AU2006228997A1 - Packaging films - Google Patents

Description

WO 2006/102723 PCT/AU2006/000452 1 PACKAGING FILMS The present invention relates to films for use 5 in packages, such as containers, for products. The films are referred to hereinafter as "packaging films" 10 The present invention also relates to packages, such as containers, that are made at least in part from the packaging films. In particular, although by no means exclusively, 15 the present invention relates to single or multiple layer packaging films for use in packages for food and beverage products that are made from packaging materials, such as polymer blends or other materials that are suitable for packaging food and beverage products. 20 Known packaging materials for use in packages for food and beverage products include, by way of example, polymeric materials such as low density polyethylene, high density polyethylene, polypropylene, ionomers, and 25 ethylene and propylene copolymers. The present invention relates more particularly, although by no means exclusively, to packaging films (and packages, such as containers, that are made at least in 30 part from the packaging films) for use in packages for food and beverage products in situations where it is desirable or essential to limit adverse interactions between the packaging materials and the products which modify the concentrations of desirable components present 35 in the products after filling the packages. Most particularly, the present invention relates WO 2006/102723 PCT/AU2006/000452 2 to packages, such as containers, for flavour sensitive products, such as wine, with the packages being made at least in part from packaging materials, such as packaging films, typically multiple layer co-extruded films, that 5 are selected so that there is minimal, if any, absorption, ie scalping, of critical flavour components of the products by the packaging materials that affects adversely characteristic flavour profiles of the products. 10 Specifically, a problem with current packaging films for use in packages, such as containers, for food and beverage products is that the polymeric materials used to make the films, such as low density polyethylene, high density polyethylene, polypropylene., ionomers, and 15 ethylene and propylene copolymers, absorb flavour components of the packaged products and thereby reduce the flavour of the packaged products. The present invention relates to the use of 20 alternative polymeric materials as the product contact layers of packaging films. Specifically, the present invention relates to the use of polymeric materials which possess desirable 25 properties in terms of minimising absorption of flavour components as the product contact layers of packaging films for use in packages for food products and that also have other desirable properties for packages for food products. 30 The other desirable properties for polymeric materials for packaging films include, by way of example, heat sealing properties. Heat sealing properties are required because in many situations packages, such as the 35 bags used in casked wine or similar applications, that is formed from packaging films are formed by "heat sealing" adjacent sections of packaging films together. More WO 2006/102723 PCT/AU2006/000452 3 specifically, the polymeric materials are often heated up to their melting point, which can range from 70 to 250*C, depending on the polymer, where upon they can be welded to adjacent sections of the same or different films, forming 5 a strong and easy and cheap to manufacture bond. Hence heat sealability is a desirable property for packaging films. The "heat sealing temperature" for a given 10 polymer is understood in the art to mean the temperature range for which it will achieve a satisfactory heat seal for the intended application. As noted above, this can range from 70 to 250 0 C. A lower temperature is preferred as higher temperatures can start damaging the other 15 polymeric materials that may be found within a multilayer packaging film. For this reason a heat sealing temperature of less than 160*C is often thought to be beneficial for the manufacture of the inner bags used in casked wine. 20 According to the present invention there is provided a packaging film for use as at least a part of a package for food or beverage products, which packaging film includes one or more than one layer, and the one layer of the single layer film or a layer of the 25 multilayer film that in use contacts a packaged product is formed from a packaging material in the form of a polymeric material that is a non-scalping polymer that does not absorb or absorbs only minimal amounts of flavour components of the packaged product. 30 Preferably the polymeric material has a melting point of less than 250'C so that the packaging film can be folded or otherwise manipulated into a package shape and adjacent sections can be heat sealed together to form the 35 package. Preferably the polymeric material is heat WO 2006/102723 PCT/AU2006/000452 4 sealable with a seal strength of greater than 1 KN/m, when measured by ASTM F88-00. More preferably the seal strength of the 5 polymeric material is greater than 2.5 KN/m, when measured by ASTM F88-00. Preferably the polymeric material is heat sealable after less than 2 seconds of dwell time at the 10 heat sealing temperature. The polymeric material includes but is e not limited to aromatic polyesters and copolymers, aliphatic polyesters and copolymers, polyamide polymers and 15 copolymers, and polybutylene terephthalate (sometimes known as PBT) and copolymers. Preferably the polymeric material is polyethylene tetraphhalte glycol (PETG) 20 The packaging material may further comprise additives which impart further functional properties such as physical property modification, emission of gases or liquids, or absorption of gases or liquids. 