 150 to about 180 ⁇ m.
  • the thickness of the intermediate layer (15) is from
  • the thickness of the polymer carrier layer (11 ,12) is from 8 to 15 ⁇ m
  • the thickness of the outside layers of heat-sealable olefin polymer (16,17) is from 10 to 25 ⁇ m and from 18 to 30 ⁇ m, respectively
  • the total thickness of the packaging laminate is from 100-150 ⁇ m.
  • the thickness of the intermediate layer (15) is from
  • the thickness of the polymer carrier layer (11 ,12) is from 12 to 15 ⁇ m
  • the thickness of the outside layers of heat-sealable olefin polymer (16,17) is from 10 to 25 ⁇ m and from 18 to 30 ⁇ m, respectively
  • the total thickness of the packaging laminate is from 100 to 150 ⁇ m.
  • the thickness of the intermediate layer (15) is from 40 to 65 ⁇ m
  • the thickness of the polymer carrier layer (11 ,12) is from 8 to 12 ⁇ m
  • the thickness of the outside layers of heat-sealable olefin polymer (16,17) is from 10 to 25 ⁇ m and from 18 to 30 ⁇ m, respectively
  • the total thickness of the packaging laminate is from 100 to 150 ⁇ m.
  • the ratio between the thickness of the intermediate layer and the carrier layer is from 2 to 8,5 and the ratio of the total thickness of the packaging laminate to the thickness of the intermediate layer is from 1 ,5 to 5 when the total thickness is from 100 to 150 ⁇ m, or, the ratio between the thickness of the intermediate layer and the carrier layer is from 4 to 10 and the ratio of the total thickness of the packaging laminate to the thickness of the intermediate layer is from 1 ,7 to 3 when the total thickness is from 150 to 180 ⁇ m.
  • a further preferred important advantage is that such a packaging laminate may be transparent to provide packages having at least a portion that is transparent to make the filled contents visible.
  • a packaging container filled with beverage or liquid food preferably an aseptic packaging container, produced from the packaging laminate of the invention.
  • the packaging container according to the invention is a pouch or stand-up pouch" or similar and is durable at handling and distribution and resistant to moisture and oxygen gas during long term storage, due to the high quality packaging laminate, which in turn also provides for high seal quality and excellent gas barrier properties.
  • a further important advantage of packaging containers produced from the packaging laminate according to the invention is that they are durable to microwave cooking or thawing, as well as retorting. According to a further aspect of the invention, there is provided a method of manufacturing of the laminated packaging material of the invention.
  • Figure 1 a is a cross-sectional view of a first embodiment of a laminated packaging material according to the present invention.
  • Figure 1 b is a cross-sectional view of a second, best mode embodiment of a laminated packaging material according to the present invention.
  • Figure 1c is a cross-sectional view of a third embodiment of a laminated packaging material according to the present invention.
  • Figure 2 shows a preferred example of a packaging container produced from the packaging laminate according to the invention.
  • Figures 3a, 3b, and 3c show alternative preferred embodiments of methods of manufacturing of the packaging laminate.
  • Figure 4 show a strain-stress graph over four different polymers or polymer blends.
  • Figure 1a thus shows a packaging laminate 10, comprising a first and second carrier layer 11;12 being a film of a preferably oriented polyester, such as for example polyethyleneterephtalate (PET, OPET or BOPET), or a film of a preferably oriented polyamide (PA), onto which are coated thin gas barrier layers of SiOx 13; 14 by means of plasma enhanced chemical vapour deposition (PECVD).
  • PECVD plasma enhanced chemical vapour deposition
  • an intermediate layer 15 including a first part-layer 15a of a thermoplastic, preferably polyolefin-based, polymer having a high stiffness, such as for example high density polyethylene (HDPE ) or polypropylene (PP), and a second part-layer 15b of a thermoplastic, preferably polyolefin-based, polymer having high elastomeric properties, such as for example very low density polyethylene (VLDPE), ultra low density polyethylene (ULDPE), polyethylene-based copolymers or terpolymers, polyolefin-based elastomers or plastomers.
  • a thermoplastic preferably polyolefin-based, polymer having a high stiffness, such as for example high density polyethylene (HDPE ) or polypropylene (PP)
  • the intermediate layer 15 is thicker than any of the surrounding layers in the packaging laminate, and provides as such a distancing element between the two carrier layer films of oriented polymer.
