LAMINATED PACKAGING MATERIAL COMPRISING A BARRIER FILM AND PACKAGING CONTAINERS MANUFACTURED THEREFROM
20190077132 ยท 2019-03-14
Inventors
- Cesare Lorenzetti (Bulle, CH)
- Pierre Fayet (Lausanne, CH)
- Jerome Larrieu (Bulle, CH)
- Celine Denecker (Romont, CH)
Cpc classification
B32B2255/10
PERFORMING OPERATIONS; TRANSPORTING
B65D75/48
PERFORMING OPERATIONS; TRANSPORTING
B65D75/12
PERFORMING OPERATIONS; TRANSPORTING
B32B7/12
PERFORMING OPERATIONS; TRANSPORTING
B65D85/72
PERFORMING OPERATIONS; TRANSPORTING
B32B2255/00
PERFORMING OPERATIONS; TRANSPORTING
International classification
B32B7/12
PERFORMING OPERATIONS; TRANSPORTING
Abstract
A packaging laminate that includes a barrier film having a PECVD barrier coating of diamond-like carbon is disclosed, along with a method of manufacturing such films, and laminated packaging materials comprising such films, in particular intended for liquid food packaging are disclosed. Packaging containers that include the laminated packaging material or being made from the laminated packaging material, in particular to a packaging container intended for liquid food packaging are also disclosed.
Claims
1. A laminated packaging material for packaging of liquid food products, the laminated packaging material comprising: a barrier film, wherein the barrier film comprises: a substrate layer in the form of a web or sheet, a first barrier coating of an amorphous diamond-like carbon (DCL) coated to be in contiguous contact with the substrate layer, and a second thermoplastic barrier layer, comprising a polyamide that is coated and in contiguous contact with the free surface of the first DLC barrier coating, wherein the laminated packaging material further comprises a first outermost liquid tight, heat sealable polymer layer applied on the barrier-coated side of the substrate layer, the first outermost polymer layer is providing the outermost surface of a packaging container made from the laminate packaging material and a second, innermost liquid tight, heat sealable polymer layer on the opposite, inner and second side of the barrier film, the second, innermost polymer layer is providing the innermost surface of a packaging container made from the packaging material to be in contact with the packed product.
2. The laminated packaging material in claim 1, wherein the substrate layer is a polymer film substrate.
3. The laminated packaging material in claim 1, further comprising a bulk layer of paper or paperboard or other cellulose-based material.
4. The laminated packaging material in claim 1, further comprising a bulk layer of paper or paperboard or other cellulose-based material, and a second barrier layer, wherein the second barrier layer is laminated to a first side of the bulk layer by at least one intermediate bonding layer, comprising a thermoplastic polymer, such as a polyolefin, said first outermost liquid tight, heat sealable polymer layer on the opposite, second and outer, side of the bulk layer, while said second innermost liquid tight, heat sealable polymer layer is on the inner side of the barrier film, which is opposite to the side that is bonded to the bulk layer.
5. The laminated packaging material in claim 4, wherein the at least one bonding layer comprises a layer of low density polyethylene (LDPE), and wherein the LDPE is in contiguous contact with the bulk layer, and a layer of an adhesive polyethylene, modified polyethylene, or a so-called polyethylene tie layer, between the LDPE and the second barrier layer.
6. The laminated packaging material in claim 4, wherein the at least one bonding layer is a layer comprising a blend of low density polyethylene (LDPE) and an adhesive, modified polymer or so-called compatibiliser, and wherein the bonding layer is in contiguous contact with the bulk layer, as well as the second barrier layer on the other side.
7. The laminated packaging material of claim 1, wherein the substrate layer of the barrier film has an adhesion-promoting primer coating on its other side, opposite the side coated with the barrier coating, and wherein the barrier film is bonded to the second innermost liquid tight, heat sealable polyolefin layer by the adhesion-promoting primer coating.
8. The laminated packaging material of claim 7, wherein the adhesion-promoting primer coating is formed by a composition comprising one or more compounds selected from the group consisting of aminosilanes and polyethyleneimines.
9. The laminated packaging material of claim 7, wherein the adhesion-promoting primer coating is a second coating of an amorphous diamond-like carbon (DLC).
10. The laminated packaging material of claim 1, wherein the barrier film of the laminated packaging material is a double barrier film, which comprises a first barrier film laminated and bonded to a further identical or similar second barrier film by an interjacent thermoplastic bonding layer.
11. The laminated packaging material of claim 1, wherein the substrate layer comprises a polymer film comprising a polymer selected from the group consisting of a polyester a polyamide, an ethylene vinyl alcohol copolymer (EVOH), a polyolefin and a blend of any of said polymers, or wherein the substrate layer comprises a multilayer film having a surface layer comprising any of said polymers or blends thereof.