25 According to the present invention there is provided a package, such as a container, for food or beverage products that is formed at least in part from the above-described packaging film. 30 Preferably the package includes one or more than one heat sealed section formed by heat sealing adjacent sections of the polymeric material of the contact layer of the packaging film together with a seal strength of 35 greater than 1 KN/m, when measured by ASTM F88-00. Preferably the seal strength is greater than 2.5 WO 2006/102723 PCT/AU2006/000452 5 KN/m. The package may be a container in the form of a flexible film container, such as a "wine cask" or "bag-in 5 box" container for wine. The flexible film container may also be used for containing olive oil, water, and other foods, beverages and fluids that are particularly sensitive to changes in 10 taste after storage in containers made from polymeric materials due to absorption of one or more flavour components by the polymer materials. A further example of the use of the flexible film 15 container is where the flexible film container is used to contain wine during fermentation, storage or other production processes, such as that disclosed by Australian patent 763503 entitled "Materials handling apparatus and method", in the name of Australian Vineyards Development 20 Pty Ltd. This patent discloses the use of a flexible bag within a rigid support structure that retains fruit must in wine during in-bag fermentation of wine. The successful use of non-scalping polymers in 25 packaging films used as packages to contain wine in accordance with the present invention has been demonstrated by the applicant in a series of trials in which volatiles in wine being stored in contact with a series of resins were measured using known flavour 30 extraction methods and gas chromatograph test methods. The trials are discussed below and the results of the trials are presented in Figures 1 to 4. 35 In each trial, a fresh sample of bottled, commercially available wine was used (new bottle, screw cap closure). Each sample was measured for volatiles WO 2006/102723 PCT/AU2006/000452 6 before packing and then was used as- a control. Control samples were stored at 4C. The headspace of the bottled wine was flushed with nitrogen after each sampling period and then the bottle was resealed with a screw cap. 5 A reference material (naphthalene 1 ppb) was also measured for all samples to track any changes in gas chromatography technique performance. 10 The volatiles were measured using the following procedure: an aliquot of wine was placed in a clean 20ml headspace vial, capped and subjected to a solid phase microextraction - gas chromatography - mass spectrum (SPME-GC/MS) method. The method measured volatile flavour 15 components from the wine and tracked the loss of these components over time. A sample of wine was extracted at 37*C for 30 minutes in the method. All samples were analysed in duplicate. 20 All of the trials focused on measuring the concentration of 1, 1, 6-trimethyl-1, 2-dihydronaphthalene (TDN) as this is known to be an oxygen in-sensitive volatile characteristic flavour component of both white and red wines. Pollnitz et al (Proceedings Eleventh 25 Australian Wine Industry Technical Conference, pages 162 to 164) noted that "The compound most affected by storage in wine cask bladder was 1, 1, 6-trimethyl-1, 2-dihydronaphthalene 30 (TDN). This has a kerosene like aroma at high concentrations and is an important contributor to the aroma and flavour of some Riesling wines. Some 97% was apparently absorbed by the packaging; 75% of this absorption took place in the 24 hours of contact". 35 TDN is also thought to be representative of other volatile non-polar flavour components, even if the WO 2006/102723 PCT/AU2006/000452 7 absorption of these other compounds is not as strong. First trial 5 Trial 1 was initiated to evaluate the scalping properties of the currently available bag-in-box structure. A pinot noir wine was chosen for the study as 10 pinot noir wines are characterised by delicate bouquets of flavour volatiles and therefore are likely to be impacted by flavour volatile scalping. Samples bags (100 mm x 194 mm) were hand sealed 15 on two sides, 50 ml of pinot noir wine was added to each bag, headspaces were flushed for 2 minutes with nitrogen and the bags were sealed. Bags were sampled at 1, 3 and 5 days. Sampling 20 was done in duplicate. The results of the trial are presented in Figure 1. 25 Figure 1 shows the scalping behaviour of a typical, currently available, bag-in-box packaging film in the trial. The results of this trial show a significant loss of TDN in the first day of the trial, consistent with the findings of Pollnitz et al discussed above. 30 Second trial Four polymer resins were tested in this trial. 35 Brief details of the resins are set out in Table 1 below. The trade names of the resins was not noted as this was a preliminary trial.

