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WO2012093036A1 - Non-foil packaging laminate, method for manufacturing of the packaging laminate and packaging container produced thereof - Google Patents

Non-foil packaging laminate, method for manufacturing of the packaging laminate and packaging container produced thereof Download PDF

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Publication number
WO2012093036A1
WO2012093036A1 PCT/EP2011/073760 EP2011073760W WO2012093036A1 WO 2012093036 A1 WO2012093036 A1 WO 2012093036A1 EP 2011073760 W EP2011073760 W EP 2011073760W WO 2012093036 A1 WO2012093036 A1 WO 2012093036A1
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WO
WIPO (PCT)
Prior art keywords
layer
packaging laminate
paper
liquid
foil packaging
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.)
Ceased
Application number
PCT/EP2011/073760
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French (fr)
Inventor
Nils Toft
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Tetra Laval Holdings and Finance SA
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Tetra Laval Holdings and Finance SA
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Publication date
Application filed by Tetra Laval Holdings and Finance SA filed Critical Tetra Laval Holdings and Finance SA
Priority to RU2013136199/05A priority Critical patent/RU2586143C2/en
Priority to CN201180062715.4A priority patent/CN103313852B/en
Publication of WO2012093036A1 publication Critical patent/WO2012093036A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • B32B23/00Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose
    • B32B23/04Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising such cellulosic plastic substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B23/08Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising such cellulosic plastic substance 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

Definitions

  • the present invention relates to a non-foil packaging laminate for induction heat sealing into packages for liquid food or beverage.
  • the invention also relates to a method for manufacturing of the packaging laminate and to a packaging container made from the packaging laminate, thus employing a method of induction heat sealing the non-foil packaging laminate.
  • Packaging containers of the single use disposable type for liquid foods are often produced from a packaging laminate based on paperboard or carton.
  • One such commonly occurring packaging container is marketed under the trademark Tetra Brik Aseptic® and is principally employed for aseptic packaging of liquid foods such as milk, fruit juices etc, sold for long term ambient storage.
  • the packaging material in this known packaging container is typically a laminate comprising a bulk core layer of paper or paperboard and outer, liquid-tight layers of thermoplastics.
  • the laminate in these packaging containers normally comprises at least one additional layer, most commonly an aluminium foil.
  • the aluminium foil On the inside of the laminate, i.e. the side intended to face the filled food contents of a container produced from the laminate, there is an innermost layer, applied onto the aluminium foil, which innermost, inside layer may be composed of one or several part layers, comprising heat sealable adhesive polymers and/or polyolefins. Also on the outside of the paper or paperboard layer, there is an outermost heat sealable polymer layer.
  • the aluminium foil moreover renders the packaging material
  • thermosealable by inductive thermosealing which is a rapid and efficient sealing technique for obtaining mechanically strong, liquid- and gas-tight sealing joints or seams during the production of the containers.
  • the packaging containers are generally produced by means of modern, high-speed packaging machines of the type that form, fill and seal packages from a web or from prefabricated blanks of packaging material.
  • Packaging containers may thus be produced by reforming a web of the laminated packaging material into a tube by both of the longitudinal edges of the web being united to each other in an overlap joint by welding together the inner- and outermost heat sealable thermoplastic polymer layers.
  • the tube is filled with the intended liquid food product and is thereafter divided into individual packages by repeated transversal seals of the tube at a predetermined distance from each other below the level of the contents in the tube.
  • the packages are separated from the tube by incisions along the transversal seals and are given the desired geometric configuration, normally parallelepipedic, by fold formation along prepared crease lines in the packaging material.
  • the main advantage of this continuous tube-forming, filling and sealing packaging method concept is that the web may be sterilised continuously just before tube-forming, thus providing for the possibility of an aseptic packaging method, i.e. a method 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 micro-organisms in the filled product.
  • an aseptic packaging method i.e. a method 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 micro-organisms in the filled product.
  • Another important advantage of the continuous Tetra Brik® -type packaging method is, as stated above, the possibility of continuous high-speed packaging, which has considerable impact on cost efficiency.
  • a layer of an aluminium foil in the packaging laminate provides excellent gas barrier properties compared to most polymeric gas barrier materials.
  • the conventional aluminium-foil based packaging laminate for liquid food aseptic packaging is the most cost-efficient packaging material, at its level of
  • packaging laminates involving two or more barrier layers, of which one is a metallised layer may present feasible alternatives to foil- based laminates, however, with the abovementioned complication that the present induction heat sealing equipment cannot be used.
  • thermoplastic layer by means of a metallised layer, by means of induction sealing technology, provided that certain less revolutionary adaptations were made on the existing machines.
  • the metallised layers first tested were primarily coated on oriented PET film substrates.
  • the metallised layer should have a certain combination of thickness, or optical density, with layer quality.
  • quality is primarily meant that the layer should be homogeneous and have substantially the same thickness all across the width and length of the laminated packaging material.
  • PET-film substrates are generally quite expensive for what they provide in a packaging laminate of the above described kind. Actually, the about only significant contribution it has to the packaging laminate is that of acting as a carrier for the metallised layer. While it is believed that the induction sealing technology is feasible and possible to adapt also to other, less expensive, polymer substrates, it has been seen that the sealing process will probably need more calibration and surveillance in order to operate efficiently and reliably. It has also been seen that the choice of substrate may influence the quality and durability of the metallised layer during the heat sealing process.
  • non- aluminium foil packaging material for aseptic, liquid food packaging e.g. of milk or other beverage
  • non-foil packaging material is sealable by means of induction sealing in the installed base of filling and sealing equipment.
  • a non-foil packaging laminate for induction heat sealing into packages for liquid food or beverage
  • the packaging laminate comprising at least one, first, layer of paper or other cellulose-based material, which first paper layer is situated at the inner side of the packaging laminate and is pre-coated to receive and support an induction heat susceptible metal vapour deposited layer, in order to induce heat sealing in a thermoplastic polymer material
  • the packaging laminate further comprising such a metal vapour deposited layer applied onto the inner side of said pre-coated first layer of paper or cellulose-based material, and further comprising an oriented film laminated to the metal vapour deposited layer; and further comprising an innermost layer of liquid tight, heat sealable thermoplastic polymer material applied onto the inner side of the oriented film; and/or said oriented film comprises a liquid-tight heat-seal layer, representing the innermost layer of the film, wherein said oriented film is stretched in at least one direction at a stretching ratio of 2 or more, and has a core layer of a material having
  • the oriented film is applied onto the metal vapour deposited layer by an intermediate bonding layer and/or said oriented film comprises an adhesive layer on its outer side to be laminated to the metal vapour deposited layer.
  • a method of manufacturing a non-foil packaging laminate comprising the steps of providing a first layer of paper or other cellulose-based material, pre-coating the paper or cellulose-based material layer for receiving and supporting an induction heat susceptible metal vapour deposition coating, by an induction sealing durable layer onto the inner side of the paper or cellulose-based material layer, applying said induction heat susceptible metal layer onto the inner side of the thus coated paper layer, providing an oriented film (20), stretched in at least one direction at a stretching ratio of 2 or more, and having a core layer of a material having a higher melting point than the material of the innermost layer of the non-foil packaging laminate, laminating the oriented film to the metal coated paper layer, providing one or more layer(s) of liquid tight, heat sealable thermoplastic polymer material applied onto the inner side of the oriented film, and/or providing a liquid-tight heat-seal layer as a part of the oriented film representing the innermost layer of the film, wherein either the liquid
  • the objects of the present invention are by realized by a packaging container manufactured from the above described packaging laminate.
  • the objects of the present invention are realized by a method of heat sealing a non-foil packaging laminate, comprising the steps of providing a non-foil packaging laminate as defined above, in the form of a continuous web, forming the web-formed packaging laminate into a continuous tubular shape and applying a longitudinal seal in the longitudinal direction, filling the packaging laminate tube with a liquid foodstuff, forming heat-sealing zones by means of induction heating, at predetermined intervals in the traversing direction of the filled tube, and cutting through the centre of each traversing sealing zone, thereby forming individual containers.
  • FIG. 1 a, 1 a2, 1 b, 1 b2, 1 b3, 1 b4, 1 c and 1 c2 are schematically showing, in cross-section, first, second, third and fourth embodiments of a packaging laminate produced according to the invention
  • Fig. 2 is schematically showing a method of liquid coating of a polymer composition onto a paper substrate layer
  • Fig. 3 is showing a diagrammatic view of a plant for vapour deposition of a preferred metal layer onto a substrate
  • Fig. 4a, and 4b are schematically showing example methods of
  • Fig. 5a and 5b are showing examples of packaging containers produced from the packaging laminate according to the invention.
  • Fig. 6 is showing the principle of how such packaging containers are manufactured from the packaging laminate in a continuous form, fill and seal process.
  • a non-foil packaging laminate for induction heat sealing into packages for liquid food or beverage comprising at least one, first, layer of paper or other cellulose-based material, which first paper layer is situated at the inner side of the packaging laminate and is pre-coated to receive and support an induction heat susceptible metal vapour deposited layer, in order to induce heat sealing in a thermoplastic polymer material
  • the packaging laminate further comprising such a metal vapour deposited layer applied onto the inner side of said pre-coated first layer of paper or cellulose-based material, and further comprising an oriented film laminated onto the metal vapour deposited layer; and further comprising an innermost layer of liquid tight, heat sealable thermoplastic polymer material applied onto the inner side of the oriented film; and/or said oriented film comprises a liquid-tight heat-seal layer, representing the innermost layer of the film, wherein said oriented film is stretched in at least one direction at a stretching ratio of 2 or more, and
  • the oriented film is laminated to the metal vapour deposited layer by an intermediate bonding layer and/or said oriented film comprises an adhesive polymer layer on its outer side to be laminated to the metal vapour deposited layer.
  • the first layer of paper or other cellulose- based material is coated onto its inner side with an induction sealing durable coating layer having a higher melting point than the innermost layer of heat sealable material.
  • said layer of an induction heat susceptible metal vapour deposition coating which is adapted to induce heat sealing in an adjacent thermoplastic polymer layer.
  • the most cost-efficient way of providing such a coating onto the paper layer, in order to prepare it for metal vapour deposition coating is to apply it by means of a liquid coating method, often also generally referred to as liquid film coating or dispersion coating, of a liquid composition onto the paper layer and subsequently drying it, the liquid composition containing an induction sealing durable polymer binder dispersed or dissolved in an aqueous or solvent medium.
  • a liquid coating method often also generally referred to as liquid film coating or dispersion coating
  • the induction sealing durable coating layer is formed from a composition mainly comprising a polymer selected from the group consisting of polyvinyl alcohol (PVOH), water dispersible ethylene vinyl alcohol (EVOH), ethylene vinyl alcohol vinyl acetate copolymer,
  • the thus coated layer has a higher melting point than the innermost layer of thermoplastic material or the liquid-tight heat-seal layer of the oriented film, by which it is intended to heat seal the packaging laminate into filled and sealed packages.
  • the sealing durable coating layer is a thermomechanically stabile layer
  • the outer and innermost thermoplastic heat sealable material, as well as the liquid-tight heat-seal layer is based on polyolefins, more preferably based on polyethylene and most preferably based on low density polyethylene, such as for example LDPE, LLDPE, m-LLDPE and VLDPE and blends thereof.
  • the induction sealing durable coating layer is formed from a composition mainly comprising PVOH, water dispersible EVOH or starch.
  • a water dispersible EVOH has a higher amount of vinyl alcohol units compared to melt processable EVOH, and are more similar in nature to PVOH than to EVOH.
  • Pure PVOH and starch-based polymers may be more or less biologically degradable, why such polymers may be more desirable for some packaging applications.
  • the induction sealing durable coating layer may be preferred to be formed from a composition mainly comprising a polymer selected from the group consisting of polyvinyl alcohol (PVOH), water dispersible ethylene vinyl alcohol (EVOH), ethylene vinyl alcohol vinyl acetate copolymer,
  • PVDC polyvinylidene chloride
  • PA water dispersible polyamide
  • starch starch derivatives, and combinations of two or more thereof.
  • PVOH as a liquid coating barrier polymer enjoys many desirable properties, with the result that it is the most preferred barrier material in many contexts. Among these, mention might be made of the good film formation properties, compatibility with foods and economic value, together with its high oxygen gas barrier properties.
  • PVOH provides a packaging laminate with high odour barrier properties, which is especially important for the packaging of milk.
  • polyvinyl alcohol is suitably applied by means of a liquid coating process, i.e. in the form of an aqueous or solvent-based dispersion or solution which, on application, is spread out to a thin, uniform layer on the substrate and thereafter dried.
  • liquid gas barrier composition is water-based, because such composition usually have a better work environment friendliness than solvent- based systems, as well.
  • a polymer or compound with functional carboxylic acid groups may be included in the composition.
  • the polymer with functional carboxylic acid groups is selected from among ethylene acrylic acid copolymer (EAA) and ethylene methacrylic acid copolymers (EMAA) or mixtures thereof.
  • EAA ethylene acrylic acid copolymer
  • EAA ethylene methacrylic acid copolymers
  • One known such particularly preferred barrier layer mixture consists of PVOH, EAA and an inorganic laminar compound.
  • the EAA copolymer is then included in the barrier layer in an amount of about 1 -20 weight %, based on dry coating weight.
  • compositions may be made more durable by drying and curing at elevated temperatures.
  • Crosslinking can also be induced by the presence of polyvalent compounds, e.g. metal compounds such as metal-oxides, although such compounds are less preferred in the coating compositions for this purpose.
  • EVOH water-dispersible ethylene vinyl alcohol polymer
  • Conventional EVOH polymers are normally intended for extrusion and are not possible to disperse/dissolve in an aqueous medium in order to produce a thin liquid coated barrier film of 5 g/m2 or below, preferably 3,5 g/m2 or below. It is believed that the EVOH should comprise a rather high amount of vinyl alcohol monomer units to be water-dispersible or dissolvable and that the properties should be as close to those of liquid coating grades of PVOH as possible.
  • extruded EVOH layer is not an alternative to liquid coated EVOH, because it inherently has less similar properties to PVOH than EVOH grades for extrusion coating, and because it cannot be applied at a cost-efficient amount below 5 g/m2 as a single layer by extrusion coating or extrusion lamination, i.e. it requires co-extruded adhesive polymer layers, which are generally very expensive polymers. Furthermore, very thin extruded layers cool off too quickly and do not contain enough heat energy to sustain sufficient lamination bonding to the adjacent layers.
  • polymer binders suitable for liquid coating
  • polysaccharides in particular starch or starch derivatives, such as preferably oxidised starch, cationic starch and hydroxpropylated starch.
  • modified starches are hypochlorite oxidised potato starch (Raisamyl 306 from Raisio), hydroxypropylated corn starch (Cerestar 05773).
  • starch or starch derivatives such as preferably oxidised starch, cationic starch and hydroxpropylated starch.
  • modified starches are hypochlorite oxidised potato starch (Raisamyl 306 from Raisio), hydroxypropylated corn starch (Cerestar 05773).
  • other starch forms and derivatives may be feasible liquid coating binders.
  • polymer binders are coatings comprising mixtures of carboxylic acid containing polymers, such as acrylic acid or methacrylic acid polymers, and polyalcoholic polymers, such as PVOH or starch. A cross-linking reaction of these polymer binders are preferred, as mentioned above, for resistance to high humidity.
  • the binder polymer is PVOH, because it has all the good properties mentioned above, i.e. in addition to good induction heat sealing resistance, also good film formation properties, gas barrier properties, cost efficiency, food compatibility and odour barrier properties.
  • a PVOH-based gas barrier composition performs best when the PVOH has a degree of saponification of at least 98 %, preferably at least 99 %, although also PVOH with lower degrees of saponification will provide good properties.
  • the liquid composition additionally comprises inorganic particles in order to further improve the oxygen gas barrier properties.
  • the polymer binder material may for example be mixed with an inorganic compound which is laminar in shape, or flake-formed.
  • an oxygen gas molecule has to migrate a longer way, via a tortuous path, through the oxygen barrier layer, than the normal straight path across a barrier layer.
  • the inorganic laminar compound is a so-called nanopartide compound dispersed to an exfoliated state, i.e. the lamellae of the layered inorganic compound are separated from each other by means of a liquid medium.
  • the layered compound preferably may be swollen or cloven by the polymer dispersion or solution, which at dispersion has penetrated the layered structure of the inorganic material. It may also be swollen by a solvent before added to the polymer solution or polymer dispersion.
  • the inorganic laminar compound is dispersed to a delaminated state in the liquid gas barrier composition and in the dried barrier layer.
  • clay minerals or clays includes minerals of the kaolinite, antigorite, smectite, vermiculite, bentonite or mica type, respectively. Specifically, laponite, kaolinite, dickite, nacrite, halloysite, antigorite, chrysotile, pyrophyllite, montmorillonite, hectorite, saponite, sauconite, sodium tetrasilicic mica, sodium taeniolite, commonmica, margarite, vermiculite, phlogopite, xanthophyllite and the like may be mentioned as suitable clay minerals.
  • Preferred nano-particles are those of montmorillonite, most preferred purified montmorillonite or sodium-exchanged montmorillonite (Na-MMT).
  • the nano-sized inorganic laminar compound or clay mineral preferably has an aspect ratio of 50-5000 and a particle size of up to about 5 ⁇ in the exfoliated state.
  • the inorganic particles mainly consist of such laminar bentonite particles having an aspect ratio of from 50 to 5000.
  • the barrier layer includes from about 1 to about 40 weight %, more preferably from about 1 to about 30 weight % and most preferably from about 5 to about 20 weight %, of the inorganic laminar compound based on dry coating weight. If the amount is too low, the gas barrier properties of the coated and dried barrier layer will not be markedly improved compared to when no inorganic laminar compound is used. If the amount is too high, the liquid composition will become more difficult to apply as a coating and more difficult to handle in storage tanks and conduits of the applicator system.