12. The laminated packaging material of claim 1, wherein the second barrier layer comprises a polyamide selected from the group consisting of aliphatic polyamides, semi-aromatic polyamides, and blends of two or more of said aliphatic and semi-aromatic polyamides.
13. The laminated packaging material of claim 1, wherein the second barrier layer further comprises an ethylene vinyl alcohol copolymer (EVOH).
14. The laminated packaging material of claim 1, wherein the first, amorphous diamond-like carbon barrier coating is 2 to 50 nm thick.
15. The laminated packaging material of claim 1, wherein the second amorphous diamond-like carbon coating, acting as an adhesion-promoting primer coating, is 2 to 50 nm thick.
16. The laminated packaging material of claim 1, wherein the substrate layer is a polyethylene film.
17. The laminated packaging material of claim 1, wherein the substrate layer is an oriented PET film.
18. The laminated packaging material of claim 1, wherein the substrate layer is 8 to 12 m thick.
19. The packaging container comprising the laminated packaging material as defined in claim 1.
20. The laminated packaging material of claim 1, wherein the second amorphous diamond-like carbon coating, acting as an adhesion-promoting primer coating, is 2 to 10 nm thick.
Description
EXAMPLES AND DESCRIPTION OF PREFERRED EMBODIMENTS
[0073] In the following, preferred embodiments of the invention will be described with reference to the drawings, of which:
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EXAMPLES
[0081] Films from 12 m thick biaxially oriented polyethyleneterephthalate (BOPET Hostaphan RNK12 and RNK12-2DEF by Mitsubishi) were deposition coated with various coatings by plasma enhanced chemical vapour deposition (PECVD) under vacuum conditions, in a roll-to-roll plasma reactor. A diamond-like amorphous hydrogenated carbon coating, DLC, was coated on some film samples, in line with the invention, while other PECVD barrier coatings were coated on other samples. The other PECVD barrier coatings, subject of comparative examples, were SiOx, wherein x varied between 1.5 and 2.2, SiOxCy coatings and SiOxCyNz coatings, respectively, wherein (y+z)/x is from 1 to 1.5. These other silicon-containing barrier coatings were formed from organosilane pre-cursor gas compounds. The film samples according to the invention, were coated by depositing an amorphous, hydrogenated diamond-like coating DLC from a plasma formed from pure acetylene gas.
[0082] The plasma employed was capacitively coupled to the power delivered at 40 kHz frequency, and magnetically confined by unbalanced magnetron electrodes placed at a distance from the circumferential surface of a rotating drum, which functioned as a combined film-web transporting means and electrode. The polymer film substrate was cooled by cooling means within the drum web-transporting means.
[0083] The DLC coating was in a first example applied to a thickness of about 15-30 nm, and in a second example to a thickness of only about 2-4 nm.
[0084] The SiOx coatings were coated to a thickness of about 10 nm.
[0085] The thus barrier-coated substrate film samples, were subsequently extrusion coated with a 15 g/m2 thick layer of low density polyethylene (LDPE), of a type corresponding to LDPE materials of the laminate bonding layer that is conventionally used in order to extrusion laminate paperboard to aluminium foil in liquid carton packaging laminates.
[0086] The adhesion between the thus extrusion coated LDPE layer and the barrier-coated substrate PET film, was measured by a 180 peel test method under dry and wet conditions (by putting distilled water at the peeling interface) as described above. An adhesion of more than 200 N/m ensures that the layers do not delaminate under normal manufacturing conditions, e.g. when bending and fold-forming the laminated material. A wet adhesion of this same level ensures that the layers of the packaging laminate do not delaminate after filling and package formation, during transport, distribution and storage.
TABLE-US-00001 TABLE 1 PE- PE- laminate laminate Water Peel force Peel force Oxygen Vapour (N/m) (N/m) wet Coating type Barrier Barrier Dry adhesion adhesion SiOx (x = 1.5-2.2) <3 cc at 3 N/A 40-50 0 Mean 1.5 cc SiOxCy (y/x = 1-1.5) <3 cc at 3
1 40-50 40-50 Mean 1.5 cc SiOxCyNz <3 cc at 3
1 200-300 100 (y + z/x = 1-1.5) Mean 1.5 cc DLC ~25 nm <3 cc at 3
0.8 350-400 350-400 Mean 1.5 cc DLC ~25 nm on 0.5 0.05 0.5 350-400 350-400 both sides of film DLC 2-4 nm 60-80 5-6 350-400 350-400 DLC 2-4 nm on 60-80 5-6 350-400 350-400 both sides of film
[0087] As can be seen from the results summarised in Table 1, there is some insufficient dry adhesion between pure SiOx barrier coatings and thereonto extrusion coated LDPE, while the adhesion deteriorates completely under wet/humid conditions.