  • the two part-layers 15a, 15b are essentially of the same thickness and may in an alternative embodiment switch place with each other.
  • Figure 1b shows a preferred packaging laminate 10' in which the intermediate layer 15, besides said first 15a and second 15b part-layers, includes a third part-layer 15c which is identical to said second part-layer 15b.
  • the first part-layer 15a is arranged in-between the second 15b and third 15c part layers.
  • Figure 1c shows yet an embodiment of a packaging laminate 10" in which the intermediate layer 15, besides said first 15a and second 15b part- layers, includes a third part-layer 15d which is identical to said first part-layer 15a.
  • the second part-layer 15b is arranged in-between the first 15a and third 15c part layers.
  • the preferred oriented polymer films have a certain degree of inherent stiffness in that they are oriented and thus may have a relatively higher degree of crystallinity than non- oriented polymer films.
  • the sandwich construction of two relatively stiff carrier layers laminated on each side of a thicker intermediate polymer layer provides for a laminate having surprisingly good bending stiffness in relation to its thickness.
  • the arrangement of the two PECVD-deposited SiOx- layers has proved to result in a much more than two-fold increased gas barrier, compared to a laminate or film containing merely one SiOx-layer.
  • the arrangement of an intermediate layer also acting as a "buffer" for penetration of gas, in particular oxygen gas provides for surprisingly improved gas barrier properties, which indicates a synergistic effect resulting from this particular arrangement.
  • the OTR value of the total construction will be about 2 cc/m2*24h at 23 °C and 50% RH.
  • the OTR value is improved to about 0,2 cc/m2*24h at 23 °C and 50% RH.
  • the OTR value of the total construction will be about 0,8 cc/m2*24h at 23 °C and 50% RH.
  • the OTR value is improved to about 0,16 cc/m2*24h at 23 °C and 50% RH .
  • the improvement of the gas barrier by the "buffer effect” is at least four- to five-fold the improvement from using just double gas barrier films directly laminated to each other.
  • a heat-sealable olefin polymer preferably a low density polyethylene (LDPE) or a linear low density polyethylene (LLDPE), which include also so-called metallocene-catalysed LLDPE ' s (m-LLDPE), i.e. LLDPE polymers catalysed by means of a single site catalyst.
  • a heat-sealable olefin polymer preferably a layer of LDPE, more preferably a layer of LLDPE and most preferably a first part-layer 17a of LDPE and a second outermost part-layer 17b of LLDPE.
  • the outside layers 16, 17 are applied each in a quantity of from about 10 to about 30 ⁇ m, for optimal heat sealability properties in relation to cost efficiency.
  • binder layers of adhesive polymers, tie layers and primers known in the art.
  • Such binder layers and primers are adapted to the specific choices of polymer in the various layers and may be selected from polyolefins and modified polyolefins, preferably polyethylene- based polymers, such as for example LDPE and modified LDPE.
  • binder layers are LPDE homo- or copolymers or graft copolymers of polyethylene, grafted with monomers comprising carboxylic or glycidyl functional groups, such as acrylic monomers or maleic anhydride (MAH) monomers, for example ethylene (meth)acrylic acid copolymer (E(M)AA), ethylene-glycidyl(meth)acrylate copolymer (EG(M )A) or MAH-grafted polyethylene (MAH-g-PE).
  • E(M)AA ethylene (meth)acrylic acid copolymer
  • EG(M )A ethylene-glycidyl(meth)acrylate copolymer
  • MAH-g-PE MAH-grafted polyethylene
  • a polyethylene base polymer graft modified by an unsaturated alkoxysilane compound such as described in US Patent No. 5,731 ,092, herein incorporated by reference. See especially column 1 , line 39 to column 3, line 21 and Examples 1 and 2.
  • the polyethylene base polymer graft modified by an unsaturated alkoxysilane compound is blended with a non-grafted polyethylene, such as preferably low density polyethylene (LDPE).
  • LDPE low density polyethylene
  • the number of adhesion points between the grafted sites in the binder and the silicon oxide can be vastly increased if the grafted polyolefin is blended with a non-grafted polyolefin, i.e. the number of adhesion points increases despite less grafted sites in the binder polymer.
  • This most preferred embodiment is based on the insight that it is not only the number of grafted sites that affects the degree of adhesion, but also their ability to physically come in contact with the silicon oxide.
  • the adhesion in an individual adhesion point of the plurality of adhesion points will not be as good as in an individual adhesion point of a binding layer composed solely of a grafted polyolefin.