  • the barrier layer includes from about 99 to about 60 weight %, more preferably from about 99 to about 70 weight % and most preferably from about 95 to about 80 weight % of the polymer based on the dry coating weight.
  • An additive, such as a dispersion stabiliser or the like, may be included in the gas barrier composition, preferably in an amount of not more than about 1 weight % based on the dry coating.
  • the inorganic particles mainly consist of laminar talcum particles having an aspect ratio of from 10 to 500.
  • composition normally comprises an amount of from 10 to 50 weight-%, more preferably from 20 to 40 weight-% of the talcum particles, based on dry weight. Below 20 weight-%, there is no significant increase in gas barrier properties, while above 50 weight-%, the coated layer may be more brittle and breakable because there is less internal cohesion between the particles in the layer. Above 5o weight %, the polymer binder seems to be in too low amount to surround and disperse the particles and laminate them to each other within the layer.
  • colloidal silica particles exhibiting a particle size of 3-150 nm, preferably 4-100 nm and even more preferred 5-70 nm, which particles are preferably amorphous and spherical.
  • the use of colloidal silica particles moreover has the advantage that the liquid barrier composition may be applied at a dry content of 15-40 weight %, preferably 20-35 weight % and even more preferred 24-31 weight %, whereby the demand on forcible drying is decreased.
  • inorganic particles that may be used are particles of kaolin, mica, calcium carbonate etc.
  • the preferred polymer binder also when employing inorganic particles for providing oxygen barrier properties, is PVOH, for examples the once above, partly due to its advantageous properties mentioned above.
  • PVOH is advantageous from a mixing point of view, i.e. it is generally easy to disperse or exfoliate inorganic particles in an aqueous solution of PVOH to form a stable mixture of PVOH and particles, thus enabling a good coated film with a
  • the said induction heat sealing durable layer is applied at a total amount of from 0.5 to 7 g/m 2 , preferably from 0.5 to 5 g/m 2 , more preferably 0.5 to 3 g/m 2 , dry weight.
  • 0.5 g/m 2 there will be a too low effect of induction sealing durability, and there is a risk of pinholes being formed, depending on paper or substrate characteristics, in connection with the removal of water or solvent for drying the applied barrier layer, if the applied layer is too thin.
  • the coated layer will not bring cost-efficiency to the packaging laminate, due to high cost of polymers in general and due to high energy cost for evaporating off the dispersion liquid.
  • PVOH a recognisable level of oxygen barrier is achieved by PVOH at 0.5 g/m 2 and above, and a good balance between barrier properties and costs is achieved between 0.5 and 3.5 g/m 2 .
  • the oxygen gas barrier layer is applied in two consecutive steps with intermediate drying, as two part-layers. If thus applied as two part-layers, each layer is suitably applied in amounts from 0.3 to 3.5 g/m 2 , preferably from 0.5 to 2,5 g/m 2 , and allows a higher quality total layer from a lower amount of liquid gas barrier composition. More preferably, the two part-layers are applied at an amount of from 0.5 to 2 g/sm 2 each, preferably from 0.5 to 1 .5 g/m 2 each.
  • the metal vapour deposition coating layer is applied by means of physical vapour deposition (PVD) onto the thin coated paper substrate.
  • PVD physical vapour deposition
  • the thin metal vapour deposition coatings according to the invention are nanometer-thick, i.e. have a thickness that is most suitably counted in nanometers, for example of from 5 to 500 nm (50 to 5000 A), preferably from 5 to 200 nm, more preferably from 5 to 100 nm and most preferably from 5 to 50 nm.
  • vapour deposition coating having induction heat durability is made of a metal compound, and preferably an induction heat sealing inducing metal vapour deposition coating layer is a layer substantially consisting of aluminium. Normally, an aluminium metallised layer inherently has a thin surface portion consisting of an aluminium oxide due to the nature of the metallisation coating process used.
  • the metal vapour deposition coating layer has an optical density (OD) of from 1 to 5, preferably of from 1 .5 to 3.5, more preferably from 2 to 3.
  • OD optical density
  • An aluminium-based thin vapour deposited layer preferably has a thickness of from 5 to 100 nm, more preferably from 5-50 nm, which corresponds to less than 1 % of the aluminium metal material present in an aluminium foil of conventional thickness, i.e. 6,3 ⁇ .
  • a step of surface treatment of the substrate film may be carried out before vapour deposition coating, especially metallising, the substrate.
  • a preferred metal according to the present invention is aluminium, although any other metal capable of being vacuum deposited into a
  • homogeneous coating may be used according to the invention.
  • metals such as Au, Ag, Cr, Zn, Ti or Cu are conceivable also.
  • thin coatings of metal or a mixture of metal and metal oxide provide barrier properties against water vapour and are used also when the desired function is to prevent water vapour from migrating into and through the multilayer film or packaging laminate.
  • the metal in a metallisation coating is aluminium (Al).
  • the substrate i.e. the first, innermost situated, layer of paper or other cellulose- based material (1 1 ) should be as thin as possible, so that as many meters as possible may be rolled onto a roll of coated paper.
  • the first paper layer has a surface weight of from 20 to 100 g / m2, preferably from 20 to 70 g/m2, more preferably from 30-60 g/m2.
  • the thinner the paper can be the more cost-efficient it can be in the metal vapour deposition coating process. Seen from a stiffness perspective, a thicker first paper layer also contributes to a higher stiffness and grip-ability of the total packaging laminate structure.
  • a second layer of paper or paperboard, for use as a stabilising layer, in a common carton package for liquid packaging usually has a thickness of from about 100 pm up to about 600 pm, and a surface weight of approximately 100- 500 g/m2, preferably about 200-400 g/m2, more preferably from 200 to 300 g/m2 and may be a conventional paper or paperboard of suitable packaging quality.
  • a thinner packaging laminate may be used, having a thinner paper layer.
  • Packaging containers made from such packaging laminates are not fold-formed and more similar to pillow-shaped flexible pouches.
  • a suitable single paper layer for such pouch-packages then usually has a surface weight of from about 30 to about 140 g/m2, preferably from about 50 to about 120 g/m2, more preferably from 50 to about 1 10 g/m2, most preferably from 50 to 70 g/m2.
  • such a low cost packaging laminate may alternatively comprise two or more thin paper layers, of which the first, inner paper layer is vapour deposition coated with an induction heat susceptible material, according to the present invention.
  • the second outer paper layer suitably has a surface weight of from 20 to 100 g / m2, preferably from 20 to 70 g/m2, more preferably from 20-50 g/m2.
  • an oriented film is applied on the metallised layer (metal vapour deposited layer).
  • the use of an oriented film provides beneficial barrier properties.
  • the application of a film may reduce the cost of the final package and improve or alternate its properties.
  • the film will also work as protective layer for the
  • Suitable films are oriented films, stretched in at least one direction at a stretching ratio of 2 or more, and having a core layer of a material having a higher melting point than the heat sealable material of the innermost layer of the packaging laminate. Generally the melting point of the core layer is above 130 °C.
  • the stretching ratio is dependent on the material used in the film but the ratio may be up to about 10. In certain aspects of the invention it is preferred to have a stretching ratio of 3 or more.
  • suitable films are mono-oriented films, having at least a core layer from a polymer material selected from polypropylene (OPP), polyethylene terephthalate (OPET), polyamide (OPA), polyethylene naphthalate (OPEN), polybutylene terephthalate (OPBT), trimethylene
  • a polymer material selected from polypropylene (OPP), polyethylene terephthalate (OPET), polyamide (OPA), polyethylene naphthalate (OPEN), polybutylene terephthalate (OPBT), trimethylene
  • biaxially-oriented films such as biaxially-oriented polypropylene (BOPP), polyethylene terephthalate (BOPET), polyamide (BOPA), polyethylene naphthalate (BOPEN), polybutylene terephthalate (BOPBT), trimethylene terephthalate (BOPTT), or oriented films from two or more of the mentioned polymers, i.e. polypropylene, polyethylene terephthalate, polyamide, polyethylene naphthalate, polybutylene terephthalate, trimethylene terephthalate, blended or copolymerized and thereafter used to form a mono-oriented or biaxially oriented film.
  • BOPP biaxially-oriented polypropylene
  • BOPET polyethylene terephthalate
  • BOPA polyethylene terephthalate
  • BOPEN polyethylene naphthalate
  • BOPBT polybutylene terephthalate
  • trimethylene terephthalate BOPTT
  • oriented films from two or more of the mentioned polymers, i.e
  • Some beneficial properties of said films are high tensile strength facilitating high-speed conversion, good puncture and flex-crack resistance over a wide range of temperatures, potentially good barrier to water vapour, resistance to oils and greases and moisture resistance as well as resistance to wrinkling or shrink due to environmental condition changes.
  • the oriented film may be a film that comprises additional layers in which case the core layer of the film is represented by the above exemplified films.
  • the core layer of the film is a polymer which is selected from mono-oriented polypropylene (OPP), polyethylene terephthalate (OPET), polyamide (OPA), polyethylene naphthalate (OPEN), polybutylene terephthalate (OPBT), trimethylene terephthalate (OPTT); biaxially-oriented polypropylene (BOPP), polyethylene terephthalate (BOPET), polyamide (BOPA), polyethylene naphthalate (BOPEN), polybutylene terephthalate (BOPBT), trimethylene terephthalate (BOPTT).
  • the film may additionally include one or more of the following: a bonding layer, an adhesive layer and a liquid-tight heat-seal layer.
  • the bonding layer is used in order to facilitate bonding between pre-manufactured webs or films and usually consists of a thermoplastic polymer.
  • the adhesive layer is used for improving the adhesion between the film and other layers and normally consists of an adhesive polymer containing functional adhesion-promoting groups.
  • the adhesive layer is a layer of the oriented film.
  • the adhesive layer may be applied before the stretching, for example by co- extrusion with the core layer or applied after the stretching, for example by dispersion coating.
  • Such an adhesive polymer layer on the outer side of the oriented film enables lamination by means of applying heat and pressure when joining the oriented film and the coated paper web in a roller nip of a lamination station, without extruding an additional intermediate bonding layer between the two pre-manufactured webs.
  • the thickness of the oriented film is between 4 and 25 ⁇ . This generally applies when the film does not comprise a liquid-tight heat-seal innermost layer as then the film may be thicker.
  • the film is bound to the metallised layer by a separate bonding layer, which is usually applied by extrusion lamination of an intermediate melt extrusion layer when laminating the pre-manufacture film to the pre-coated, metallised, paper layer.
  • both an adhesive layer as a part of the oriented film and an intermediate bonding layer is present and employed for laminating the oriented film to the metal-coated paper.
  • material suitable as bonding layers, for extrusion lamination layers are polymers based on low density polyethylene polymers and selected from modified or un-modified LDPE or LLDPE polymers, co-polymers or graft co-polymers of ethylene polymers with functional-group containing monomer units, such as carboxylic or glycidyl functional groups, e.g. (meth)acrylic acid monomers or maleic anhydride (MAH) monomers, (i.e.
  • ethylene acrylic acid copolymer EAA or ethylene methacrylic acid copolymer (EMAA)
  • EAA ethylene acrylic acid copolymer
  • EEMAA ethylene methacrylic acid copolymer
  • EAA ethylene acrylic acid copolymer
  • EEMAA ethylene methacrylic acid copolymer
  • EAA ethylene acrylic acid copolymer
  • EEMAA ethylene methacrylic acid copolymer
  • MAH-g-PE maleic anhydride-grafted polyethylene
  • modified polyethylene is an ethylene acrylic acid copolymer (EAA) or an ethylene methacrylic acid copolymer (EMAA).
  • adhesive layers are carboxylic acid functionalized
  • polyethylenes based on LDPE or LLDPE including co-polymers or graft co- polymers with functional-group containing monomer units, such as carboxylic or glycidyl functional groups, e.g. (meth)acrylic acid monomers or maleic anhydride (MAH) monomers, (i.e. ethylene acrylic acid copolymer (EAA) or ethylene methacrylic acid copolymer (EMAA)), ethylene-glycidyl(meth)acrylate copolymer (EG(M)A) or MAH-grafted polyethylene (MAH-g-PE).
  • EAA ethylene acrylic acid copolymer
  • EEMAA ethylene methacrylic acid copolymer
  • EAA ethylene acrylic acid copolymer
  • EAA ethylene methacrylic acid copolymer
  • EAA ethylene methacrylic acid copolymer
  • EAA ethylene-glycidyl(meth)acrylate copolymer
  • MAH-g-PE
  • the adhesive layer is selected from ethylene acrylic acid copolymer (EAA), ethylene methacrylic acid copolymer (EMAA)), ethylene- glycidyl(meth)acrylate copolymer (EG(M)A), and maleic anhydride-grafted polyethylene (MAH-g-PE), preferably ethylene acrylic acid copolymer (EAA) or ethylene methacrylic acid copolymer (EMAA).
  • EAA ethylene acrylic acid copolymer
  • EAA ethylene methacrylic acid copolymer
  • EAA ethylene methacrylic acid copolymer
  • EAA ethylene methacrylic acid copolymer
  • EAA ethylene methacrylic acid copolymer
  • EAA ethylene methacrylic acid copolymer
  • EAA ethylene methacrylic acid copolymer
  • EAA ethylene methacrylic acid copolymer
  • EAA ethylene methacrylic acid copolymer
  • EAA ethylene methacrylic acid copo
  • liquid-tight, heat sealable layers are required as the innermost part of the packaging material to be in direct contact with the product filled in a packaging container manufactured from the packaging material.
  • a liquid-tight heat-seal layer comprised in the oriented film may be an alternative or a complementary layer to providing a separate innermost liquid-tight, heat sealable layer.
  • the term liquid-tight heat-seal layer generally refers to a layer of the oriented film.
  • the liquid-tight heat-seal layer is selected from the same type of polyolefins as the outermost and innermost liquid-tight, heat sealable layers.
  • thermoplastics for the liquid-tight heat-seal layer and for the outermost and innermost liquid-tight, heat sealable layers are based on polyolefins, such as for example polyethylenes or polypropylenes, preferably polyethylenes and more preferably low density polyethylenes such as, for example LDPE, linear LDPE (LLDPE) or single site catalyst metallocene polyethylenes (m-LLDPE), Ultralow- density linear polyethylene (vLLDPE) or blends of two or more thereof.
  • polyolefins such as for example polyethylenes or polypropylenes, preferably polyethylenes and more preferably low density polyethylenes such as, for example LDPE, linear LDPE (LLDPE) or single site catalyst metallocene polyethylenes (m-LLDPE), Ultralow- density linear polyethylene (vLLDPE) or blends of two or more thereof.
  • LDPE linear LDPE
  • m-LLDPE single site catalyst metallocene polyethylenes
  • An adhesive layer may thus be applied, as a co-extruded part of the innermost layer of liquid-tight, heat sealable thermoplastic polymer material onto the inner side of the oriented film.
  • the innermost layer of a liquid-tight heat sealable thermoplastic material is often also aseptically tight.
  • the vapour deposition metal coated first paper layer may be bonded to a second paper or paperboard layer by one or more intermediate polymer layer(s), for example a thermoplastic polymer layer and more preferably a layer from a polymer selected from polyolefins and polyolefin-based co-polymers, often known as modified or adhesive polymers, especially LDPE or polyethylene-based polymers or co-polymers, or adhesive polymers, as described in the foregoing paragraph.
  • intermediate polymer layer(s) for example a thermoplastic polymer layer and more preferably a layer from a polymer selected from polyolefins and polyolefin-based co-polymers, often known as modified or adhesive polymers, especially LDPE or polyethylene-based polymers or co-polymers, or adhesive polymers, as described in the foregoing paragraph.
  • particles or pigments providing light barrier properties may be blended into one or more layers of the laminate.
  • One example is light absorbing particles such as carbon black.
  • the black colour of an intermediate layer is then advantageously hidden towards the outside by a paper or paperboard layer, and towards the inner side of the laminate, by a metallised, e.g. aluminium, layer.
  • Another example is light-reflective particles such as titanium dioxide. Such particles may furthermore be adding to a whiter
  • white pigments may improve the light barrier properties of the packaging laminate as well as improving the appearance of the packaging material towards the outside.
  • thermoplastic bonding layer including a layer of melt-extrudable barrier layer, for the bonding of the metal vapour deposition coated inside first paper layer to a further, second layer of paper or paperboard.
  • additional melt extrusion polymer layer(s) in the converting process at the lamination stage e.g. a further barrier layer and possibly one or two melt co- extrusion bonding layers.
  • a thin layer of a barrier polymer layer may be co-extrusion coated together with optional bonding layer(s) and the innermost heat sealable layer(s) onto the metal- coated inner side of the first paper layer.
  • Such a co-extruded inside barrier layer would have to be kept thin, in order to easily transfer the induced heat through from the metal vapour deposition coating to the heat sealable layer.
  • a liquid-film oxygen barrier coating layer may be coated onto the other, outer side of the first, innermost paper layer.
  • an liquid-film oxygen barrier coating layer may be applied onto the inner side of any further paper layer in the packaging laminate structure.
  • a packaging container manufactured from the non-foil packaging laminate of the invention.
  • the packaging container is suitable for long-term, aseptic packaging of liquid or wet food, and has good package integrity with strong, durable seals, from induction heat sealing.
  • the method comprises the steps of providing at least a first layer of paper or other cellulose-based material, pre-coating the paper or cellulose-based material layer for receiving and supporting an induction heat susceptible metal vapour deposition coating, by an induction sealing durable layer onto the inner side of the paper or cellulose-based material layer, applying said induction heat susceptible metal layer onto the inner side of the thus coated paper layer, providing an oriented film, and laminating the oriented film to the metal coated paper layer.