[0088] When experimenting with more advanced SiOx formulas, containing also carbon and nitrogen atoms, some improvement is seen in the dry and/or wet adhesion properties, as compared to the pure SiOx coating, but the wet adhesion properties remain insufficient, i.e. below 200 N/m.
[0089] The dry adhesion of a DLC coating to extrusion coated LDPE is slightly better than for the best of the tested SiOxCyNz coatings. The more important and unforeseeable difference, compared to the SiOxCyNz coatings is that the adhesion remains constant under wet or humid conditions, such as are the conditions for laminated beverage carton packaging.
[0090] Furthermore, and rather surprisingly, the excellent adhesion of DLC coatings at values above 200 N/m, remain unaffected also when the DLC coating is made thinner, and as thin as 2 nm, i.e. where there is actually no notable barrier properties obtained any longer. This is the case both regarding dry and wet conditions for the sample films.
[0091] Of course, when such films are laminated into packaging laminates of paperboard and thermoplastic polymer materials, it is advantageous to coat such a DLC coating on both sides of the film, in order to provide excellent adhesion on both sides of the film. Alternatively, the adhesion to adjacent layers on the opposite side of the substrate film, may be secured by a separately applied chemical primer composition, such as the 2 DEF primer from Mitsubishi. A DLC adhesion-promoting layer is preferable from both environmental and cost perspective, since it only involves carbon atoms in the adhesion layer, and since it may be made very thin in order to just provide adhesion, or thicker in order to provide also barrier properties. At any thickness of a DLC-coating, the adhesion obtained is at least as good as that of a chemical primer (such as the 2 DEF from Mitsubishi) under both dry and wet conditions.
[0092] Thus, by the DLC-coated barrier films described above, high-integrity packaging laminates are provided, which have maintained excellent adhesion between layers also when used in liquid packaging, i.e. at subjecting the packaging material to wet conditions, and which may consequently protect other layers of the laminate from deterioration, in order to provide as good laminated material properties as possible. Since DLC coatings in general provide both good oxygen barrier properties and water vapour barrier properties, it is a highly valuable type of barrier coating to be used in carton package laminates for liquid food products.
[0093] In a second example, a DLC-coated, 30 g/m2 thick LLDPE blown film was measured to have an OTR from 30 to 50 cc/m2/day/atm at 23 C. and 50% relative humidity RH. When coated with a second barrier layer of 4-6 g/m2 of a blend of about 70 weight-% PA6 and about 30 weight-% PA-MXD6, the OTR was decreased down to 3-5 cc/m2/day/atm, i.e. the oxygen barrier was times improved. The adhesion between the polyamide extrudate and the DLC barrier coating was very high, i.e. above 400 N/m.
[0094] In a third example, a similarly DLC-coated, 12 m thick BOPET film was measured to have an OTR from 1.5 to 2 cc/m2/day/atm at 23 C. and 50% relative humidity RH. When coated with a second barrier layer of 4-6 g/m2 of a blend of about 70 weight-% PA6 and about 30 weight-% PA-MXD6, the OTR was decreased down to 0.4-0.9 cc/m2/day/atm i.e. the oxygen barrier was 3-5 times improved. The adhesion between the polyamide extrudate and the DLC barrier coating was very high, i.e. above 400 N/m.
[0095] It is clear that the improvement level obtained by laminating the DLC barrier coating to a further thermoplastic oxygen gas barrier layer, is high enough to compensate for a substrate layer having only low initial oxygen barrier properties, such as polyethylene of a lower density, such as LLDPE. This phenomenon can thus be used in a laminated packaging material structure according to the invention, further adding outermost heat sealable and liquid-tight layers to the laminated structure, and in the preferred case also comprising a paperboard core layer, to provide for dimensionally stable packages, filled with or to be filled with liquid or semi-liquid or semi-solid food. Such packages were produced and the oxygen barrier properties were very favourable and deemed suitable for liquid food packaging with higher requirements on shelf life and long-term storage.
[0096] Further, relating to the attached figures:
[0097] In
[0098] According to an alternative embodiment, the barrier film 11 as schematically shown in
[0099] In
[0100] On each side the barrier film is laminated to a layer of a thermoplastic and heat sealable polymer layer 12,13. Thus, the outermost layers of thermoplastic and heat sealable polymer are each contacting the adhesion-promoting primer coatings 11c, of a DLC primer coating of each of the barrier films 11; 11d. A possible alternative adhesion-promoting coating 11c could be a chemical primer coating of the type 2 DEF from Mitsubishi.