  • the preferred embodiment in addition solves the problem related to these contradictory aspects of grafted and non-grafted polyolefin binders, by providing a binder that is a blend of a grafted polyolefin and a non-grafted polyolefin.
  • the improved flexibility that is achieved due to the presence of a non-grafted polyolefin provides for an increased number of adhesion points, while the grafted polyolefin provides for improved adhesion in those points, all in all resulting in adhesion properties that are better than the adhesion properties of a grafted polyolefin binder per se and a non-grafted polyolefin binder per se.
  • the thickness referred to as the total thickness of the intermediate layer also includes the thicknesses of such binder layers.
  • FIG. 2 shows a preferred example of a packaging container 20 produced from a packaging laminate 10, 10' or 10" according to the invention.
  • the packaging container is particularly suitable for small beverage packages for direct use by means of a drinking straw or the like.
  • such a package has a volume of about 330 ml or less, preferably from about 100 to about 250 ml, for example about 125 ml, 200 ml or about 250 ml.
  • It may be a pouch of any configuration, but is preferably shaped as a wedge 21 , such that it is easy to handle and dimensionally stable when put on a shelf in the food store or on a table or the like.
  • the bottom part 22 of the package is fold formed such that the transversal heat seal 24 of the bottom is hidden under the triangular corner flaps 23, which are folded and sealed against the bottom of the package.
  • the packaging container 20 is preferably transparent.
  • Figure 3a shows a preferred embodiment 30a of a method of producing the packaging laminate 10', 10" according to the invention.
  • a first web 331 of a polymer carrier layer 332 coated with a SiOx gas barrier layer 333, and a second web 334 of a polymer carrier layer 335 coated with a SiOx gas barrier layer 336, are advanced towards an extrusion station 337, the two SiOx layers 333 and 336 preferably facing each other, and laminated to each other by means of co-extruding an intermediate, three-part polymer layer 338 between them and pressing the two webs 331 ,334 and the intermediate layer 338 together when passing a roller nip after the extrusion station 337.
  • the intermediate polymer layer 338 may also be coextruded together with adjacent layers of binder polymer 339 for improved bonding to the SiOx-layers on the two webs 331 and 334.
  • the resulting laminated web 340 is advanced to an extrusion station 341 , where an outside layer of a heat- sealable polyolefin 342 is extruded onto the outside of the polymer carrier layer 335.
  • the thus resulting web 343 is further advanced to an extrusion station 344, where an outside layer of a heat-sealable polyolefin 345 is extruded onto the outside of the polymer carrier layer 332.
  • the resulting packaging laminate 346 will then be wound up and stored onto a reel, not shown.
  • Figure 3b shows another preferred embodiment 30b of a method of producing the packaging laminate 10', 10" according to the invention.
  • a first web 331 of a polymer carrier layer 332 coated with a SiOx gas barrier layer 333, and a second web 334 of a polymer carrier layer 335 coated with a SiOx gas barrier layer 336, are advanced towards an extrusion station 337, the two SiOx layers 333 and 336 preferably facing each other, and laminated to each other by means of co-extruding an intermediate, three-part polymer layer 338 between them and pressing the two webs 331,334 and the intermediate layer 338 together when passing a roller nip after the extrusion station 337.
  • the intermediate polymer layer 338 may also be coextruded together with adjacent layers of binder polymer 339 for improved bonding to the SiOx layers on the two webs 331 and 334.
  • the resulting laminated web 340 is advanced to a hot roller nip 34I', where an outside layer of a premanufactured film comprising at least one layer of a heat-sealable polyolefin 342' is laminated to the outside of the polymer carrier layer 335, by means of application of heat and pressure in the hot roller nip 341'.
  • the thus resulting web 343' is further advanced to a hot roller nip 344', where an outside layer of a heat-sealable polyolefin 345' is laminated to the outside of the polymer carrier layer 332, by application of heat and pressure in the hot roller nip 344 ' .
  • the resulting packaging laminate 346 ' will then be wound up and stored onto a reel, not shown.
  • Figure 3c shows a further preferred embodiment 30c of a method of producing the packaging laminate 10', 10" according to the invention.