  • the film itself may comprise a liquid-tight heat- seal layer representing the innermost layer of the film, and optionally an adhesive layer representing the side of the film applied onto the induction heat susceptible metal layer.
  • the method comprises applying an intermediate bonding layer between the induction heat susceptible metal layer and the oriented film.
  • an outermost layer of a heat sealable thermoplastic polymer material may be provided and laminated on the outermost, opposite side, of the packaging laminate.
  • the outermost heat sealable polymer layer is then laminated on the outer side of the second paper layer.
  • An induction heat susceptible metal layer is sufficiently homogeneous and continuous in nature, to be able to transmit an electrical current as a result of an induced magnetic field, and to become heated such that a thermoplastic polymer layer will be heated and melted to provide melt sealing of said polymer. If the metal layer is dis-continuous due to un-even coating or due to cracks, there will be no heating provided in the sealing area.
  • the method further comprises the steps of providing a liquid composition containing a polymer binder dispersed or dissolved in an aqueous or solvent-based liquid medium and forming a thin induction sealing durable layer, comprising said polymer binder, contiguous to the inner side of the first paper layer, by coating the liquid composition onto the inner side of said layer of paper or other cellulose-based material and subsequently drying to evaporate the liquid, said polymer binder having a melting point higher than the thermoplastic polymer material of the innermost heat sealable layer.
  • the induction sealing durable polymer contained in the liquid composition is selected from a group consisting of polyvinyl alcohol (PVOH), water dispersible ethylene vinyl alcohol (EVOH), ethylene vinyl alcohol vinyl acetate copolymer, polyvinylidene chloride (PVDC), water dispersible polyamide (PA), starch, starch derivatives and combinations of two or more thereof.
  • PVOH polyvinyl alcohol
  • EVOH water dispersible ethylene vinyl alcohol
  • PVDC polyvinylidene chloride
  • PA water dispersible polyamide
  • starch starch derivatives and combinations of two or more thereof.
  • the induction sealing durable layer (12) is applied in a total amount of from 0.5 to 7 g/m 2 , preferably from 0.5 to 5 g/m 2 , more preferably from 0.5 to 3 g/m 2 , dry weight.
  • each layer may suitably be applied in amounts from 0.3 to 3.5 g/m 2 , preferably from 0.5 to 2.5 g/m 2 , which allows a higher quality total layer from a lower amount of liquid polymer composition. More preferably, the two part-layers may be applied at an amount of from 0.5 to 2 g/sm 2 each, preferably from 0.5 to 1 .5 g/m 2 each.
  • the first paper layer to be metal vapour deposition coated may be coated also on the other, outer side by a liquid composition of a polymer in aqueous or solvent based dispersion or solution, before the metallisation process step. It is desirable to avoid moisture in the vacuum chamber for metallisation, because it may reduce the speed at which the metallisation process can be carried out.
  • any back transfer of paper dust in the subsequent handling of coated paper webs on reels may be prevented by such a coating on the back- side.
  • a gas barrier coating layer may be coated onto the outer side of the first paper layer.
  • a gas barrier coating layer may be coated also onto the inside of said second paper layer.
  • the method of the invention further comprises the step of extrusion laminating the vapour deposited thin paper substrate to the inner side of the second paper layer, by means of an intermediate polymer bonding layer, preferably a thermoplastic polymer bonding layer.
  • a further aspect of the invention is a method of heat sealing a non-foil packaging laminate, comprising the steps of providing a non-foil packaging laminate as defined previously, in the form of a continuous web, forming the web- formed packaging laminate into a continuous tubular shape and applying a longitudinal seal in the longitudinal direction, filling the packaging laminate tube with a liquid foodstuff, forming heat-sealing zones by means of induction heating, at predetermined intervals in the traversing direction of the filled tube, and cutting through the centre of each traversing sealing zone, thereby forming individual containers.
  • FIG. 1 a there is shown, in cross-section, a first embodiment of a packaging laminate 10a for aseptic packaging and long-term storage under ambient conditions, produced according to the invention.
  • the laminate comprises a first paper layer 1 1 , having a surface weight of 50 g /m2,
  • the paper is prepared to receive a metal vapour deposition coating 12, which can work as an induction heat susceptible material and transmit heat to effect heat sealing in the innermost oriented film 20.
  • the thin paper, subsequently to be metal vapour-deposition coated may be prepared by means of coating or by means of impregnating the paper layer or by means of mixing chemicals into the paper pulp at the stage of manufacturing of the paper web, or by any combination of these means or other means, for preparation.
  • the prepared thin paper web is subsequently vapour deposition metallised to an optical density (OD) of about 3.
  • An outer liquid tight and heat sealable layer 15 of polyolefin is applied on the outside of the core layer 1 1 , which side is to be directed towards the outside of a packaging container produced from the packaging laminate.
  • the polyolefin of the outer layer 15 may be a conventional low density polyethylene (LDPE) of a heat sealable quality.
  • An oriented film 20 is laminated on the inside of the vapour deposited layer 12, which is to be directed towards the inside of a packaging container produced from the packaging laminate, and the oriented film 20 will be in contact with the packaged product.
  • the core layer of the oriented film is preferably selected from mono-oriented films, such as polypropylene (OPP), polyethylene terephthalate (OPET), polyamide (OPA), polyethylene naphthalate (OPEN), polybutylene terephthalate (OPBT), trimethylene terephthalate (OPTT); biaxially-oriented films, such as biaxially-oriented polypropylene (BOPP), polyethylene terephthalate (BOPET), polyamide (BOPA), polyethylene
  • mono-oriented films such as polypropylene (OPP), polyethylene terephthalate (OPET), polyamide (OPA), polyethylene naphthalate (OPEN), polybutylene terephthalate (OPBT), trimethylene terephthalate (OPTT); biaxially-oriented films, such as biaxially-oriented polypropylene (BOPP), polyethylene terephthalate (BOPET), polyamide (BOPA), polyethylene
  • BOPEN polybutylene terephthalate
  • BOPBT polybutylene terephthalate
  • BOPTT trimethylene terephthalate
  • oriented films from two or more of the mentioned polymers, i.e. polypropylene, polyethylene terephthalate, polyamide, polyethylene naphthalate, polybutylene terephthalate, trimethylene terephthalate, the polymers being blended or copolymerized and thereafter used to form a mono- oriented or biaxially oriented film.
  • the oriented film comprises one or more liquid-tight heat-seal layer(s) which represent the innermost side of the oriented film and consequently will be in contact with the packaged product.
  • the liquid-tight heat-seal layer representing the innermost part of the film is a liquid tight, heat sealable thermoplastic polymer material, such as a polymer based on low density polyethylene, such as LDPE and/or LLDPE.
  • the low density polyethylene includes an LLDPE produced by polymerising an ethylene monomer with a C4-C8, more preferably a C6-C8, alpha-olefin alkylene monomer in the presence of a metallocene catalyst, i.e. a so called metallocene -LLDPE (m-LLDPE).
  • the oriented film 20 may additionally comprise an adhesive layer on its outer side to be laminated to the metal vapour deposited layer 12.
  • the oriented film is laminated on the inside of the vapour deposited layer 12, which is to be directed towards the inside of a packaging container produced from the packaging laminate.
  • the low density polyethylene includes an LLDPE produced by polymerising an ethylene monomer with a C4-C8, more preferably a C6-C8, alpha-olefin alkylene monomer in the presence of a metallocene catalyst, i.e.
  • the innermost heat sealable layer 14 may consist of two or several part-layers of the same or different kinds of polymers.
  • the oriented film (20) may or may not include a liquid-tight heat-seal layer representing the layer of the film directed towards the inside on the oppositeside of the film as the vapour deposited layer 12. It is often preferred to have one liquid-tight, heat sealable layer only, in particular for cost reasons. Nevertheless there are applications where two heat-sealable layers, one as a liquid-tight heat-seal layer of the oriented film and the other as a liquid-tight, heat sealable thermoplastic polymer material 14. Throughout the specification it applies that whenever the innermost liquid- tight, heat sealable layer 14 is present the Iiquid-tight heat-seal layer of the film may be present or absent.
  • the oriented film 20 is bonded to the metal vapour deposition layer by means of an adhesive layer, such as an ethylene acrylic acid copolymer.
  • the adhesive layer is a layer of the oriented film.
  • a bonding layer 19 may be applied as an intermediate layer between the oriented film and the metal-coated paper layer.
  • Suitable bonding layers are based on low density polyethylene polymers and selected from modified or un-modified LDPE or LLDPE polymers, co-polymers or graft co-polymers of ethylene polymers with functional-group containing monomer units, such as carboxylic or glycidyl functional groups, e.g.
  • (meth)acrylic acid monomers or maleic anhydride (MAH) monomers i.e. ethylene acrylic acid copolymer (EAA) or ethylene methacrylic acid copolymer (EMAA)
  • EAA ethylene acrylic acid copolymer
  • EEMAA ethylene methacrylic acid copolymer
  • EAA ethylene acrylic acid copolymer
  • EEMAA ethylene methacrylic acid copolymer
  • MAH-g-PE maleic anhydride-grafted polyethylene
  • Another example of such modified polymers or adhesive polymers are so called ionomers based on low density polyethylene.
  • the modified polyethylene is an ethylene acrylic acid copolymer (EAA) or an ethylene methacrylic acid copolymer (EMAA).
  • the described modified polymers may be suitable also in the optional adhesive layer comprised in the film.
  • a second embodiment of a packaging laminate 10b for aseptic packaging and long-term storage under ambient conditions produced according to the invention.
  • the laminate comprises a first paper layer 1 1 , having a surface weight of 50 g /m2, and a thin induction sealing durable layer 13 formed by liquid coating of a liquid polymer composition, and subsequent drying, onto the paper layer 1 1 .
  • the composition comprises an aqueous solution of PVOH, and after drying, the coated layer thus comprises PVOH.
  • the PVOH has a saponification degree of at least 99 %.
  • the coated thin paper web is subsequently vapour deposition metallised on its coated side to an optical density (OD) of about 3.
  • the resulting packaging laminate thus comprises a thin paper substrate 1 1 , first coated with PVOH and then a thin vapour deposition coating layer 12 of aluminium metal at a thickness of about 50 nm.
  • An innermost oriented film 20 is bonded to the metal vapour deposition layer by means of an adhesive layer and/or a bonding layer 19 (as shown in Fig 1 b3), on the inside of the vapour deposited layer 12, which is to be directed towards the inside of a packaging container produced from the
  • the core layer of the oriented film is preferably selected from biaxially oriented polymer layers.
  • the oriented film is bonded to the inside of the vapour deposited layer 12 by an adhesive layer comprised in the film (Fig 1 b2) or by a bonding layer 19 (Fig 1 b4).
  • a low density polyethylene such as for example LDPE and/or LLDPE
  • the low density polyethylene includes an LLDPE produced by polymerising an ethylene monomer with a C4-C8, more preferably a C6-C8, alpha-olefin alkylene monomer in the presence of a metallocene catalyst, i.e. a so called metallocene -LLDPE (m-LLDPE).
  • the innermost heat sealable layer 14 may consist of two or several part-layers of the same or different kinds of polymers.
  • the innermost liquid-tight, heat sealable layer 14 additionally comprises an adhesive layer in order to improve bonding between the liquid-tight, heat sealable layer 14 and the oriented film 20.
  • the oriented film comprises an adhesive layer on its inner side where onto the liquid-tight, heat sealable layer 14 is to be laminated or extrusion coated.
  • An outer liquid tight and heat sealable layer 15 of polyolefin is applied on the outside of the core layer 1 1 , which side is to be directed towards the outside of a packaging container produced from the packaging laminate.
  • the polyolefin of the outer layer 15 may be a conventional low density polyethylene, such as LDPE and/ or LLDPE of a suitable heat sealable quality.
  • a packaging laminate 10c for aseptic packaging and long-term storage under ambient conditions produced according to the invention.
  • the laminate comprises a first paper layer 1 1 , having a surface weight of 50 g/m2, and a thin induction sealing durable layer 13 formed by liquid coating of a liquid polymer composition, and subsequent drying, onto the paper layer 1 1.
  • the composition comprises an aqueous solution of PVOH and 30 weight-% bentonite particles, and after drying, the coated layer thus comprises PVOH and optionally exfoliated bentonite particles homogeneously distributed in a laminar fashion within the PVOH layer.
  • the PVOH has a saponification degree of at least 99 %.
  • the prepared thin paper web is subsequently vapour deposition metallised to an optical density (OD) of about 3.
  • the packaging laminate thus comprises a thin paper substrate 1 1 , first coated with PVOH and then coated with a thin vapour deposition coating layer 12 of aluminium metal at a thickness of about 50 nm.
  • the packaging laminate comprises a second core, paperboard layer 16 having a surface weight of at least 200 g/m2 or, preferably of about 300 g/m2.
  • the first and second paper layers are suitably bonded to each other by means of an intermediate layer 17.
  • the intermediate layer is conventionally based on a polyolefin-based polymer, preferably a low density polyethylene (LDPE).
  • LDPE low density polyethylene
  • the intermediate bonding layer 17 is preferably formed by means of extrusion laminating the metal-coated first paper layer and the second
  • the intermediate layer 17 may be one or more layers.
  • the outer liquid tight and heat sealable layer 15 is defined as in Figures 1 a and 1 b.
  • the oriented film is bonded to the inside of the vapour deposited layer 12 by a thin induction sealing durable layer 13 formed by liquid coating of a liquid polymer composition, and subsequent drying, onto the paper layer 1 1.
  • a thin induction sealing durable layer 13 formed by liquid coating of a liquid polymer composition, and subsequent drying, onto the paper layer 1 1.
  • an adhesive layer is laminated to the vapour deposited layer 12.
  • An innermost liquid tight and heat sealable thermoplastic polymer material 14 is arranged on the inside of the oriented film 20.
  • the low density polyethylene includes an LLDPE produced by polymerising an ethylene monomer with a C4-C8, more preferably a C6-C8, alpha-olefin alkylene monomer in the presence of a metallocene catalyst, i.e. a so called metallocene - LLDPE (m-LLDPE).
  • the innermost heat sealable layer 14 may consist of two or several part-layers of the same or different kinds of polymers. As described above for Fig 1 b2 the innermost liquid-tight, heat sealable layer 14 additionally may comprise an adhesive layer, or the oriented film may comprise an adhesive layer on its inner side where the liquid-tight, heat sealable layer 14 is to
  • a bonding layer as described for Fig 1 b3 and Fig 1 b4, between the vapour deposited layer 12 and the oriented film 20.
  • the first paper layer which is to be metal vapour deposition coated, may be coated also on the other, outer side by a liquid composition of a polymer in aqueous or solvent based dispersion or solution, before the metallisation process step. It is desirable to avoid moisture in the vacuum chamber for metallisation, because it may reduce the speed at which the metallisation process can be carried out. Furthermore, any back transfer of paper dust in the subsequent handling of coated paper webs on reels may be prevented.
  • the first paper layer 1 1 may be a thin paper layer of about 50 g/m2 or even less. Since the paper layer is very thin, it may need an additional light barrier by added pigments in one or more of the layers of the laminate. There may, for example, be light reflecting white pigments, such as for example titanium dioxide ( ⁇ 02), and/or light absorbing pigments, such as for example carbon black, added to the liquid coated induction heat sealing durable layer 13, such as PvOH. Such pigments are advantageously hidden towards the inside by the metal vapour deposition coating 12, and at least to some extent by the paper layer 1 1 , towards the outside.
  • light reflecting white pigments such as for example titanium dioxide ( ⁇ 02)
  • light absorbing pigments such as for example carbon black
  • Fig. 2 the method of liquid coating of a polymer composition onto a paper, or paperboard layer is grammatically schematically shown.
  • the paper layer 21 a is fed from a storage reel towards a liquid coating station 22a, where the liquid polymer composition is applied at an amount such that the amount of coated and dried layer is about 1 -3 g/m2, when the coated paper has passed the drying station 22b.
  • the liquid coating operation is carried out in two steps, i.e. by first coating 0.5-1 .5 g/m2, drying in an intermediate step and then coating a second time at 0.5-1 .5 glm2 and finally drying the total liquid coated layer to obtain a coated paper layer 21 b.
  • Fig. 3 is a diagrammatic view of an example of a plant for vapour deposition coating of a metal layer 12 onto the coated thin first paper layer produced in Fig. 2.
  • the thin paper web 21 b from Fig. 2 is subjected, on the coating receiving side, to continuous evaporation deposition 30. of a metallised layer of aluminium, possibly in a mixture with aluminium oxide, and the coating is given a thickness of 5-100 nm, preferably 5-50 nm, so that the metal coated paper of the invention 34a is formed.
  • the aluminium vapour comes from a solid piece evaporation source 31 .
  • Fig. 4a the lamination process 40a is shown, wherein the induction heat sealing durable and/or oxygen barrier coated paper layer 34a, further coated with a thin metal vapour deposited coating 21 b, is heat laminated to an oriented film 50, having an adhesive layer 50a on the side facing towards the metallised layer, and an innermost heat sealable layer of LDPE and/or LLDPE 14, 43b is extrusion coated onto the inner side of the oriented film 50 and pressed together in a roller nip 45b. Subsequently, the laminated paper and film passes a second extruder 47 and lamination nip 48, where an outermost heat sealable layer of LDPE 46 is coated onto the outer side of the paper layer.
  • the finished packaging laminate 49b is wound onto a storage reel, not shown.
  • Fig. 4b an alternative embodiment is shown, wherein the induction heat sealing durable and/or oxygen barrier coated paper layer 34a, further coated with a thin metal vapour deposited coating 21 b is extrusion laminated with a bonding layer 50b to oriented film 50, in a first lamination station, and thereafter extrusion coated with the outermost polymer layer(s) 46, in a second extrusion coating station, and pressed together in a roller nip 45c.