[0101] In a further embodiment not shown, the outermost layer of a thermoplastic and heat sealable polymer layer 12; 22; 32, which is to constitute the outside of a packaging container made of the laminated material, is applied onto a bulk layer 14; 21; 31, which is laminated and positioned between the double barrier film obtained above and the outermost layer 12, the double barrier film being the double structure in which the intermediate bonding layer is bonding together the DLC barrier coating surfaces 11b of two barrier films 11; 11d. The double barrier film may contain further DLC coatings 11c for barrier and/or for adhesion-promotion purposes.
[0102] In
[0103] The bulk layer 21 is laminated to a barrier film 28, comprising a substrate layer 24 of a polymer film, in this case an oriented PET film having a thickness of 12 m, which is coated on a first side with a layer of a thin
[0104] PECVD vapour deposited layer of amorphous, DLC barrier material, 25, at a thickness of from 2-50 nm, such as from 5 to 40 nm, and further corona treated and coated with a second thermoplastic barrier layer 29 from a blend of PA-6 and PA-MXD6 at a 70:30 blending ratio and at about 5 g/m2. On its second, opposite, side, the polymer film substrate is coated with an adhesion-promoting primer 27, in this case 2-DEF, a priming composition from Mitsubishi Chemicals. The first, DLC-coated, side of the thus barrier-coated film 24 is laminated to the bulk layer 21 by an intermediate layer 26 of bonding thermoplastic polymer or by a functionalised polyolefin-based adhesive polymer, in this example by a low density polyethylene (LDPE) and by the further second thermoplastic barrier layer 29, by coextrusion laminating the molten layers 26 and 29 between the bulk layer and the DLC-coated film, while entering a lamination roller nip. The intermediate bonding layer 26 is thus formed by means of extrusion laminating the bulk layer and the DLC-coated film to each other, with the second thermoplastic barrier layer 29 being adjacent and in direct contact with the DLC coating. The thickness of the intermediate bonding layer 26 is preferably from 7 to 20 m, more preferably from 12-18 m. Excellent adhesion will be obtained between these layers, providing good integrity of the laminated material, in that the PECVD-coated DLC barrier coating is containing substantial amounts of carbon material, which exhibits good adhesion compatibility with organic polymers, such as polyolefins, such as in particular polyethylene and polyethylene-based co-polymers. The innermost heat sealable layer 23 consists of two or several part-layers of the same or different kinds of LDPE or LLDPE or blends thereof and has likewise good adhesion and integrity with the adjacent primer-coated side of the barrier film.
[0105] In
[0106] The bulk layer 31 is laminated to a barrier film 38, comprising a substrate layer 34 of a polymer film, in this case an oriented PET film having a thickness of 12 m, which is coated on a first side with a layer of a thin PECVD vapour deposited layer of amorphous, DLC barrier material, 35a, at a thickness of from 2-50 nm, such as from 5 to 40 nm, such as from 10 to nm, and further corona treated and coated with a second thermoplastic barrier layer 35c from a blend of PA-6 and PA-MXD6 at a 70:30 blending ratio and at about 5 g/m2. On its second, opposite, side, the polymer film substrate is coated with a second amorphous DLC coating 35b. The second amorphous DLC coating may add barrier properties too, but can also act merely as an adhesion promoting primer coating, and may then have a thickness as low as 2-4 nm. The first, DLC-coated, side of the thus barrier-coated film 34 is laminated to the bulk layer 31 by an intermediate layer 36 of bonding thermoplastic polymer or by a functionalised polyolefin-based adhesive polymer, in this example by a low density polyethylene (LDPE) and the further second thermoplastic barrier layer 35c, being coextrusion laminated between the bulk layer and the DLC-coated film. The intermediate bonding layer 36 and the second thermoplastic barrier layer 35c are thus formed while melt co-extrusion laminating the bulk layer and the DLC-coated barrier film to each other. The thickness of the intermediate bonding layer 36 is preferably from 7 to 20 m, more preferably from 12-18 m. The innermost heat sealable layer 33 may consist of two or several part-layers of the same or different kinds of LDPE or LLDPE or blends thereof. Excellent adhesion will be obtained between these layers on the inside of the bulk layer 31, providing good integrity of the laminated material, in that the PECVD-coated DLC barrier coating is containing substantial amounts of carbon material, which exhibits good adhesion compatibility with organic polymers, such as polyolefins, such as in particular polyethylene and polyethylene-based co-polymers.
[0107] In
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[0113] We have thus seen that the laminated packaging material of the invention, enable the providing of packaging containers with good integrity properties also under wet conditions, i.e. for the packaging of liquid or wet food products with long shelf life.
[0114] The invention is not limited by the embodiments shown and described above, but may be varied within the scope of the claims.