  • a first web 331 of a polymer carrier layer 332 coated with a SiOx gas barrier layer 333, and a second web 334 of a polymer carrier layer 335 coated with a SiOx gas barrier layer 336, are advanced towards a hot roller nip 337', the two SiOx layers 333 and 336 preferably facing each other, at the same time as a web of a pre-manufactured, co-extruded film of an intermediate, three-part polymer layer 338 ' is advanced between the two webs 331 , 334 towards the nip 337'.
  • the three webs are laminated to each other by application of heat and pressure when passing the hot roller nip 337' .
  • the intermediate polymer layer 338' may be a premanufactured film having outer layers of binder polymer 339 for improved bonding to the SiOx-layers on the webs 331 ,334.
  • the resulting laminated web 340 ' is advanced to a hot roller nip 341 ' , where an outside layer of a pre-manufactured film comprising at least one layer of a heat-sealable polyolefin 342 ' is laminated to the outside of the polymer carrier layer 335, by means of application of heat and pressure in the hot roller nip 341 ' .
  • the thus resulting web 343" is further advanced to a hot roller nip 344 ' , where an outside layer of a pre-manufactured film comprising at least one layer of a heat-sealable polyolefin 345 ' is laminated to the outside of the polymer carrier layer 332, by application of heat and pressure in the hot roller nip 344 ' .
  • the resulting packaging laminate 346" will then be wound up and stored onto a reel, not shown.
  • the extrusion stations 341 and 344 may be passed in the opposite order according to an alternative preferred embodiment.
  • the lamination of the outside heat-sealable polyolefin films may be carried out in the opposite order, i.e. by first laminating the premanufactured film 345 ' to the outer side of the polymer carrier layer 332, in the hot roller nip 344 ' , thus resulting in a web 347.
  • the web 347 is further advanced to a hot roller nip 341 ', in which the outside heat-sealable premanufactured film 342 ' is then laminated to the outer side of the polymer carrier layer 335, thus resulting in the packaging laminate 346' or
  • the surface of the SiOx gas barrier layer 333, 336 is treated by a surface oxidation treatment such as corona treatment, in order to provide improved adhesion to the intermediate polymer layer 338; 338' or the binder layers 339; 339' .
  • the various premanufactured webs 331, 334, 338' , 342' and 345' are laminated to each other by means of primer lamination, i.e. lamination by means of coating and drying a primer or anchoring agent onto one of the webs and then laminating through a roller nip.
  • the packaging laminate 10, 10', 10" may be provided with a printed decor layer in order to render the packaging container more attractive and informative to consumers and to protect its contents against light, which printed decor may be applied onto the SiOx layer 333 or 336, which is directed towards the outside of a package formed from the packaging laminate.
  • the carrier layer 332 may be applied onto the other side of the carrier layer 332 or onto the outside layer of heat-sealable polyolefin 342, 345; 342', 345'.
  • the printed outside should preferably be covered by a thin, transparent protective polymer layer.
  • Figure 4 shows a strain-stress graph over four different polymers or polymer blends, hence giving a comparative measure of the elastomeric properties of the polymers/polymer blends.
  • Curve 1 represents 100 % HDPE
  • curve 2 represents a blend of 60 %
  • curve 3 represents a blend of 75 % VLDPE and 25
  • Comparative simulation transport tests were carried out on packages made from laminate structures according to the invention having exactly the same outermost sealing layers, two SiOx-coated carrier layers of the same thickness and type and an intermediate layer having the same total thickness in all tests.
  • the packages were all produced in the same way. The only difference between the packages tested was the internal composition of the intermediate layer of the laminate structures.
  • 20 packages were simulation transport tested, i.e. placed on a shaking table and exposed to repetitive vibrations during 30 minutes. See results in Table 1.
  • Reference examples are a laminate with an intermediate layer of 45 g/m 2 solely VLDPE and a laminate with an intermediate layer of 45 g/m 2 solely HDPE, respectively.
  • Laminates according to the invention and with three part-layers all of the same thickness had better stiffness values and the one with most VLDPE, i.e. VLDPE/HDPE/VLDPE, and all three part-layers of the same thickness also had the lowest failure rate.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Thermal Sciences (AREA)
  • Laminated Bodies (AREA)
  • Wrappers (AREA)