  • the laminated paper and film passes a third extrusion lamination station 48, where an innermost heat sealable layer of LDPE and/or LLDPE 14, 43b is coated onto the inner side of the film 50.
  • the finished packaging laminate 49c is wound onto a storage reel, not shown.
  • a packaging laminate comprising an additional, second paperboard layer
  • the second paperboard is bonded to the first metal-coated paperboard by extrusion laminating the metal- coated first paper layer and the second paper layer using an intermediate layer of a polyolefin-based polymer, preferably a low density polyethylene (LDPE) and thereafter performing the steps shown in Fig 4a and 4b respectively.
  • a polyolefin-based polymer preferably a low density polyethylene (LDPE)
  • Fig. 5a shows one example of a packaging container 50 produced from the packaging laminate 10c according to the invention.
  • the packaging container is particularly suitable for beverages, sauces, soups or the like.
  • a package has a volume of about 100 to 1000 ml. It may be of any configuration, but is preferably brick-shaped, having longitudinal and transversal seals 51 and 52, respectively, and optionally an opening device 53.
  • the packaging container may be shaped as a wedge. In order to obtain such a "wedge-shape", only the bottom part of the package is fold formed such that the transversal heat seal of the bottom is hidden under the triangular corner flaps, which are folded and sealed against the bottom of the package. The top section transversal seal is left unfolded. In this way the half-folded packaging container is still is easy to handle and dimensionally stable when put on a shelf in the food store or on a table or the like.
  • Fig. 5b shows an alternative, example of a packaging container 50b produced from the packaging laminate 10b according to the invention. Since the packaging laminate 10b is thinner by having a thinner paper core layer, it is not dimensionally stable enough to form a parallellepipedic or wedge-shaped packaging container, and is not fold formed after transversal sealing 52b. It will thus remain a pillow-shaped pouch-like container and distributed and sold like this.
  • Fig. 6 shows the principle as described in the introduction of the present application, i.e. a web of packaging material is formed into a tube 61 by the longitudinal edges 62, 62' of the web being united to one another in an overlap longitudinal joint 63.
  • the tube is filled 64 with the intended liquid food product and is divided into individual packages by repeated transversal seals 65 of the tube at a pre-determined distance from one another below the level of the filled contents in the tube.
  • the packages 66 are separated by incisions in the transversal seals and are given the desired geometric configuration by fold formation along prepared crease lines in the material.
  • an aqueous coating composition for the induction heat sealing durable layer An aqueous dispersion of exfoliated laminar montmorillonite particles (Kunipia F from Kunimine Kogyo Co.) having an aspect ratio of about 50-5000 is blended with an aqueous solution of about 30 weight-% of PVOH
  • exfoliated laminar mineral particles may be stabilised by means of a stabiliser additive.
  • the laminar mineral particles are exfoliated directly in the PVOH-solution at 60-90 °C during 1 -8 hours.
  • the PVOH-coated paper was coated with an aluminium metal coating by means of a vapour deposition process up to optical density 3, onto the PVOH layer.
  • the thus metallised, PVOH-coated paper was laminated to a thick paperboard of 260 mN (about 270 g/m2) by means of an extrusion laminating thermoplastic bonding layer of low density polyethylene (LDPE), and the thus laminated paper sandwich was subsequently coated with thermoplastic heat sealable layers (LDPE) on the outer most side.
  • LDPE low density polyethylene
  • the inner side was coated by means of extrusion laminating a BOPP film using LDPE as a bonding layer onto the inner side of the laminated paper sandwich.
  • An innermost layer of liquid tight, heat sealable LDPE was coated by means of extrusion coating to the inner side of the BOPP film.
  • the thus formed laminate product was used and tested for heat seal quality in a Tetra Brik Aseptic ® conventional filling machine, employing adapted induction heat sealing of the packaging containers produced. It has for example been seen that to reach sufficient heating efficiency by a very thin metallised layer, the frequency used in the induction sealing process needs to be increased significantly.
  • An aqueous composition of aqueous dissolved and dispersed PVOH, having a saponification degree of above 99 %, and 10 weight-% exfoliated bentonite clay, was prepared in a similar way to Example 1 and coated by means of liquid coating, in two consecutive steps with drying in between, onto a thin paper web having a surface weight of 50 g/m2, with 3 g/m2 PVOH coating in total.
  • the wet applied coating is dried by hot air to evaporate the water.
  • the PVOH-coated paper was coated with an aluminium metal coating by means of a vapour deposition process up to optical density 3, onto the PVOH layer.
  • the thus metallised, PVOH-coated paper was laminated to a thin paper of 50 g/m2 by means of an extrusion laminating thermoplastic bonding layer of low density polyethylene (LDPE).
  • LDPE low density polyethylene
  • the inner side was further coated by means of heat laminating a BOPP film having an adhesive layer of EAA onto the inner side of the laminated paper sandwich.
  • the inner side of the BOPP film was co-extrusion coated with two layers of LDPE. Where the innermost layer is a liquid, tight, heat sealable LDPE extruded at a temperature about 280 °C.
  • thermoplastic heat sealable layers LDPE
  • Tetra Brik Aseptic ® conventional filling machine employing adapted induction heat sealing of the packaging containers produced.
  • COMPARATIVE EXAMPLE 1 A 12 ⁇ substrate film of an oriented PET (polyethylene terephthalate), was coated with an aluminium metal coating by means of a vapour deposition process to an optical density of about 3.
  • PET-film was laminated to a thick paperboard of about 260 mN (or about 270 g/m2) by means of an extrusion laminating thermoplastic bonding layer of low density polyethylene (LDPE), and
  • LDPE low density polyethylene
  • thermoplastic heat sealable layers LDPE
  • Tetra Brik Aseptic ® conventional filling machine employing adapted induction heat sealing of the packaging containers produced.
  • the heat seal quality and the integrity of the produced packages was acceptable according to evaluation by a test panel of tearing properties of the seals and of the package integrity using the red ink test, in comparison to the above examples.
  • the sealing results from test run to test run were not as consistent and reliable as for laminated material with thin paper substrates.
  • a thin paper web having a surface weight of 50 g/m2 was co-extrusion coated by a first layer of LDPE at 10 g/m2 and a second layer of EAA (ethylene acrylic acid copolymer) at 5 g/m2.
  • EAA ethylene acrylic acid copolymer
  • the extrusion-coated paper was further coated with an aluminium metal coating by means of a vapour deposition process, onto the EAA layer.
  • the thus metallised, LDPE/EAA-coated paper was laminated with thermoplastic heat sealable layers on both sides and tested for heat seal quality in a test rig, simulating the real conditions in a conventional filling machine of the Tetra Brik Aseptic ® type, employing adapted induction heat sealing of the packaging containers produced. Furthermore, the laminated paper was tested in the conventional filling machine of the Tetra Brik Aseptic ® type, employing adapted induction heat sealing of the packaging containers produced.
  • Example 3 was prepared in a similar way to Example 1 except that no exfoliated laminar montmorillonite particles were present.
  • Thin paper webs of different surface weights were coated by means of liquid coating in two consecutive steps, with drying in between, with an aqueous composition of aqueous dissolved and dispersed PVOH, having a saponification degree of above 99 %, and 10 weight-% exfoliated bentonite clay, as set out in Table 1 .
  • the wet applied coatings were dried by hot air to evaporate the water.
  • the PVOH-coated paper webs were coated with an aluminium metal coating by means of a vapour deposition process, onto the PVOH layer.
  • the thus metallised, PVOH-coated was on the inner side coated by means of extrusion laminating a BOPET film using LDPE as a bonding layer onto the inner side of the laminated paper sandwich.
  • An innermost layer of liquid tight, heat sealable LDPE was coated by means of extrusion coating to the inner side of the BOPP film.
  • the thus obtained laminate was thereafter coated with thermoplastic liquid-tight heat sealable layers on the outer side of the laminate and tested for heat seal quality in a test rig, simulating the real conditions in a conventional filling machine of the Tetra Brik Aseptic ® type, employing adapted induction heat sealing of the packaging containers produced.
  • PVOH polyvinyl styrene
  • An excellent example of such a barrier composition comprises PVOH and from 10 to 50, preferably from 20 to 40 weight- % of talcum particles.
  • Another example of such a barrier composition comprises PVOH and from 10 to 50 weight-% of talcum particles and from 1 to 40 weight %, nanoparticles such as those described above, e.g. clays.

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Abstract

The present invention relates to a non-foil packaging laminate for liquid food packaging comprising a layer of paper or other cellulose-based material, outermost liquid tight, heat sealable layers of polyolefin-based polymers and, vapour-deposition coated onto the inner side of the layer of paper or cellulose- based material,an induction heat susceptible metal coating. The invention also relates to a method for manufacturing of the packaging laminate,to a packaging container that is made from the packaging laminate and to a method of induction heat sealing the packaging laminate into packaging containers.

Description

NON-FOIL PACKAGING LAMINATE, METHOD FOR
MANUFACTURING OF THE PACKAGING LAMINATE AND PACKAGING CONTAINER PRODUCED THEREOF
Technical field
The present invention relates to a non-foil packaging laminate for induction heat sealing into packages for liquid food or beverage. The invention also relates to a method for manufacturing of the packaging laminate and to a packaging container made from the packaging laminate, thus employing a method of induction heat sealing the non-foil packaging laminate.
Background of the invention
Packaging containers of the single use disposable type for liquid foods are often produced from a packaging laminate based on paperboard or carton. One such commonly occurring packaging container is marketed under the trademark Tetra Brik Aseptic® and is principally employed for aseptic packaging of liquid foods such as milk, fruit juices etc, sold for long term ambient storage. The packaging material in this known packaging container is typically a laminate comprising a bulk core layer of paper or paperboard and outer, liquid-tight layers of thermoplastics. In order to render the packaging container gas-tight, in particular oxygen gas-tight, for example for the purpose of aseptic packaging and packaging of milk or fruit juice, the laminate in these packaging containers normally comprises at least one additional layer, most commonly an aluminium foil.
On the inside of the laminate, i.e. the side intended to face the filled food contents of a container produced from the laminate, there is an innermost layer, applied onto the aluminium foil, which innermost, inside layer may be composed of one or several part layers, comprising heat sealable adhesive polymers and/or polyolefins. Also on the outside of the paper or paperboard layer, there is an outermost heat sealable polymer layer.
The aluminium foil moreover renders the packaging material
thermosealable by inductive thermosealing which is a rapid and efficient sealing technique for obtaining mechanically strong, liquid- and gas-tight sealing joints or seams during the production of the containers. The packaging containers are generally produced by means of modern, high-speed packaging machines of the type that form, fill and seal packages from a web or from prefabricated blanks of packaging material. Packaging containers may thus be produced by reforming a web of the laminated packaging material into a tube by both of the longitudinal edges of the web being united to each other in an overlap joint by welding together the inner- and outermost heat sealable thermoplastic polymer layers. The tube is filled with the intended liquid food product and is thereafter divided into individual packages by repeated transversal seals of the tube at a predetermined distance from each other below the level of the contents in the tube. The packages are separated from the tube by incisions along the transversal seals and are given the desired geometric configuration, normally parallelepipedic, by fold formation along prepared crease lines in the packaging material.
The main advantage of this continuous tube-forming, filling and sealing packaging method concept is that the web may be sterilised continuously just before tube-forming, thus providing for the possibility of an aseptic packaging method, i.e. a method 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 micro-organisms in the filled product. Another important advantage of the continuous Tetra Brik® -type packaging method is, as stated above, the possibility of continuous high-speed packaging, which has considerable impact on cost efficiency.
A layer of an aluminium foil in the packaging laminate provides excellent gas barrier properties compared to most polymeric gas barrier materials. The conventional aluminium-foil based packaging laminate for liquid food aseptic packaging is the most cost-efficient packaging material, at its level of
performance, available on the market today. Any other material to compete must be more cost-efficient regarding raw materials, have comparable food preserving properties and have a comparably low complexity in the converting into a finished packaging laminate. There is now a trend growing towards developing such packaging materials having no aluminium-foil in the laminated structure, seeking to improve the environmental profile of the resulting material. It is then of course desirable to lower the costs for manufacturing of the packaging material and keeping the necessary properties for aseptic long-term storage of the package containers produced from the packaging laminate.
At the same time, it would be ideal if the packaging laminate were directly suitable for use in the already installed base of filling and packaging machines presently running at the dairies and filling sites all over the world. The absence of aluminium foil from a packaging laminate has, however, presented a technical problem to be solved regarding the heat sealing of the outermost thermoplastic layers, since there is no longer a material in the laminate that is susceptible to induce a current to generate heat, emanating from a magnetic field in the way that has been done with aluminium foil. Instead, alternative technologies have been discussed and developed such as heat generation by means of ultrasonic vibrations or old conventional convection and hot-air sealing methods. The implementation of such alternative sealing technologies leads to it being necessary to entirely re-build the sealing part of the packaging machines already installed at dairies and filling sites.
It has evolved that packaging laminates involving two or more barrier layers, of which one is a metallised layer, may present feasible alternatives to foil- based laminates, however, with the abovementioned complication that the present induction heat sealing equipment cannot be used.
However, it has now been seen that contrary to all previous belief, it would be possible to actually generate sufficient heat for heat melting an adjacent thermoplastic layer by means of a metallised layer, by means of induction sealing technology, provided that certain less revolutionary adaptations were made on the existing machines. The metallised layers first tested were primarily coated on oriented PET film substrates.
In connection with continued work on adapting the induction sealing technology for metallised layers, it has, however, been noticed that different substrates vary in suitability for metallisation and subsequent induction heat sealing. In order to work well, it seems the metallised layer should have a certain combination of thickness, or optical density, with layer quality. By quality is primarily meant that the layer should be homogeneous and have substantially the same thickness all across the width and length of the laminated packaging material.
PET-film substrates are generally quite expensive for what they provide in a packaging laminate of the above described kind. Actually, the about only significant contribution it has to the packaging laminate is that of acting as a carrier for the metallised layer. While it is believed that the induction sealing technology is feasible and possible to adapt also to other, less expensive, polymer substrates, it has been seen that the sealing process will probably need more calibration and surveillance in order to operate efficiently and reliably. It has also been seen that the choice of substrate may influence the quality and durability of the metallised layer during the heat sealing process.
Accordingly, there is still a need for a cost-efficient and robust, i.e. reliable also at moderate variations in manufacturing and handling conditions, non- aluminium foil packaging material for aseptic, liquid food packaging, e.g. of milk or other beverage, which material provides sufficient barrier properties in packaging containers for long-term aseptic storage, under ambient conditions, and which non-foil packaging material is sealable by means of induction sealing in the installed base of filling and sealing equipment.
Summary of the invention
It is, therefore, an object of the present invention to overcome or alleviate the above-described problems in producing a non-foil induction heat sealable paper or paperboard packaging laminate.
It is a another object of the invention to provide a non-foil, paper or paperboard packaging laminate, suitable for long-term, aseptic packaging of liquid or wet food, which can be heat sealed into packaging containers with good tightness to liquid and gas, by means of induction heat sealing.
It is a further object of the invention to provide a cost-efficient non-foil, paper or paperboard packaging laminate, suitable for long-term, aseptic packaging of liquid or wet food, which can be heat sealed into packaging containers with good tightness to liquid and gas, by means of induction heat sealing, which packaging containers have good barrier properties not only against gas and water vapour, but also towards light and odour substances. These objects are thus attained according to a non-foil packaging laminate for induction heat sealing into packages for liquid food or beverage, the packaging laminate comprising at least one, first, layer of paper or other cellulose-based material, which first paper layer is situated at the inner side of the packaging laminate and is pre-coated to receive and support an induction heat susceptible metal vapour deposited layer, in order to induce heat sealing in a thermoplastic polymer material, the packaging laminate further comprising such a metal vapour deposited layer applied onto the inner side of said pre-coated first layer of paper or cellulose-based material, and further comprising an oriented film laminated to the metal vapour deposited layer; and further comprising an innermost layer of liquid tight, heat sealable thermoplastic polymer material applied onto the inner side of the oriented film; and/or said oriented film comprises a liquid-tight heat-seal layer, representing the innermost layer of the film, wherein said oriented film is stretched in at least one direction at a stretching ratio of 2 or more, and has a core layer of a material having a higher melting point than the material of the innermost layer(s).
In one aspect the oriented film is applied onto the metal vapour deposited layer by an intermediate bonding layer and/or said oriented film comprises an adhesive layer on its outer side to be laminated to the metal vapour deposited layer.
In one aspect of the invention it is provided a method of manufacturing a non-foil packaging laminate, comprising the steps of providing a first layer of paper or other cellulose-based material, pre-coating the paper or cellulose-based material layer for receiving and supporting an induction heat susceptible metal vapour deposition coating, by an induction sealing durable layer onto the inner side of the paper or cellulose-based material layer, applying said induction heat susceptible metal layer onto the inner side of the thus coated paper layer, providing an oriented film (20), stretched in at least one direction at a stretching ratio of 2 or more, and having a core layer of a material having a higher melting point than the material of the innermost layer of the non-foil packaging laminate, laminating the oriented film to the metal coated paper layer, providing one or more layer(s) of liquid tight, heat sealable thermoplastic polymer material applied onto the inner side of the oriented film, and/or providing a liquid-tight heat-seal layer as a part of the oriented film representing the innermost layer of the film, wherein either the liquid tight, heat sealable thermoplastic polymer material or the liquid-tight heat-seal layer of the film represents the innermost layer of the non- foil-packaging laminate.
In one aspect the objects of the present invention are by realized by a packaging container manufactured from the above described packaging laminate.