WO 2006/102723 PCT/AU2006/000452 8 Table 1 Resins Density (g/cm 3 ) Low density polyethylene (LDPE) 0.920 High density polyethylene (HDPE) 0.949 Polylactic acid (PLA) 1.250 Polyethylene Tetrathapalate (PET) 1.370 5 The loss of 1, 1, 6-trimethyl-1, 2 dihydronaphthalene from sauvignon blanc and pinot noir wines in contact with the four resins was measured. The sauvignon blanc was a Waipara Hills 2003 10 sauvignon blanc (Malborough region, New Zealand) and the pinot noir was a Trentham Estate 2004 pinot noir (Trentham Cliff, New South Wales, Australia). For this and the subsequent trial the following 15 conditions were used: 0.2 gram of each resin was placed in a 20ml empty vial and the vial was filled with wine until no headspace was present. Vials were capped with a Teflon coated butyl septa. 20 The vials were sampled at 1, 3, 6, 9, 12, 17 and 30 days after exposure to the resin. The results of the trial are presented in Figures 2 and 3. 25 Figures 2 and 3 show a loss of 1, 1, 6-trimethyl 1, 2-dihydronaphthalene for the wine samples packed with the LDPE and HDPE. In contrast, there was no consistent change in TDN level for the wine packed with PLA and PET. 30 It is noted that PLA and PET have undesirable WO 2006/102723 PCT/AU2006/000452 Received 5 June 2006 properties for bag-in-box applications that would need to be addressed prior to the use of the polymeric materials in these applications. PLA is prone to flex cracking and PET is hard to heat seal, which is important as the inner 5 lawyer of the bag is heat sealed to form the bag structure. The reason why polyesters show improved scalping behaviour is that the higher density of polyesters (due to a more crystalline structure) compared to LDPE and HDPE 10 and other polymers currently used as packaging films for food and beverage products physically blocks the absorption of the volatile compounds in the polymers. Third trial 15 In the third trial an expanded list of resins was used. Brief particulars of the resins are set out in Table 2. 20 Table 2 Resins Type of Density Trade Name resin (g/cm 3 ) LDPE Polyolefin 0.920 LD10AC Modified linear low Polyolefin 0.895 DOWPF1140 density polyethylene (mLLDPE) mLLDPE Polyolefin 0.923 Evolue SP2320 mLLDPE Polyolefin 0.930 Evolue SP3010 HDPE Polyolefin 0.949 HYX800 Polypropylene (PP) Polyolefin 0.910 Inspire D114 Polyethylene Polyester 1.270 Skygreen K2012 Tetraphhalte glycol (PETG) Ethylvinyl Acatate EVA Polyolefin 0.939 Elvax 3165 Surlyn Polyolefin 0.920 1601-2 PET Polyester 1.370 As before WO 2006/102723 PCT/AU2006/000452 r L/A UUUO/UUU'I*Ie 10 Received 5 June 2006 The same test procedure and the same sauvignon blanc wine used in the second trial were used in this trial. 5 The vials were sampled at 1, 3, 5, and 7 days after exposure to the resins. The results are shown in Table 3, with key 10 results plotted in Figure 4. Table 3 - The scalping of 1, 1, 6-trimethyl-1, 2 dihydronaphthalene from sauvignon blanc by three of the resins over a 30 days period - numerical results. 15 Type of Fresh Day 1 Day 3 Day 5 Day 7 resin LDPE - LD10AC Polyolefin 5400 3900 2400 1700 1500 mLLDPE d = 0895 Polyolefin 5400 4000 2700 1800 1800 - DOWPF1140 mLLDPE d = 0.923 Polyolefin 5400 420 3600 1500 2200 - Evolue SP2320 mLLDPE d=0.930 - Polyolefin 5400 5100 3800 2500 1700 Evolue SP3010 HDPE - HYX800 Polyolefin 5400 5000 4900 3600 3800 Inspire PP - Polyolefin 5400 4400 5100 4300 5000 Inspire D114 PETG - Skygreen Polyester 5400 4600 8500 8500 9100 K2012 EVA - Elvax 3165 Polyolefin 5400 5300 2500 1000 1400 Surlyn - 1601-2 Polyolefin 5400 5800 3400 1800 2000 PET Polyester 5400 5600 7300 8200 10200 Table 3 and Figure 4 show a range of scalping behaviour. In particular, the two polyesters show an increase in the TDN level, while the polyolefins all 20 showed a decrease in TDN.