Abstract

Laminé pour emballage faisant barrière contre les gaz (10), résistant aux fissurations provoquées par des tensions et à la flexion et offrant une intégrité entre les couches laminées. Ce laminé comprend des couches extérieures d'oléfine thermo-scellables (16, 17), deux couches polymères porteuses (11, 12) recouvertes chacune d'une couche de SiOx faisant barrière contre les gaz (13, 14), et une couche polymère intermédiaire (15) constitué par une première (15a) et une seconde (15b) couches partielles, la première couche partielle (15a) présentant une rigidité plus grande que la seconde couche partielle (15b) et la seconde couche partielle (15b) possédant des propriétés élastomères plus marquées que la première couche partielle (15a). La construction structurelle rigide en sandwich constituée par les deux couches porteuses rigides séparée par la couche intermédiaire amortisseuse empêche la fissuration par tension des couches de SiOx. L'invention concerne également un récipient d'emballage réalisé dans ledit laminé et un procédé de fabrication de ce laminé.
PCT/SE2005/000538 2004-05-10 2005-04-13 Lamine en plastique pour emballage faisant barriere contre les gaz WO2005108065A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP05722324A EP1747096A1 (fr) 2004-05-10 2005-04-13 Lamine en plastique pour emballage faisant barriere contre les gaz
JP2007513100A JP2007536140A (ja) 2004-05-10 2005-04-13 プラスチック製ガスバリア包装用積層体

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
SE0401215A SE527944C2 (sv) 2004-05-10 2004-05-10 Förpackningslaminat i plast och med gasbarriär, förpackningsbehållare samt metod för framställning av förpackningslaminatet
SE0401215-9 2004-05-10

Publications (1)

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WO2005108065A1 true WO2005108065A1 (fr) 2005-11-17

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JP (1) JP2007536140A (fr)
AR (1) AR048782A1 (fr)
SA (1) SA05260101B1 (fr)
SE (1) SE527944C2 (fr)
WO (1) WO2005108065A1 (fr)

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WO2013169690A1 (fr) * 2012-05-07 2013-11-14 The Procter & Gamble Company Matériaux flexibles destinés à des récipients flexibles
WO2013169688A1 (fr) * 2012-05-07 2013-11-14 The Procter & Gamble Company Matériaux flexibles pour récipients flexibles
US9327867B2 (en) 2013-08-01 2016-05-03 The Procter & Gamble Company Enhancements to tactile interaction with film walled packaging having air filled structural support volumes
US9688459B2 (en) 2013-08-01 2017-06-27 The Procter & Gamble Company Disposable flexible containers having surface elements
US9802719B2 (en) 2012-08-06 2017-10-31 The Procter & Gamble Company Methods of making flexible containers
US10465053B2 (en) 2014-05-15 2019-11-05 Dow Global Technologies Llc Barrier film, methods of manufacture thereof and articles comprising the same
US11472146B2 (en) 2013-08-01 2022-10-18 The Procter & Gamble Company Flexible containers having improved seam and methods of making the same
US11548709B1 (en) 2021-02-01 2023-01-10 Aeroflexx, Llc Flexible recyclable package