In one aspect the objects of the present invention are realized by a method of heat sealing a non-foil packaging laminate, comprising the steps of providing a non-foil packaging laminate as defined above, in the form of a continuous web, forming the web-formed packaging laminate into a continuous tubular shape and applying a longitudinal seal in the longitudinal direction, filling the packaging laminate tube with a liquid foodstuff, forming heat-sealing zones by means of induction heating, at predetermined intervals in the traversing direction of the filled tube, and cutting through the centre of each traversing sealing zone, thereby forming individual containers.
Brief description of the drawings
In the following, preferred embodiments of the invention will be described with reference to the drawings, of which:
Fig. 1 a, 1 a2, 1 b, 1 b2, 1 b3, 1 b4, 1 c and 1 c2 are schematically showing, in cross-section, first, second, third and fourth embodiments of a packaging laminate produced according to the invention,
Fig. 2 is schematically showing a method of liquid coating of a polymer composition onto a paper substrate layer,
Fig. 3 is showing a diagrammatic view of a plant for vapour deposition of a preferred metal layer onto a substrate,
Fig. 4a, and 4b are schematically showing example methods of
manufacturing the packaging laminates described in Figure 1 ,
Fig. 5a and 5b are showing examples of packaging containers produced from the packaging laminate according to the invention, and
Fig. 6 is showing the principle of how such packaging containers are manufactured from the packaging laminate in a continuous form, fill and seal process.
Description of the invention According to one aspect of the invention, the general objects are attained by a non-foil packaging laminate for induction heat sealing into packages for liquid food or beverage, the packaging laminate comprising at least one, first, layer of paper or other cellulose-based material, which first paper layer is situated at the inner side of the packaging laminate and is pre-coated to receive and support an induction heat susceptible metal vapour deposited layer, in order to induce heat sealing in a thermoplastic polymer material, the packaging laminate further comprising such a metal vapour deposited layer applied onto the inner side of said pre-coated first layer of paper or cellulose-based material, and further comprising an oriented film laminated onto the metal vapour deposited layer; and further comprising an innermost layer of liquid tight, heat sealable thermoplastic polymer material applied onto the inner side of the oriented film; and/or said oriented film comprises a liquid-tight heat-seal layer, representing the innermost layer of the film, wherein said oriented film is stretched in at least one direction at a stretching ratio of 2 or more, and has a core layer of a material having a higher melting point than the material of the innermost layer(s).
The oriented film is laminated to the metal vapour deposited layer by an intermediate bonding layer and/or said oriented film comprises an adhesive polymer layer on its outer side to be laminated to the metal vapour deposited layer. According to a well-functioning embodiment of the invention, in order to provide a smooth receiving surface for the metal vapour deposition coating and to prepare the paper to support said metal coating in a good way during a subsequent heat sealing operation, the first layer of paper or other cellulose- based material is coated onto its inner side with an induction sealing durable coating layer having a higher melting point than the innermost layer of heat sealable material. Subsequently, onto the inner side of the induction heat sealing durable coating layer is further applied said layer of an induction heat susceptible metal vapour deposition coating, which is adapted to induce heat sealing in an adjacent thermoplastic polymer layer.
The most cost-efficient way of providing such a coating onto the paper layer, in order to prepare it for metal vapour deposition coating, is to apply it by means of a liquid coating method, often also generally referred to as liquid film coating or dispersion coating, of a liquid composition onto the paper layer and subsequently drying it, the liquid composition containing an induction sealing durable polymer binder dispersed or dissolved in an aqueous or solvent medium.
According to some good-working examples, the induction sealing durable coating layer is formed from a composition mainly comprising a polymer selected from the group consisting of polyvinyl alcohol (PVOH), water dispersible ethylene vinyl alcohol (EVOH), ethylene vinyl alcohol vinyl acetate copolymer,
polyvinylidene chloride (PVDC), water dispersible polyamide (PA), water dispersible polyester, polysaccharide, polysaccharide derivatives, including starch and starch derivatives, and combinations of two or more thereof. Importantly, the thus coated layer has a higher melting point than the innermost layer of thermoplastic material or the liquid-tight heat-seal layer of the oriented film, by which it is intended to heat seal the packaging laminate into filled and sealed packages. The sealing durable coating layer is a thermomechanically stabile layer, Preferably, the outer and innermost thermoplastic heat sealable material, as well as the liquid-tight heat-seal layer, is based on polyolefins, more preferably based on polyethylene and most preferably based on low density polyethylene, such as for example LDPE, LLDPE, m-LLDPE and VLDPE and blends thereof.
Where it is desirable to use a polymer that has a more cost-efficient and positive environmental profile, the induction sealing durable coating layer is formed from a composition mainly comprising PVOH, water dispersible EVOH or starch. A water dispersible EVOH has a higher amount of vinyl alcohol units compared to melt processable EVOH, and are more similar in nature to PVOH than to EVOH. Pure PVOH and starch-based polymers may be more or less biologically degradable, why such polymers may be more desirable for some packaging applications.
In addition, some polymer binders suitable for liquid coating, also have gas barrier properties, which make them even more desirable in a packaging laminate. Accordingly, the induction sealing durable coating layer may be preferred to be formed from a composition mainly comprising a polymer selected from the group consisting of polyvinyl alcohol (PVOH), water dispersible ethylene vinyl alcohol (EVOH), ethylene vinyl alcohol vinyl acetate copolymer,
polyvinylidene chloride (PVDC), water dispersible polyamide (PA), starch, starch derivatives, and combinations of two or more thereof. In comparison with aluminium foil, PVOH as a liquid coating barrier polymer enjoys many desirable properties, with the result that it is the most preferred barrier material in many contexts. Among these, mention might be made of the good film formation properties, compatibility with foods and economic value, together with its high oxygen gas barrier properties. In particular, PVOH provides a packaging laminate with high odour barrier properties, which is especially important for the packaging of milk.
Like many other conceivable such high-temperature melting polymers such as, for example, starch or starch derivatives, polyvinyl alcohol is suitably applied by means of a liquid coating process, i.e. in the form of an aqueous or solvent-based dispersion or solution which, on application, is spread out to a thin, uniform layer on the substrate and thereafter dried.
Aqueous systems generally have certain environmental advantages. Preferably, the liquid gas barrier composition is water-based, because such composition usually have a better work environment friendliness than solvent- based systems, as well.
In order to improve the water vapour and oxygen barrier properties of a PVOH coating, a polymer or compound with functional carboxylic acid groups may be included in the composition. Suitably, the polymer with functional carboxylic acid groups is selected from among ethylene acrylic acid copolymer (EAA) and ethylene methacrylic acid copolymers (EMAA) or mixtures thereof. One known such particularly preferred barrier layer mixture consists of PVOH, EAA and an inorganic laminar compound. The EAA copolymer is then included in the barrier layer in an amount of about 1 -20 weight %, based on dry coating weight.
It is believed that the improved oxygen and water barrier properties result from an esterification reaction between the PVOH and the EAA at an increased drying temperature, whereby the PVOH is crosslinked by hydrophobic EAA polymer chains, which thereby are built into the structure of the PVOH. Such a mixture is, however, more expensive because of the cost of the additives.
Furthermore, the compositions may be made more durable by drying and curing at elevated temperatures. Crosslinking can also be induced by the presence of polyvalent compounds, e.g. metal compounds such as metal-oxides, although such compounds are less preferred in the coating compositions for this purpose.
Special kinds of water-dispersible ethylene vinyl alcohol polymer (EVOH) have lately been developed and may be conceivable for an oxygen barrier liquid coating composition. Conventional EVOH polymers, however, are normally intended for extrusion and are not possible to disperse/dissolve in an aqueous medium in order to produce a thin liquid coated barrier film of 5 g/m2 or below, preferably 3,5 g/m2 or below. It is believed that the EVOH should comprise a rather high amount of vinyl alcohol monomer units to be water-dispersible or dissolvable and that the properties should be as close to those of liquid coating grades of PVOH as possible. An extruded EVOH layer is not an alternative to liquid coated EVOH, because it inherently has less similar properties to PVOH than EVOH grades for extrusion coating, and because it cannot be applied at a cost-efficient amount below 5 g/m2 as a single layer by extrusion coating or extrusion lamination, i.e. it requires co-extruded adhesive polymer layers, which are generally very expensive polymers. Furthermore, very thin extruded layers cool off too quickly and do not contain enough heat energy to sustain sufficient lamination bonding to the adjacent layers.
Other examples of polymer binders, suitable for liquid coating, are the polysaccharides, in particular starch or starch derivatives, such as preferably oxidised starch, cationic starch and hydroxpropylated starch. Examples of such modified starches are hypochlorite oxidised potato starch (Raisamyl 306 from Raisio), hydroxypropylated corn starch (Cerestar 05773). However, also other starch forms and derivatives may be feasible liquid coating binders.
Further examples of polymer binders are coatings comprising mixtures of carboxylic acid containing polymers, such as acrylic acid or methacrylic acid polymers, and polyalcoholic polymers, such as PVOH or starch. A cross-linking reaction of these polymer binders are preferred, as mentioned above, for resistance to high humidity.
Most preferably, however, the binder polymer is PVOH, because it has all the good properties mentioned above, i.e. in addition to good induction heat sealing resistance, also good film formation properties, gas barrier properties, cost efficiency, food compatibility and odour barrier properties. A PVOH-based gas barrier composition performs best when the PVOH has a degree of saponification of at least 98 %, preferably at least 99 %, although also PVOH with lower degrees of saponification will provide good properties.
According to one embodiment, the liquid composition additionally comprises inorganic particles in order to further improve the oxygen gas barrier properties.
The polymer binder material may for example be mixed with an inorganic compound which is laminar in shape, or flake-formed. By the layered
arrangement of the flake-shaped inorganic particles, an oxygen gas molecule has to migrate a longer way, via a tortuous path, through the oxygen barrier layer, than the normal straight path across a barrier layer.
According to one embodiment, the inorganic laminar compound is a so- called nanopartide compound dispersed to an exfoliated state, i.e. the lamellae of the layered inorganic compound are separated from each other by means of a liquid medium. Thus the layered compound preferably may be swollen or cloven by the polymer dispersion or solution, which at dispersion has penetrated the layered structure of the inorganic material. It may also be swollen by a solvent before added to the polymer solution or polymer dispersion. Thus, the inorganic laminar compound is dispersed to a delaminated state in the liquid gas barrier composition and in the dried barrier layer. The term clay minerals or clays includes minerals of the kaolinite, antigorite, smectite, vermiculite, bentonite or mica type, respectively. Specifically, laponite, kaolinite, dickite, nacrite, halloysite, antigorite, chrysotile, pyrophyllite, montmorillonite, hectorite, saponite, sauconite, sodium tetrasilicic mica, sodium taeniolite, commonmica, margarite, vermiculite, phlogopite, xanthophyllite and the like may be mentioned as suitable clay minerals. Preferred nano-particles are those of montmorillonite, most preferred purified montmorillonite or sodium-exchanged montmorillonite (Na-MMT). The nano-sized inorganic laminar compound or clay mineral preferably has an aspect ratio of 50-5000 and a particle size of up to about 5 μηι in the exfoliated state.
Preferably, the inorganic particles mainly consist of such laminar bentonite particles having an aspect ratio of from 50 to 5000.
Suitably, the barrier layer includes from about 1 to about 40 weight %, more preferably from about 1 to about 30 weight % and most preferably from about 5 to about 20 weight %, of the inorganic laminar compound based on dry coating weight. If the amount is too low, the gas barrier properties of the coated and dried barrier layer will not be markedly improved compared to when no inorganic laminar compound is used. If the amount is too high, the liquid composition will become more difficult to apply as a coating and more difficult to handle in storage tanks and conduits of the applicator system. Preferably, the barrier layer includes from about 99 to about 60 weight %, more preferably from about 99 to about 70 weight % and most preferably from about 95 to about 80 weight % of the polymer based on the dry coating weight. An additive, such as a dispersion stabiliser or the like, may be included in the gas barrier composition, preferably in an amount of not more than about 1 weight % based on the dry coating.
According to another embodiment, the inorganic particles mainly consist of laminar talcum particles having an aspect ratio of from 10 to 500. The
composition normally comprises an amount of from 10 to 50 weight-%, more preferably from 20 to 40 weight-% of the talcum particles, based on dry weight. Below 20 weight-%, there is no significant increase in gas barrier properties, while above 50 weight-%, the coated layer may be more brittle and breakable because there is less internal cohesion between the particles in the layer. Above 5o weight %, the polymer binder seems to be in too low amount to surround and disperse the particles and laminate them to each other within the layer.
Alternatively, good oxygen barrier properties may be achieved when there is made use of colloidal silica particles, exhibiting a particle size of 3-150 nm, preferably 4-100 nm and even more preferred 5-70 nm, which particles are preferably amorphous and spherical. The use of colloidal silica particles moreover has the advantage that the liquid barrier composition may be applied at a dry content of 15-40 weight %, preferably 20-35 weight % and even more preferred 24-31 weight %, whereby the demand on forcible drying is decreased.
Other alternatives of inorganic particles that may be used are particles of kaolin, mica, calcium carbonate etc.
The preferred polymer binder, also when employing inorganic particles for providing oxygen barrier properties, is PVOH, for examples the once above, partly due to its advantageous properties mentioned above. In addition, PVOH is advantageous from a mixing point of view, i.e. it is generally easy to disperse or exfoliate inorganic particles in an aqueous solution of PVOH to form a stable mixture of PVOH and particles, thus enabling a good coated film with a
homogeneous composition and morphology.
Preferably, according to the invention, the said induction heat sealing durable layer is applied at a total amount of from 0.5 to 7 g/m2, preferably from 0.5 to 5 g/m2, more preferably 0.5 to 3 g/m2, dry weight. Below 0.5 g/m2, there will be a too low effect of induction sealing durability, and there is a risk of pinholes being formed, depending on paper or substrate characteristics, in connection with the removal of water or solvent for drying the applied barrier layer, if the applied layer is too thin. On the other hand, at above 7 g/m2, the coated layer will not bring cost-efficiency to the packaging laminate, due to high cost of polymers in general and due to high energy cost for evaporating off the dispersion liquid.
Additionally, a recognisable level of oxygen barrier is achieved by PVOH at 0.5 g/m2 and above, and a good balance between barrier properties and costs is achieved between 0.5 and 3.5 g/m2.
According to one embodiment of the invention, the oxygen gas barrier layer is applied in two consecutive steps with intermediate drying, as two part-layers. If thus applied as two part-layers, each layer is suitably applied in amounts from 0.3 to 3.5 g/m2, preferably from 0.5 to 2,5 g/m2, and allows a higher quality total layer from a lower amount of liquid gas barrier composition. More preferably, the two part-layers are applied at an amount of from 0.5 to 2 g/sm2 each, preferably from 0.5 to 1 .5 g/m2 each.
The metal vapour deposition coating layer is applied by means of physical vapour deposition (PVD) onto the thin coated paper substrate. The thin metal vapour deposition coatings according to the invention are nanometer-thick, i.e. have a thickness that is most suitably counted in nanometers, for example of from 5 to 500 nm (50 to 5000 A), preferably from 5 to 200 nm, more preferably from 5 to 100 nm and most preferably from 5 to 50 nm.
Generally, below 5 nm the induction heat sealing durable properties may be too low to be useful and above 200 nm, the coating may be less flexible and, thus, more prone to cracking when applied onto a flexible substrate. Commonly, such a vapour deposition coating having induction heat durability is made of a metal compound, and preferably an induction heat sealing inducing metal vapour deposition coating layer is a layer substantially consisting of aluminium. Normally, an aluminium metallised layer inherently has a thin surface portion consisting of an aluminium oxide due to the nature of the metallisation coating process used.
Suitably, the metal vapour deposition coating layer has an optical density (OD) of from 1 to 5, preferably of from 1 .5 to 3.5, more preferably from 2 to 3.
An aluminium-based thin vapour deposited layer preferably has a thickness of from 5 to 100 nm, more preferably from 5-50 nm, which corresponds to less than 1 % of the aluminium metal material present in an aluminium foil of conventional thickness, i.e. 6,3 μηι.
In order to improve the adhesion of the coating to the substrate, a step of surface treatment of the substrate film may be carried out before vapour deposition coating, especially metallising, the substrate.
A preferred metal according to the present invention is aluminium, although any other metal capable of being vacuum deposited into a
homogeneous coating may be used according to the invention. Thus, less preferred and less common metals such as Au, Ag, Cr, Zn, Ti or Cu are conceivable also. Generally, thin coatings of metal or a mixture of metal and metal oxide provide barrier properties against water vapour and are used also when the desired function is to prevent water vapour from migrating into and through the multilayer film or packaging laminate. Most commonly however, the metal in a metallisation coating is aluminium (Al).
In order to render a metal vapour deposition coating process cost-efficient, the substrate, i.e. the first, innermost situated, layer of paper or other cellulose- based material (1 1 ) should be as thin as possible, so that as many meters as possible may be rolled onto a roll of coated paper. Preferably, the first paper layer has a surface weight of from 20 to 100 g / m2, preferably from 20 to 70 g/m2, more preferably from 30-60 g/m2. When the paper is too thin, it will naturally be more difficult to handle in subsequent coating and lamination processes. On the other hand, the thinner the paper can be, the more cost-efficient it can be in the metal vapour deposition coating process. Seen from a stiffness perspective, a thicker first paper layer also contributes to a higher stiffness and grip-ability of the total packaging laminate structure.
A second layer of paper or paperboard, for use as a stabilising layer, in a common carton package for liquid packaging, usually has a thickness of from about 100 pm up to about 600 pm, and a surface weight of approximately 100- 500 g/m2, preferably about 200-400 g/m2, more preferably from 200 to 300 g/m2 and may be a conventional paper or paperboard of suitable packaging quality.