WO 2006/102723 PCT/AU2006/000452 11 It is believed that the rise in TDN levels with the two polyesters PETG and PET may be due to the absorption properties of SPME, which have been known to 5 vary, and/or TDN generation in the vial. TDN is a grape derived flavour - therefore, generation of this flavour compound post bottling is unlikely. The rise in concentration will be monitored in on-going trials. 10 This issue does prevent a conclusion that PETG and PET are suitable non-scalping because the overall trend of the results is that polyolefins (such as polyethylene) scalp non-polar flavours from wine and polyesters (such as PET, PLA, and PETG) do not scalp such 15 flavours from wine. Since PETG has suitable heating sealing properties for bag making, the results indicate that PETG, is particularly suitable for producing bag in box wines 20 that do not scalp. The heat sealability of PETG has been recognised previously. Specifically, US patent 4405400 in the name of Petersen-Hoj discloses the use of PETG as a sealing 25 layer in conjunction with other polymers. Many modifications may be made to the present invention described above without departing from the spirit and scope of the invention. 30

Claims (10)

1. A packaging film for use as at least a part of a 5 package for food or beverage products, which packaging film includes one or more than one layer, and the one layer of the single layer film or a. layer of the multilayer film that in use contacts a packaged product is formed from a packaging material in the form of a 10 polymeric material that is a non-scalping polymer that does not absorb or absorbs only minimal amounts of flavour components of the packaged product.

2. The packaging film defined in claim 1 wherein the 15 polymeric material has a melting point of less than 250'C so that the film can be folded or otherwise manipulated into a package shape and adjacent sections can be heat sealed together to form the package. 20

3. The packaging film defined in claim 1 or claim 2 wherein the polymeric material is heat sealable with a seal strength of greater than 1 KN/m, when measured by ASTM F88-00. 25

4. The packaging film defined in claim 3 wherein the seal strength is greater than 2.5 KN/m, when measured by ASTM F88-00.

5. The packaging film defined in any one of the 30 preceding claims wherein the polymeric material includes any one or more than one of aromatic polyesters and copolymers, aliphatic polyesters and copolymers, polyamide polymers and copolymers, and polybutylene terephthalate and co-polymers. 35

6. The packaging film defined in claim 5 wherein the polymeric material is polyethylene tetraphhalte glycol WO 2006/102723 PCT/AU2006/000452 13 (PETG)

7. A package, such as a container, for food or beverage products that is formed at least in part from the 5 packaging film defined in any one of the preceding claims.

8 The package defined in claim 7 in the form of a flexible film container, such as a "wine cask" or "bag-in box" container for wine. 10

9. The package defined in claim 7 or claim 8 includes one or more than one heat sealed section formed by heat sealing adjacent sections of the polymeric material of the contact layer of the packaging film 15 together with a seal strength of greater than 1 KN/m, when measured by ASTM F88-00.

10. The package defined in claim 9 wherein the seal strength is greater than 2.5 KN/m. 20