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EP0385054A1 (fr) * 1989-01-11 1990-09-05 Tetra Laval Holdings & Finance SA Matériau d'emballage stratifié formant barrière au gaz et à l'arôme et procédé pour sa fabrication
WO1999019229A1 (fr) * 1997-10-09 1999-04-22 Tetra Laval Holdings & Finance, S.A. Stratifie d'emballage dote de proprietes barriere au gaz et a l'arome
WO2000030846A1 (fr) * 1998-11-26 2000-06-02 Tetra Laval Holdings & Finance S.A. Structure multicouche d'emballage et contenants d'emballage ainsi fabriques, et procede de fabrication de cette structure
WO2002026494A2 (fr) * 2000-09-26 2002-04-04 Elopak Systems Ag Ameliorations relatives a des films
EP1300240A1 (fr) * 2001-10-02 2003-04-09 Atofina Research S.A. Récipient en plastique brillant à haute résistance à la corrosion fissurante

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EP0385054A1 (fr) * 1989-01-11 1990-09-05 Tetra Laval Holdings & Finance SA Matériau d'emballage stratifié formant barrière au gaz et à l'arôme et procédé pour sa fabrication
WO1999019229A1 (fr) * 1997-10-09 1999-04-22 Tetra Laval Holdings & Finance, S.A. Stratifie d'emballage dote de proprietes barriere au gaz et a l'arome
WO2000030846A1 (fr) * 1998-11-26 2000-06-02 Tetra Laval Holdings & Finance S.A. Structure multicouche d'emballage et contenants d'emballage ainsi fabriques, et procede de fabrication de cette structure
WO2002026494A2 (fr) * 2000-09-26 2002-04-04 Elopak Systems Ag Ameliorations relatives a des films
EP1300240A1 (fr) * 2001-10-02 2003-04-09 Atofina Research S.A. Récipient en plastique brillant à haute résistance à la corrosion fissurante

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013169688A1 (fr) * 2012-05-07 2013-11-14 The Procter & Gamble Company Matériaux flexibles pour récipients flexibles
CN104284775A (zh) * 2012-05-07 2015-01-14 宝洁公司 用于柔性容器的柔性材料
WO2013169690A1 (fr) * 2012-05-07 2013-11-14 The Procter & Gamble Company Matériaux flexibles destinés à des récipients flexibles
US9469088B2 (en) 2012-05-07 2016-10-18 The Procter & Gamble Company Flexible materials for flexible containers
US9682537B2 (en) 2012-05-07 2017-06-20 The Procter & Gamble Company Flexible materials for flexible containers
US9815258B2 (en) 2012-05-07 2017-11-14 The Procter & Gamble Company Flexible containers
US10005261B2 (en) 2012-05-07 2018-06-26 The Procter & Gamble Company Flexible containers
US10040581B2 (en) 2012-08-06 2018-08-07 The Procter & Gamble Company Methods of making flexible containers
US10414523B2 (en) 2012-08-06 2019-09-17 The Procter & Gamble Company Methods of making flexible containers
US9802719B2 (en) 2012-08-06 2017-10-31 The Procter & Gamble Company Methods of making flexible containers
US9327867B2 (en) 2013-08-01 2016-05-03 The Procter & Gamble Company Enhancements to tactile interaction with film walled packaging having air filled structural support volumes
US9688459B2 (en) 2013-08-01 2017-06-27 The Procter & Gamble Company Disposable flexible containers having surface elements
US11472146B2 (en) 2013-08-01 2022-10-18 The Procter & Gamble Company Flexible containers having improved seam and methods of making the same
US10465053B2 (en) 2014-05-15 2019-11-05 Dow Global Technologies Llc Barrier film, methods of manufacture thereof and articles comprising the same
US11548709B1 (en) 2021-02-01 2023-01-10 Aeroflexx, Llc Flexible recyclable package

Also Published As

Publication number Publication date
SE0401215L (sv) 2005-11-11
SE527944C2 (sv) 2006-07-18
SE0401215D0 (sv) 2004-05-10
SA05260101B1 (ar) 2008-05-19
EP1747096A1 (fr) 2007-01-31
AR048782A1 (es) 2006-05-24
JP2007536140A (ja) 2007-12-13

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