On the other hand, for low-cost aseptic, long-term packaging of liquid food, a thinner packaging laminate may be used, having a thinner paper layer.
Packaging containers made from such packaging laminates are not fold-formed and more similar to pillow-shaped flexible pouches. A suitable single paper layer for such pouch-packages then usually has a surface weight of from about 30 to about 140 g/m2, preferably from about 50 to about 120 g/m2, more preferably from 50 to about 1 10 g/m2, most preferably from 50 to 70 g/m2.
According to one embodiment, such a low cost packaging laminate may alternatively comprise two or more thin paper layers, of which the first, inner paper layer is vapour deposition coated with an induction heat susceptible material, according to the present invention. When there are two papers in the packaging laminate structure, the second outer paper layer suitably has a surface weight of from 20 to 100 g / m2, preferably from 20 to 70 g/m2, more preferably from 20-50 g/m2.
In order to further improve the properties of the non-foil packaging laminate an oriented film is applied on the metallised layer (metal vapour deposited layer). The use of an oriented film provides beneficial barrier properties. The application of a film may reduce the cost of the final package and improve or alternate its properties. The film will also work as protective layer for the
metallised layer during the lamination process, thus reducing the risk of cracks or pinholes. Suitable films are oriented films, stretched in at least one direction at a stretching ratio of 2 or more, and having a core layer of a material having a higher melting point than the heat sealable material of the innermost layer of the packaging laminate. Generally the melting point of the core layer is above 130 °C. The stretching ratio is dependent on the material used in the film but the ratio may be up to about 10. In certain aspects of the invention it is preferred to have a stretching ratio of 3 or more. Examples of suitable films are mono-oriented films, having at least a core layer from a polymer material selected from polypropylene (OPP), polyethylene terephthalate (OPET), polyamide (OPA), polyethylene naphthalate (OPEN), polybutylene terephthalate (OPBT), trimethylene
terephthalate (OPTT); biaxially-oriented films, such as biaxially-oriented polypropylene (BOPP), polyethylene terephthalate (BOPET), polyamide (BOPA), polyethylene naphthalate (BOPEN), polybutylene terephthalate (BOPBT), trimethylene terephthalate (BOPTT), or oriented films from two or more of the mentioned polymers, i.e. polypropylene, polyethylene terephthalate, polyamide, polyethylene naphthalate, polybutylene terephthalate, trimethylene terephthalate, blended or copolymerized and thereafter used to form a mono-oriented or biaxially oriented film. Some beneficial properties of said films are high tensile strength facilitating high-speed conversion, good puncture and flex-crack resistance over a wide range of temperatures, potentially good barrier to water vapour, resistance to oils and greases and moisture resistance as well as resistance to wrinkling or shrink due to environmental condition changes.
The oriented film may be a film that comprises additional layers in which case the core layer of the film is represented by the above exemplified films. In certain aspects of the invention the core layer of the film is a polymer which is selected from mono-oriented polypropylene (OPP), polyethylene terephthalate (OPET), polyamide (OPA), polyethylene naphthalate (OPEN), polybutylene terephthalate (OPBT), trimethylene terephthalate (OPTT); biaxially-oriented polypropylene (BOPP), polyethylene terephthalate (BOPET), polyamide (BOPA), polyethylene naphthalate (BOPEN), polybutylene terephthalate (BOPBT), trimethylene terephthalate (BOPTT).
The film may additionally include one or more of the following: a bonding layer, an adhesive layer and a liquid-tight heat-seal layer. The bonding layer is used in order to facilitate bonding between pre-manufactured webs or films and usually consists of a thermoplastic polymer. The adhesive layer is used for improving the adhesion between the film and other layers and normally consists of an adhesive polymer containing functional adhesion-promoting groups.
According to the present invention the adhesive layer is a layer of the oriented film. The adhesive layer may be applied before the stretching, for example by co- extrusion with the core layer or applied after the stretching, for example by dispersion coating. Such an adhesive polymer layer on the outer side of the oriented film, enables lamination by means of applying heat and pressure when joining the oriented film and the coated paper web in a roller nip of a lamination station, without extruding an additional intermediate bonding layer between the two pre-manufactured webs.
Generally the thickness of the oriented film is between 4 and 25 μηι. This generally applies when the film does not comprise a liquid-tight heat-seal innermost layer as then the film may be thicker.
In certain embodiments of the present invention there is no adhesive layer in the film itself but the film is bound to the metallised layer by a separate bonding layer, which is usually applied by extrusion lamination of an intermediate melt extrusion layer when laminating the pre-manufacture film to the pre-coated, metallised, paper layer.
In certain embodiments of the present invention both an adhesive layer as a part of the oriented film and an intermediate bonding layer is present and employed for laminating the oriented film to the metal-coated paper.
Alternative examples of material suitable as bonding layers, for extrusion lamination layers are polymers based on low density polyethylene polymers and selected from modified or un-modified LDPE or LLDPE polymers, co-polymers or graft co-polymers of ethylene polymers with functional-group containing monomer units, such as carboxylic or glycidyl functional groups, e.g. (meth)acrylic acid monomers or maleic anhydride (MAH) monomers, (i.e. ethylene acrylic acid copolymer (EAA) or ethylene methacrylic acid copolymer (EMAA)), ethylene- glycidyl(meth)acrylate copolymer (EG(M)A) or maleic anhydride-grafted polyethylene (MAH-g-PE) may be used. Another example of such modified polymers or adhesive polymers are so called ionomers based on low density polyethylene. In one embodiment the modified polyethylene is an ethylene acrylic acid copolymer (EAA) or an ethylene methacrylic acid copolymer (EMAA).
It may in certain aspects be beneficial to use LDPE or LLDPE as bonding layer.
Examples of adhesive layers are carboxylic acid functionalized
polyethylenes based on LDPE or LLDPE including co-polymers or graft co- polymers with functional-group containing monomer units, such as carboxylic or glycidyl functional groups, e.g. (meth)acrylic acid monomers or maleic anhydride (MAH) monomers, (i.e. ethylene acrylic acid copolymer (EAA) or ethylene methacrylic acid copolymer (EMAA)), ethylene-glycidyl(meth)acrylate copolymer (EG(M)A) or MAH-grafted polyethylene (MAH-g-PE). Another example of such modified polymers or adhesive polymers are so called ionomers or ionomer polymers. Preferably, the adhesive layer is selected from ethylene acrylic acid copolymer (EAA), ethylene methacrylic acid copolymer (EMAA)), ethylene- glycidyl(meth)acrylate copolymer (EG(M)A), and maleic anhydride-grafted polyethylene (MAH-g-PE), preferably ethylene acrylic acid copolymer (EAA) or ethylene methacrylic acid copolymer (EMAA). The adhesive layer may be included in the film by any conventional technique such as dispersion coating and subsequent drying onto the core substrate layer of the film or coextrusion coating of the adhesive layer onto the core e layer.
One or more liquid-tight, heat sealable layers are required as the innermost part of the packaging material to be in direct contact with the product filled in a packaging container manufactured from the packaging material. A liquid-tight heat-seal layer comprised in the oriented film may be an alternative or a complementary layer to providing a separate innermost liquid-tight, heat sealable layer. The term liquid-tight heat-seal layer generally refers to a layer of the oriented film. The liquid-tight heat-seal layer is selected from the same type of polyolefins as the outermost and innermost liquid-tight, heat sealable layers. Suitable thermoplastics for the liquid-tight heat-seal layer and for the outermost and innermost liquid-tight, heat sealable layers are based on polyolefins, such as for example polyethylenes or polypropylenes, preferably polyethylenes and more preferably low density polyethylenes such as, for example LDPE, linear LDPE (LLDPE) or single site catalyst metallocene polyethylenes (m-LLDPE), Ultralow- density linear polyethylene (vLLDPE) or blends of two or more thereof. Such liquid-tight, heat sealable layers are conventionally used and may additionally comprise an adhesive layer for providing improved adhesion to the core layer of the oriented film. An adhesive layer may thus be applied, as a co-extruded part of the innermost layer of liquid-tight, heat sealable thermoplastic polymer material onto the inner side of the oriented film. The innermost layer of a liquid-tight heat sealable thermoplastic material is often also aseptically tight.
The vapour deposition metal coated first paper layer may be bonded to a second paper or paperboard layer by one or more intermediate polymer layer(s), for example a thermoplastic polymer layer and more preferably a layer from a polymer selected from polyolefins and polyolefin-based co-polymers, often known as modified or adhesive polymers, especially LDPE or polyethylene-based polymers or co-polymers, or adhesive polymers, as described in the foregoing paragraph.
In order to further improve the light barrier of a packaging laminate according to the invention, if necessary, particles or pigments providing light barrier properties may be blended into one or more layers of the laminate. One example is light absorbing particles such as carbon black. The black colour of an intermediate layer is then advantageously hidden towards the outside by a paper or paperboard layer, and towards the inner side of the laminate, by a metallised, e.g. aluminium, layer. Another example is light-reflective particles such as titanium dioxide. Such particles may furthermore be adding to a whiter
appearance of the packaging laminate.
For thinner low-cost segment packaging laminates, which have a thinner paper core layer, such light reflecting inorganic, white pigments may improve the light barrier properties of the packaging laminate as well as improving the appearance of the packaging material towards the outside.
For higher performance packaging laminates, e.g. requiring longer aseptic shelf life for more sensitive products, it is of course possible to add further barrier layers. One simple way of, for example, increasing further the oxygen barrier properties of the packaging laminate may be to use a thermoplastic bonding layer including a layer of melt-extrudable barrier layer, for the bonding of the metal vapour deposition coated inside first paper layer to a further, second layer of paper or paperboard. According to this embodiment, the only thing to change in order to produce a higher performance packaging laminate, would be to include additional melt extrusion polymer layer(s) in the converting process at the lamination stage (e.g. a further barrier layer and possibly one or two melt co- extrusion bonding layers). According to another, more preferred, embodiment, a thin layer of a barrier polymer layer may be co-extrusion coated together with optional bonding layer(s) and the innermost heat sealable layer(s) onto the metal- coated inner side of the first paper layer. Such a co-extruded inside barrier layer would have to be kept thin, in order to easily transfer the induced heat through from the metal vapour deposition coating to the heat sealable layer.
Alternatively, a liquid-film oxygen barrier coating layer may be coated onto the other, outer side of the first, innermost paper layer. Alternatively, or additionally, an liquid-film oxygen barrier coating layer may be applied onto the inner side of any further paper layer in the packaging laminate structure.
According to a further aspect of the invention, there is provided a packaging container manufactured from the non-foil packaging laminate of the invention. The packaging container is suitable for long-term, aseptic packaging of liquid or wet food, and has good package integrity with strong, durable seals, from induction heat sealing.
According to yet a further aspect of the invention, there is provided a method for manufacturing of the packaging laminate as defined in the
independent method claim.
Thus, the method comprises the steps of providing at least a first layer of paper or other cellulose-based material, pre-coating the paper or cellulose-based material layer for receiving and supporting an induction heat susceptible metal vapour deposition coating, by an induction sealing durable layer onto the inner side of the paper or cellulose-based material layer, applying said induction heat susceptible metal layer onto the inner side of the thus coated paper layer, providing an oriented film, and laminating the oriented film to the metal coated paper layer. As described above the film itself may comprise a liquid-tight heat- seal layer representing the innermost layer of the film, and optionally an adhesive layer representing the side of the film applied onto the induction heat susceptible metal layer.
In one embodiment the method comprises applying an intermediate bonding layer between the induction heat susceptible metal layer and the oriented film.
At any stage of the method, an outermost layer of a heat sealable thermoplastic polymer material may be provided and laminated on the outermost, opposite side, of the packaging laminate. In cases when the packaging laminate structure contains a second paper layer positioned towards the outside of the packaging laminate, the outermost heat sealable polymer layer is then laminated on the outer side of the second paper layer.
An induction heat susceptible metal layer is sufficiently homogeneous and continuous in nature, to be able to transmit an electrical current as a result of an induced magnetic field, and to become heated such that a thermoplastic polymer layer will be heated and melted to provide melt sealing of said polymer. If the metal layer is dis-continuous due to un-even coating or due to cracks, there will be no heating provided in the sealing area.
In the pre-coating of the metal-receiving layer, the method further comprises the steps of providing a liquid composition containing a polymer binder dispersed or dissolved in an aqueous or solvent-based liquid medium and forming a thin induction sealing durable layer, comprising said polymer binder, contiguous to the inner side of the first paper layer, by coating the liquid composition onto the inner side of said layer of paper or other cellulose-based material and subsequently drying to evaporate the liquid, said polymer binder having a melting point higher than the thermoplastic polymer material of the innermost heat sealable layer.
Preferably, the induction sealing durable polymer contained in the liquid composition is selected from a group consisting of polyvinyl alcohol (PVOH), water dispersible ethylene vinyl alcohol (EVOH), ethylene vinyl alcohol vinyl acetate copolymer, polyvinylidene chloride (PVDC), water dispersible polyamide (PA), starch, starch derivatives and combinations of two or more thereof.
According to an embodiment, the induction sealing durable layer (12) is applied in a total amount of from 0.5 to 7 g/m2, preferably from 0.5 to 5 g/m2, more preferably from 0.5 to 3 g/m2, dry weight.
If applied as two part-layers, each layer may suitably be applied in amounts from 0.3 to 3.5 g/m2, preferably from 0.5 to 2.5 g/m2, which allows a higher quality total layer from a lower amount of liquid polymer composition. More preferably, the two part-layers may be applied at an amount of from 0.5 to 2 g/sm2 each, preferably from 0.5 to 1 .5 g/m2 each. In order to reduce the amount of moisture released from the paper layer into the vacuum chamber during the metallisation process, the first paper layer to be metal vapour deposition coated may be coated also on the other, outer side by a liquid composition of a polymer in aqueous or solvent based dispersion or solution, before the metallisation process step. It is desirable to avoid moisture in the vacuum chamber for metallisation, because it may reduce the speed at which the metallisation process can be carried out.
Furthermore, any back transfer of paper dust in the subsequent handling of coated paper webs on reels may be prevented by such a coating on the back- side.
For food products requiring better barrier properties against oxygen gas, a gas barrier coating layer may be coated onto the outer side of the first paper layer.
In cases when the packaging laminate structure contains a second paper layer positioned towards the outside of the packaging laminate, a gas barrier coating layer may be coated also onto the inside of said second paper layer.
In the case when the packaging laminate structure contains a second paper layer positioned towards the outside of the packaging laminate, the method of the invention further comprises the step of extrusion laminating the vapour deposited thin paper substrate to the inner side of the second paper layer, by means of an intermediate polymer bonding layer, preferably a thermoplastic polymer bonding layer.
A further aspect of the invention is a method of heat sealing a non-foil packaging laminate, comprising the steps of providing a non-foil packaging laminate as defined previously, in the form of a continuous web, forming the web- formed packaging laminate into a continuous tubular shape and applying a longitudinal seal in the longitudinal direction, filling the packaging laminate tube with a liquid foodstuff, forming heat-sealing zones by means of induction heating, at predetermined intervals in the traversing direction of the filled tube, and cutting through the centre of each traversing sealing zone, thereby forming individual containers.
In order to further describe the invention it will be discussed in view of the drawings. In Fig. 1 a, there is shown, in cross-section, a first embodiment of a packaging laminate 10a for aseptic packaging and long-term storage under ambient conditions, produced according to the invention. The laminate comprises a first paper layer 1 1 , having a surface weight of 50 g /m2,
The paper is prepared to receive a metal vapour deposition coating 12, which can work as an induction heat susceptible material and transmit heat to effect heat sealing in the innermost oriented film 20.
The thin paper, subsequently to be metal vapour-deposition coated, may be prepared by means of coating or by means of impregnating the paper layer or by means of mixing chemicals into the paper pulp at the stage of manufacturing of the paper web, or by any combination of these means or other means, for preparation.
The prepared thin paper web is subsequently vapour deposition metallised to an optical density (OD) of about 3.
An outer liquid tight and heat sealable layer 15 of polyolefin is applied on the outside of the core layer 1 1 , which side is to be directed towards the outside of a packaging container produced from the packaging laminate. The polyolefin of the outer layer 15 may be a conventional low density polyethylene (LDPE) of a heat sealable quality. An oriented film 20 is laminated on the inside of the vapour deposited layer 12, which is to be directed towards the inside of a packaging container produced from the packaging laminate, and the oriented film 20 will be in contact with the packaged product. The core layer of the oriented film is preferably selected from mono-oriented films, such as polypropylene (OPP), polyethylene terephthalate (OPET), polyamide (OPA), polyethylene naphthalate (OPEN), polybutylene terephthalate (OPBT), trimethylene terephthalate (OPTT); biaxially-oriented films, such as biaxially-oriented polypropylene (BOPP), polyethylene terephthalate (BOPET), polyamide (BOPA), polyethylene
naphthalate (BOPEN), polybutylene terephthalate (BOPBT), trimethylene terephthalate (BOPTT), or oriented films from two or more of the mentioned polymers, i.e. polypropylene, polyethylene terephthalate, polyamide, polyethylene naphthalate, polybutylene terephthalate, trimethylene terephthalate, the polymers being blended or copolymerized and thereafter used to form a mono- oriented or biaxially oriented film. In some embodiments, such as the ones disclosed in Fig 1 a Fig 1 b and Fig 1 c, the oriented film comprises one or more liquid-tight heat-seal layer(s) which represent the innermost side of the oriented film and consequently will be in contact with the packaged product. The liquid-tight heat-seal layer representing the innermost part of the film is a liquid tight, heat sealable thermoplastic polymer material, such as a polymer based on low density polyethylene, such as LDPE and/or LLDPE. In one embodiment the low density polyethylene includes an LLDPE produced by polymerising an ethylene monomer with a C4-C8, more preferably a C6-C8, alpha-olefin alkylene monomer in the presence of a metallocene catalyst, i.e. a so called metallocene -LLDPE (m-LLDPE). The oriented film 20 may additionally comprise an adhesive layer on its outer side to be laminated to the metal vapour deposited layer 12.
In one embodiment, similar to the embodiment disclosed in Fig 1 a and shown in cross-section in Fig 1 a2, the oriented film is laminated on the inside of the vapour deposited layer 12, which is to be directed towards the inside of a packaging container produced from the packaging laminate. An innermost liquid tight and heat sealable thermoplastic polymer material 14, such as a low density polyethylene such as LDPE and/or LLDPE, is arranged on the inside of the oriented film 20. In one embodiment the low density polyethylene includes an LLDPE produced by polymerising an ethylene monomer with a C4-C8, more preferably a C6-C8, alpha-olefin alkylene monomer in the presence of a metallocene catalyst, i.e. a so called metallocene -LLDPE. The innermost heat sealable layer 14 may consist of two or several part-layers of the same or different kinds of polymers. In one embodiment disclosed in Fig 1 a2 the oriented film (20) may or may not include a liquid-tight heat-seal layer representing the layer of the film directed towards the inside on the oppositeside of the film as the vapour deposited layer 12. It is often preferred to have one liquid-tight, heat sealable layer only, in particular for cost reasons. Nevertheless there are applications where two heat-sealable layers, one as a liquid-tight heat-seal layer of the oriented film and the other as a liquid-tight, heat sealable thermoplastic polymer material 14. Throughout the specification it applies that whenever the innermost liquid- tight, heat sealable layer 14 is present the Iiquid-tight heat-seal layer of the film may be present or absent.
In some embodiments of the invention, for example those disclosed in the figures, the oriented film 20 is bonded to the metal vapour deposition layer by means of an adhesive layer, such as an ethylene acrylic acid copolymer. The adhesive layer is a layer of the oriented film. Alternatively or complementary a bonding layer 19 may be applied as an intermediate layer between the oriented film and the metal-coated paper layer. Suitable bonding layers are based on low density polyethylene polymers and selected from modified or un-modified LDPE or LLDPE polymers, co-polymers or graft co-polymers of ethylene polymers with functional-group containing monomer units, such as carboxylic or glycidyl functional groups, e.g. (meth)acrylic acid monomers or maleic anhydride (MAH) monomers, (i.e. ethylene acrylic acid copolymer (EAA) or ethylene methacrylic acid copolymer (EMAA)), ethylene-glycidyl(meth)acrylate copolymer (EG(M)A) or maleic anhydride-grafted polyethylene (MAH-g-PE) may be used. Another example of such modified polymers or adhesive polymers are so called ionomers based on low density polyethylene. In one embodiment the modified polyethylene is an ethylene acrylic acid copolymer (EAA) or an ethylene methacrylic acid copolymer (EMAA). The described modified polymers may be suitable also in the optional adhesive layer comprised in the film.
In special cases, where a thicker heat sealable layer is needed, it is of course possible, although not preferred from a cost perspective, to apply a further Iiquid-tight, heat sealable polyethylene layer onto the inside of the innermost layer 14.
In Fig. 1 b, there is shown, in cross-section, a second embodiment of a packaging laminate 10b for aseptic packaging and long-term storage under ambient conditions, produced according to the invention. The laminate comprises a first paper layer 1 1 , having a surface weight of 50 g /m2, and a thin induction sealing durable layer 13 formed by liquid coating of a liquid polymer composition, and subsequent drying, onto the paper layer 1 1 . The composition comprises an aqueous solution of PVOH, and after drying, the coated layer thus comprises PVOH. Preferably, the PVOH has a saponification degree of at least 99 %. The coated thin paper web is subsequently vapour deposition metallised on its coated side to an optical density (OD) of about 3. The resulting packaging laminate thus comprises a thin paper substrate 1 1 , first coated with PVOH and then a thin vapour deposition coating layer 12 of aluminium metal at a thickness of about 50 nm. An innermost oriented film 20 is bonded to the metal vapour deposition layer by means of an adhesive layer and/or a bonding layer 19 (as shown in Fig 1 b3), on the inside of the vapour deposited layer 12, which is to be directed towards the inside of a packaging container produced from the
packaging laminate, and the oriented film 20 will be in contact with the packaged product. The core layer of the oriented film is preferably selected from biaxially oriented polymer layers.
In one embodiment, similar to the embodiment disclosed in Fig 1 b and as shown in cross-section in Fig 1 b2 and Fig 1 b4, the oriented film is bonded to the inside of the vapour deposited layer 12 by an adhesive layer comprised in the film (Fig 1 b2) or by a bonding layer 19 (Fig 1 b4). An innermost liquid tight and heat sealable thermoplastic polymer material 14 of a low density polyethylene such as for example LDPE and/or LLDPE, is arranged on the inside of the oriented film 20 (which may or may not comprise a liquid-tight heat-seal layer). In one
embodiment the low density polyethylene includes an LLDPE produced by polymerising an ethylene monomer with a C4-C8, more preferably a C6-C8, alpha-olefin alkylene monomer in the presence of a metallocene catalyst, i.e. a so called metallocene -LLDPE (m-LLDPE). The innermost heat sealable layer 14 may consist of two or several part-layers of the same or different kinds of polymers. In one embodiment the innermost liquid-tight, heat sealable layer 14 additionally comprises an adhesive layer in order to improve bonding between the liquid-tight, heat sealable layer 14 and the oriented film 20. In another similar embodiment the oriented film comprises an adhesive layer on its inner side where onto the liquid-tight, heat sealable layer 14 is to be laminated or extrusion coated.
In special cases, where a thicker heat sealable layer is needed, it is of course possible, although not preferred from a cost perspective, to apply a further heat sealable polyethylene layer onto the inside of the innermost layer 14.
An outer liquid tight and heat sealable layer 15 of polyolefin is applied on the outside of the core layer 1 1 , which side is to be directed towards the outside of a packaging container produced from the packaging laminate. The polyolefin of the outer layer 15 may be a conventional low density polyethylene, such as LDPE and/ or LLDPE of a suitable heat sealable quality.
In Fig. 1 c, there is shown, in cross-section, an embodiment of a packaging laminate 10c for aseptic packaging and long-term storage under ambient conditions, produced according to the invention. The laminate comprises a first paper layer 1 1 , having a surface weight of 50 g/m2, and a thin induction sealing durable layer 13 formed by liquid coating of a liquid polymer composition, and subsequent drying, onto the paper layer 1 1. The composition comprises an aqueous solution of PVOH and 30 weight-% bentonite particles, and after drying, the coated layer thus comprises PVOH and optionally exfoliated bentonite particles homogeneously distributed in a laminar fashion within the PVOH layer. Preferably, the PVOH has a saponification degree of at least 99 %.
The prepared thin paper web is subsequently vapour deposition metallised to an optical density (OD) of about 3.
The packaging laminate thus comprises a thin paper substrate 1 1 , first coated with PVOH and then coated with a thin vapour deposition coating layer 12 of aluminium metal at a thickness of about 50 nm.
In addition, the packaging laminate comprises a second core, paperboard layer 16 having a surface weight of at least 200 g/m2 or, preferably of about 300 g/m2. The first and second paper layers are suitably bonded to each other by means of an intermediate layer 17. The intermediate layer is conventionally based on a polyolefin-based polymer, preferably a low density polyethylene (LDPE). The intermediate bonding layer 17 is preferably formed by means of extrusion laminating the metal-coated first paper layer and the second
paperboard layer to each other. The intermediate layer 17 may be one or more layers.
The outer liquid tight and heat sealable layer 15 is defined as in Figures 1 a and 1 b.
In one embodiment, similar to the embodiment disclosed in Fig 1 c and as shown in cross-section in Fig 1 c2, the oriented film is bonded to the inside of the vapour deposited layer 12 by a thin induction sealing durable layer 13 formed by liquid coating of a liquid polymer composition, and subsequent drying, onto the paper layer 1 1. Between the vapour deposited layer 12 and the oriented film 20 an adhesive layer, as a part of the film 20, is laminated to the vapour deposited layer 12. An innermost liquid tight and heat sealable thermoplastic polymer material 14 is arranged on the inside of the oriented film 20. In this embodiment the low density polyethylene includes an LLDPE produced by polymerising an ethylene monomer with a C4-C8, more preferably a C6-C8, alpha-olefin alkylene monomer in the presence of a metallocene catalyst, i.e. a so called metallocene - LLDPE (m-LLDPE). The innermost heat sealable layer 14 may consist of two or several part-layers of the same or different kinds of polymers. As described above for Fig 1 b2 the innermost liquid-tight, heat sealable layer 14 additionally may comprise an adhesive layer, or the oriented film may comprise an adhesive layer on its inner side where the liquid-tight, heat sealable layer 14 is to
laminated.
As another not disclosed embodiments, similar to the embodiments disclosed in Fig 1 c and Fig 1 c2, there may be a bonding layer, as described for Fig 1 b3 and Fig 1 b4, between the vapour deposited layer 12 and the oriented film 20.
In special cases, where a thicker heat sealable layer is needed, it is of course possible, although not preferred from a cost perspective, to apply a further heat sealable polyethylene layer onto the inside of the innermost layer 14.
In order to reduce the amount of moisture released from the paper layer into the vacuum chamber during the metallisation process, the first paper layer, which is to be metal vapour deposition coated, may be coated also on the other, outer side by a liquid composition of a polymer in aqueous or solvent based dispersion or solution, before the metallisation process step. It is desirable to avoid moisture in the vacuum chamber for metallisation, because it may reduce the speed at which the metallisation process can be carried out. Furthermore, any back transfer of paper dust in the subsequent handling of coated paper webs on reels may be prevented.
According to Fig. 1 a and Fig. 1 b, the first paper layer 1 1 may be a thin paper layer of about 50 g/m2 or even less. Since the paper layer is very thin, it may need an additional light barrier by added pigments in one or more of the layers of the laminate. There may, for example, be light reflecting white pigments, such as for example titanium dioxide (ΤΊ02), and/or light absorbing pigments, such as for example carbon black, added to the liquid coated induction heat sealing durable layer 13, such as PvOH. Such pigments are advantageously hidden towards the inside by the metal vapour deposition coating 12, and at least to some extent by the paper layer 1 1 , towards the outside.
In Fig. 2, the method of liquid coating of a polymer composition onto a paper, or paperboard layer is grammatically schematically shown. The paper layer 21 a is fed from a storage reel towards a liquid coating station 22a, where the liquid polymer composition is applied at an amount such that the amount of coated and dried layer is about 1 -3 g/m2, when the coated paper has passed the drying station 22b. Preferably, the liquid coating operation is carried out in two steps, i.e. by first coating 0.5-1 .5 g/m2, drying in an intermediate step and then coating a second time at 0.5-1 .5 glm2 and finally drying the total liquid coated layer to obtain a coated paper layer 21 b.
Fig. 3 is a diagrammatic view of an example of a plant for vapour deposition coating of a metal layer 12 onto the coated thin first paper layer produced in Fig. 2. The thin paper web 21 b from Fig. 2 is subjected, on the coating receiving side, to continuous evaporation deposition 30. of a metallised layer of aluminium, possibly in a mixture with aluminium oxide, and the coating is given a thickness of 5-100 nm, preferably 5-50 nm, so that the metal coated paper of the invention 34a is formed. The aluminium vapour comes from a solid piece evaporation source 31 .
In Fig. 4a, the lamination process 40a is shown, wherein the induction heat sealing durable and/or oxygen barrier coated paper layer 34a, further coated with a thin metal vapour deposited coating 21 b, is heat laminated to an oriented film 50, having an adhesive layer 50a on the side facing towards the metallised layer, and an innermost heat sealable layer of LDPE and/or LLDPE 14, 43b is extrusion coated onto the inner side of the oriented film 50 and pressed together in a roller nip 45b. Subsequently, the laminated paper and film passes a second extruder 47 and lamination nip 48, where an outermost heat sealable layer of LDPE 46 is coated onto the outer side of the paper layer. Finally, the finished packaging laminate 49b is wound onto a storage reel, not shown. In Fig. 4b, an alternative embodiment is shown, wherein the induction heat sealing durable and/or oxygen barrier coated paper layer 34a, further coated with a thin metal vapour deposited coating 21 b is extrusion laminated with a bonding layer 50b to oriented film 50, in a first lamination station, and thereafter extrusion coated with the outermost polymer layer(s) 46, in a second extrusion coating station, and pressed together in a roller nip 45c. Subsequently, the laminated paper and film passes a third extrusion lamination station 48, where an innermost heat sealable layer of LDPE and/or LLDPE 14, 43b is coated onto the inner side of the film 50. Finally, the finished packaging laminate 49c is wound onto a storage reel, not shown.
As alternative embodiments a packaging laminate comprising an additional, second paperboard layer is possible and the second paperboard is bonded to the first metal-coated paperboard by extrusion laminating the metal- coated first paper layer and the second paper layer using an intermediate layer of a polyolefin-based polymer, preferably a low density polyethylene (LDPE) and thereafter performing the steps shown in Fig 4a and 4b respectively.
Fig. 5a shows one example of a packaging container 50 produced from the packaging laminate 10c according to the invention. The packaging container is particularly suitable for beverages, sauces, soups or the like. Typically, such a package has a volume of about 100 to 1000 ml. It may be of any configuration, but is preferably brick-shaped, having longitudinal and transversal seals 51 and 52, respectively, and optionally an opening device 53. In another embodiment, not shown, the packaging container may be shaped as a wedge. In order to obtain such a "wedge-shape", only the bottom part of the package is fold formed such that the transversal heat seal of the bottom is hidden under the triangular corner flaps, which are folded and sealed against the bottom of the package. The top section transversal seal is left unfolded. In this way the half-folded packaging container is still is easy to handle and dimensionally stable when put on a shelf in the food store or on a table or the like.
Fig. 5b shows an alternative, example of a packaging container 50b produced from the packaging laminate 10b according to the invention. Since the packaging laminate 10b is thinner by having a thinner paper core layer, it is not dimensionally stable enough to form a parallellepipedic or wedge-shaped packaging container, and is not fold formed after transversal sealing 52b. It will thus remain a pillow-shaped pouch-like container and distributed and sold like this.
Fig. 6 shows the principle as described in the introduction of the present application, i.e. a web of packaging material is formed into a tube 61 by the longitudinal edges 62, 62' of the web being united to one another in an overlap longitudinal joint 63. The tube is filled 64 with the intended liquid food product and is divided into individual packages by repeated transversal seals 65 of the tube at a pre-determined distance from one another below the level of the filled contents in the tube. The packages 66 are separated by incisions in the transversal seals and are given the desired geometric configuration by fold formation along prepared crease lines in the material.
The invention is not limited by the embodiments shown and described above, but may be varied within the scope of the claims.
Examples
EXAMPLE 1
Preparation of an aqueous coating composition for the induction heat sealing durable layer: An aqueous dispersion of exfoliated laminar montmorillonite particles (Kunipia F from Kunimine Kogyo Co.) having an aspect ratio of about 50-5000 is blended with an aqueous solution of about 30 weight-% of PVOH
(Mowiol 15-99, having a saponification degree of above 99 %) at 60-90 °C during 1 -8 hours. The dispersion of exfoliated laminar mineral particles may be stabilised by means of a stabiliser additive. Alternatively, the laminar mineral particles are exfoliated directly in the PVOH-solution at 60-90 °C during 1 -8 hours.
An aqueous composition of aqueous dissolved and dispersed PVOH and
30 weight-% exfoliated bentonite clay, was thus coated by means of liquid coating, in two consecutive steps with drying in between, onto a thin paper web having a surface weight of 50 g/m2, with 3 g/m2 PVOH coating in total. The wet applied coating is dried by hot air to evaporate the water.
In a subsequent step, the PVOH-coated paper was coated with an aluminium metal coating by means of a vapour deposition process up to optical density 3, onto the PVOH layer. The thus metallised, PVOH-coated paper was laminated to a thick paperboard of 260 mN (about 270 g/m2) by means of an extrusion laminating thermoplastic bonding layer of low density polyethylene (LDPE), and the thus laminated paper sandwich was subsequently coated with thermoplastic heat sealable layers (LDPE) on the outer most side.
The inner side was coated by means of extrusion laminating a BOPP film using LDPE as a bonding layer onto the inner side of the laminated paper sandwich. An innermost layer of liquid tight, heat sealable LDPE was coated by means of extrusion coating to the inner side of the BOPP film.
The thus formed laminate product was used and tested for heat seal quality in a Tetra Brik Aseptic ® conventional filling machine, employing adapted induction heat sealing of the packaging containers produced. It has for example been seen that to reach sufficient heating efficiency by a very thin metallised layer, the frequency used in the induction sealing process needs to be increased significantly.
The appearance and characteristics of the seals of the thus filled and sealed packaging containers were studied, by tearing the seals apart again. The appearance was noted and compared between the samples. The seal width and evenness in alignment was determined and compared by a further test, in which all packaging material is dissolved around the seal, except for the heat sealed thermoplastics. Finally, the package integrity of a filled and sealed packaging container was tested by using the red ink test. These are all tests well known by dairies and filling sites for Tetra Brik Aseptic ® packages, for sealing quality control of the daily produced, filled packaging containers.
The weighed properties and qualities of the samples of sealed packaging containers were evaluated based on many years experience from quality control of conventional packaging laminates for Tetra Brik ©Aseptic packaging
containers.
The heat seal quality and the integrity of the produced packages was very good, and on par with the seal quality of today's Tetra Brik Aseptic, aluminium foil based packages, according to evaluations by the test panel. In the red ink test, all 300 out of 300 filled and sealed packages, were liquid tight, without leakage points. EXAMPLE 2
An aqueous composition of aqueous dissolved and dispersed PVOH, having a saponification degree of above 99 %, and 10 weight-% exfoliated bentonite clay, was prepared in a similar way to Example 1 and coated by means of liquid coating, in two consecutive steps with drying in between, onto a thin paper web having a surface weight of 50 g/m2, with 3 g/m2 PVOH coating in total. The wet applied coating is dried by hot air to evaporate the water.
In a subsequent step, the PVOH-coated paper was coated with an aluminium metal coating by means of a vapour deposition process up to optical density 3, onto the PVOH layer.
The thus metallised, PVOH-coated paper was laminated to a thin paper of 50 g/m2 by means of an extrusion laminating thermoplastic bonding layer of low density polyethylene (LDPE). The inner side was further coated by means of heat laminating a BOPP film having an adhesive layer of EAA onto the inner side of the laminated paper sandwich. The inner side of the BOPP film was co-extrusion coated with two layers of LDPE. Where the innermost layer is a liquid, tight, heat sealable LDPE extruded at a temperature about 280 °C.
The coated and laminated paper sandwich was thereafter coated with thermoplastic heat sealable layers (LDPE) on both sides and tested for heat seal quality in a Tetra Brik Aseptic ® conventional filling machine, employing adapted induction heat sealing of the packaging containers produced.
Alternatively, it would be technically possible to metallise a thicker paper layer, e.g. of about 100 g/m2, and not laminating it to any further paper layers but keeping it as a single paper layer laminate, coated with outer heat sealable thermoplastic layers. Presently, however, it would not be cost efficient to vapour deposition coat a metallised layer onto such a thick paper substrate, why the above sandwich laminate was made in order to provide a laminate with a corresponding required thickness and stiffness.
The heat seal quality and the integrity of the produced package was equally very good, according to the same evaluation by the same test panel.
COMPARATIVE EXAMPLE 1 A 12 μΓΠ substrate film of an oriented PET (polyethylene terephthalate), was coated with an aluminium metal coating by means of a vapour deposition process to an optical density of about 3.
The thus metallised, PET-film was laminated to a thick paperboard of about 260 mN (or about 270 g/m2) by means of an extrusion laminating thermoplastic bonding layer of low density polyethylene (LDPE), and
subsequently coated with thermoplastic heat sealable layers (LDPE) on both sides and tested for heat seal quality in a Tetra Brik Aseptic ® conventional filling machine, employing adapted induction heat sealing of the packaging containers produced.
The heat seal quality and the integrity of the produced packages was acceptable according to evaluation by a test panel of tearing properties of the seals and of the package integrity using the red ink test, in comparison to the above examples. However, the sealing results from test run to test run were not as consistent and reliable as for laminated material with thin paper substrates.
COMPARATIVE EXAMPLE 2
A thin paper web having a surface weight of 50 g/m2 was co-extrusion coated by a first layer of LDPE at 10 g/m2 and a second layer of EAA (ethylene acrylic acid copolymer) at 5 g/m2.
In a subsequent step, the extrusion-coated paper was further coated with an aluminium metal coating by means of a vapour deposition process, onto the EAA layer.
The thus metallised, LDPE/EAA-coated paper was laminated with thermoplastic heat sealable layers on both sides and tested for heat seal quality in a test rig, simulating the real conditions in a conventional filling machine of the Tetra Brik Aseptic ® type, employing adapted induction heat sealing of the packaging containers produced. Furthermore, the laminated paper was tested in the conventional filling machine of the Tetra Brik Aseptic ® type, employing adapted induction heat sealing of the packaging containers produced.
The weighed properties and qualities of the samples of sealed packaging material and containers were evaluated based on many years experience from quality control of conventional packaging laminates for Tetra Brik ©Aseptic packaging containers, and it was seen that no properly sealed packages could be formed in the TBA filling machine, why any further testing of package integrity was unnecessary. Moreover, the results from the tear evaluation from sealing samples from the test rig showed that the seals were not good enough.
Thus, the heat seal quality and the integrity of the produced packages was not good, and not at all on par with the seal quality of today's Tetra Brik Aseptic, aluminium foil based packages, according to evaluations by the same test panel.
EXAMPLE 3
Example 3 was prepared in a similar way to Example 1 except that no exfoliated laminar montmorillonite particles were present.
The heat seal quality and the integrity of the produced packages was very good, and on par with the seal quality of today's Tetra Brik Aseptic, aluminium foil based packages, according to evaluations by the test panel. In the red ink test, all 300 out of 300 filled and sealed packages, were liquid tight, without leakage points.
EXAMPLE 4
Thin paper webs of different surface weights were coated by means of liquid coating in two consecutive steps, with drying in between, with an aqueous composition of aqueous dissolved and dispersed PVOH, having a saponification degree of above 99 %, and 10 weight-% exfoliated bentonite clay, as set out in Table 1 . The wet applied coatings were dried by hot air to evaporate the water.
In a subsequent step, the PVOH-coated paper webs were coated with an aluminium metal coating by means of a vapour deposition process, onto the PVOH layer.
The thus metallised, PVOH-coated was on the inner side coated by means of extrusion laminating a BOPET film using LDPE as a bonding layer onto the inner side of the laminated paper sandwich. An innermost layer of liquid tight, heat sealable LDPE was coated by means of extrusion coating to the inner side of the BOPP film. The thus obtained laminate was thereafter coated with thermoplastic liquid-tight heat sealable layers on the outer side of the laminate and tested for heat seal quality in a test rig, simulating the real conditions in a conventional filling machine of the Tetra Brik Aseptic ® type, employing adapted induction heat sealing of the packaging containers produced. From the results it can be seen that a thicker paper up to a certain surface weight, provides for better sealing results, than a thinner paper. It can also be seen that metal vapour deposition coating of a higher optical density (OD) provides for a somewhat better sealing result than a metal vapour deposition coating of a lower OD. Furthermore, it can be seen that thicker layers of PVOH provides for somewhat better sealing results than thinner layers. All the samples from Table 1 , provided very good seal quality in the rig tests, and should provide equally good results of package integrity in filling machine tests, similarly to what was shown in Example 1 . Although, better sealing results were perceived by the thicker paper substrates of 70 g/m2, the thinner substrates of 50 g/m2 have been generally used in the tests, because the thicker ones become much more expensive.
TABLE 1
Figure imgf000037_0001
properties a little by coating thicker or further layers of the PVOH composition, or to fill the PVOH layer with higher amount of inorganic particles. For example by coating a thicker and more densely filled gas barrier layer composition improved odour barrier properties are obtained. An excellent example of such a barrier composition comprises PVOH and from 10 to 50, preferably from 20 to 40 weight- % of talcum particles. Another example of such a barrier composition comprises PVOH and from 10 to 50 weight-% of talcum particles and from 1 to 40 weight %, nanoparticles such as those described above, e.g. clays.

Claims

A non-foil packaging laminate (10) for induction heat sealing into packages for liquid food or beverage, the packaging laminate
comprising at least one, first, layer of paper or other cellulose-based material (1 1 ), which first paper layer (1 1 ) is situated at the inner side of the packaging laminate and is pre-coated to receive and support an induction heat susceptible metal vapour deposited layer (12), in order to induce heat sealing in a thermoplastic polymer material, the packaging laminate further comprising a metal vapour deposited layer (12) applied onto the inner side of said pre-coated first layer of paper or cellulose- based material (1 1 ), and further comprising an oriented film (20) laminated to the metal vapour deposited layer (12); and further comprising an innermost layer of liquid tight, heat sealable thermoplastic polymer material (14) applied onto the inner side of the oriented film (20); or said oriented film comprises a liquid-tight heat-seal layer, representing the innermost layer of the film, wherein said oriented film (20) is stretched in at least one direction at a stretching ratio of 2 or more, and has a core layer of a material having a higher melting point than the material of the innermost layer(s).
The non-foil packaging laminate according to any one of the preceding claims, wherein said oriented film (20) is laminated to the metal vapour deposited layer (12) by an intermediate bonding layer or said oriented film (20) comprises an adhesive layer on its outer side to be laminated to the metal vapour deposited layer (12).
The non-foil packaging laminate according to claim 2, wherein said adhesive layer comprises an adhesive polymer selected from ethylene acrylic acid copolymer (EAA), ethylene methacrylic acid copolymer (EMAA)), ethylene-glycidyl(meth)acrylate copolymer (EG(M)A), and maleic anhydride-grafted polyethylene (MAH-g-PE).
4. The non-foil packaging laminate according to claim 2, wherein said bonding layer is based on low density polyethylene polymers and selected from modified or un-modified LDPE or LLDPE polymers, copolymers or graft co-polymers of ethylene polymers with functional- group containing monomer units, such as carboxylic or glycidyl functional groups, and from ionomers based on low density
polyethylene.
5. The non-foil packaging laminate according to claim 4, wherein said the bonding layer is selected from (meth)acrylic acid monomers or maleic anhydride (MAH) monomers, ethylene-glycidyl(meth)acrylate copolymer (EG(M)A) or MAH -grafted polyethylene (MAH-g-PE).
6. The non-foil packaging laminate according to any one of the preceding claims, wherein at least the core layer of the oriented film is selected from the group consisting of mono- and biaxially-oriented polymer film layers from polypropylene (OPP, BOPP), polyethylene terephthalate (OPET, BOPET), polyamide (OPA, BOPA); polyethylene naphthalate (OPEN, BOPEN), polybutyleneterephthalate (OPBT, BOPBT), trimethyleneterephthalate (OPTT, BOPTT), or from blends or
copolymers of said polymers.
7. The non-foil packaging laminate according to any one of the preceding claims, wherein at least the core layer of the oriented film is a biaxially- oriented polypropylene or a biaxially-oriented polyethylene
terephthalate.
8. The non-foil packaging laminate according to any one of the preceding claims, wherein the thickness of the oriented film is less than 30 μηι.
9. The non-foil packaging laminate according to any one of the preceding claims, characterised i n that the first layer of paper or other cellulose-based material (1 1 ) is coated onto its inner side with an induction sealing durable coating layer (13) having a higher melting point than the innermost layer of the non-foil packaging laminate, and in that, onto the inner side of the induction heat sealing durable coating layer is further applied said layer of an induction heat susceptible metal vapour deposition coating (12).
10. The non-foil packaging laminate according to claim 9, characterised i n that the induction sealing durable coating layer (13) is formed by liquid coating of a liquid composition onto said first paper layer and subsequent drying, the liquid composition containing a polymer binder dispersed or dissolved in an aqueous or solvent medium.
1 1 . The non-foil packaging laminate according to any one of claims 9-10, characterised i n that the induction sealing durable coating layer (13) is formed from a composition mainly comprising a polymer selected from the group consisting of polyvinyl alcohol (PVOH), water dispersible ethylene vinyl alcohol (EVOH), ethylene vinyl alcohol vinyl acetate copolymer, polyvinylidene chloride (PVDC), water dispersible polyamide (PA), polysaccharide, polysaccharide derivatives, starch, starch derivatives and combinations of two or more thereof.
12. The non-foil packaging laminate according to any one of claims 9-1 1 , characterised i n that the induction sealing durable coating layer (13) is formed from a composition mainly comprising a polymer selected from the group consisting of PVOH, water dispersible EVOH or starch.
13. The non-foil packaging laminate according to any one of claims 10-12, c h a ra ct e r i s e d i n that said liquid composition further comprises inorganic particles.
14. The non-foil packaging laminate according to any one of claims 9-13, c h a ra ct e r i s e d i n that said induction sealing durable coating layer
(13) is applied at a total amount of from 0.5 to 7 g/m2, preferably from 0.5 to 5 g/m2, more preferably 0.5 to 3 g/m2, dry weight.
15. The non-foil packaging laminate according to any one of claims 9-14, characterised in that the induction heat susceptible metal vapour deposition coating layer (12) is a layer substantially consisting of aluminium.
16. The non-foil packaging laminate according to any one of the preceding claims, characterised in that the metal vapour deposition coating layer (12) has an optical density (OD) of from 1 to 5, preferably of from 1.5 to 3.5, more preferably from 2 to 3.
17. The non-foil packaging laminate according to any one of the preceding claims, characterised in that the first, innermost situated, layer of paper or other cellulose-based material (11 ) has a surface weight of from 20 to 100 g / m2, preferably from 20 to 70 g/m2, more preferably from 30-60 g/m2.
The non-foil packaging laminate according to any one of the preceding claims, characterised in that it further comprises a second layer of paper or carton laminated to the outside of the first paper layer, which second paper layer has a surface weight of from 50 to 500 g/m2, preferably from 200 to 400 g/m2, most preferably from 200 to 300 g/m2.
Method of manufacturing a non-foil packaging laminate (10) according to any one of claims 1-18, comprising the steps of
- providing a first layer of paper or other cellulose-based material (21 ),
- pre-coating the paper or cellulose-based material layer for receiving and supporting an induction heat susceptible metal vapour deposition coating, by an induction sealing durable layer onto the inner side of the paper or cellulose-based material layer,
- applying said induction heat susceptible metal layer (12) onto the inner side of the thus coated paper layer,
- providing an oriented film (20), stretched in at least one direction at a stretching ratio of 2 or more, and having a core layer of a material having a higher melting point than the material of the innermost layer of the non-foil packaging laminate,
- laminating the oriented film (20) to the metal (12) coated paper layer (1 1 ),
- providing one or more layer(s) of liquid tight, heat sealable
thermoplastic polymer material (14) applied onto the inner side of the oriented film (20), or providing a liquid-tight heat-seal layer as a part of the oriented film (20) representing the innermost layer of the film, wherein either the liquid tight, heat sealable thermoplastic polymer material or the liquid-tight heat-seal layer of the film represents the innermost layer of the non-foil-packaging laminate.
The method of manufacturing a non-foil packaging laminate (10) according to claim 19, wherein the oriented film (20) is laminated to the metal coated deposited layer (12) by an intermediate bonding layer; or said oriented film (20) comprises an adhesive polymer layer on its outer side, which is laminated to the metal vapour deposited layer (12).
The method of manufacturing a non-foil packaging laminate (10) according to claim 20, wherein
the liquid tight, heat sealable thermoplastic polymer material is a low density polyethylene selected from LDPE, LLDPE, mLLDPE and VLDPE and blends thereof;
the adhesive layer is selected from ethylene acrylic acid copolymer (EAA), ethylene methacrylic acid copolymer (EMAA)), ethylene-glycidyl- (meth)acrylate copolymer (EG(M)A), and maleic anhydride-grafted polyethylene (MAH-g-PE); and
the bonding layer is based on low density polyethylene polymers and selected from modified or un-modified LDPE or LLDPE polymers, copolymers or graft co-polymers of ethylene polymers with functional- group containing monomer units, such as carboxylic or glycidyl functional groups, and from ionomers based on low density
polyethylene.
22. The method of manufacturing a non-foil packaging laminate (10) according to any one of claims 19-21 , wherein at least the core layer of the oriented film is selected from the group consisting of mono- and biaxially-oriented polymer film layers from polypropylene (OPP, BOPP), polyethylene terephthalate (OPET, BOPET), polyamide (OPA, BOPA); polyethylene naphthalate (OPEN, BOPEN), polybutyleneterephthalate (OPBT, BOPBT), trimethyleneterephthalate (OPTT, BOPTT), or from blends or copolymers of said polymers.
23. The method of manufacturing a non-foil packaging laminate (10)
according to any one of claims 19-22, wherein at least the core layer of the oriented film is a biaxially-oriented polypropylene or a biaxially- oriented polyethylene terephthalate.
24. The method of manufacturing a non-foil packaging laminate (10)
according to any one of claims 20-25, wherein the thickness of the oriented film is less than 30 μηι.
The method of manufacturing a non-foil packaging laminate (10) according to any one of claims 19-24, wherein said pre-coating is comprising the steps of
- providing a liquid composition containing a polymer binder dispersed or dissolved in an aqueous or solvent-based liquid medium,
- forming a thin induction sealing durable layer, comprising said
polymer binder, contiguous to the inner side of the first paper layer by coating (22a) the liquid composition onto the inner side of said layer of paper or other cellulose-based material and subsequently drying (22b) to evaporate the liquid, said polymer binder having a melting point higher than the innermost layer.
The method according to claim 25 wherein the induction sealing durable polymer contained in the liquid composition is selected from a group consisting of polyvinyl alcohol (PVOH), water dispersible ethylene vinyl alcohol (EVOH), ethylene vinyl alcohol vinyl acetate copolymer, polyvinylidene chloride (PVDC), water dispersible polyamide (PA), starch, starch derivatives and combinations of two or more thereof.
27. The method according to any one of claims 19-26, wherein the induction sealing durable layer (14) is applied in a total amount of from 0.5 to 7 g/m2, preferably from 0.5 to 5 g/m2, more preferably from 0.5 to 3 g/m2, dry weight.
28. Method according to any one of claims 19-27, wherein a coating layer is coated also onto the outer side of the first paper layer.
29. Packaging container (50a; 50b) manufactured from the packaging
laminate (10a; 10b) as specified in any one of claims 1 -18.
30. Method of heat sealing a non-foil packaging laminate, comprising the steps of
- providing a non-foil packaging laminate as defined in any one of claims 1 -18 in the form of a continuous web,
- forming the web-formed packaging laminate into a continuous
tubular shape and applying a longitudinal seal in the longitudinal direction,
- filling the packaging laminate tube with a liquid foodstuff,
- forming heat-sealing zones by means of induction heating, at
predetermined intervals in the traversing direction of the filled tube, and
cutting through the center of each traversing sealing zone, thereby forming individual containers.
PCT/EP2011/073760 2011-01-05 2011-12-22 Non-foil packaging laminate, method for manufacturing of the packaging laminate and packaging container produced thereof Ceased WO2012093036A1 (en)

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