EP0785893A1

EP0785893A1 - Packaging for a drink based on anethole

Info

Publication number: EP0785893A1
Application number: EP96929352A
Authority: EP
Inventors: Philippe Noble; Patrice Robichon
Original assignee: Pernod Ricard SA
Current assignee: Pernod Ricard SA
Priority date: 1995-08-21
Filing date: 1996-08-21
Publication date: 1997-07-30
Anticipated expiration: 2016-08-21
Also published as: DE69606014D1; PT785893E; MX9702934A; JPH10507980A; DE69606014T2; ATE188431T1; NO320563B1; JP3937452B2; WO1997007029A1; EP0785893B1; CA2203154C; GR3032741T3; ES2140892T3; AU6878496A; US5871791A; NO971810L; FR2738003B1; CA2203154A1; NO971810D0; DK0785893T3

Abstract

The invention relates to a packaging made up of at least one inner, containing an alcoholic or nonalcoholic beverage based on anethole, in which the inner foil of said packaging is made up of a film of polyamide including aromatic units. The packaging is preferably intended to contain weakly alcoholic beverages and the polyamide results from the polycondensation of meta-xylylenediamine with adipic acid.

Description

PACKAGING FOR ANETHOLE BEVERAGE

The present invention relates to a new packaging containing an aqueous alcoholic beverage or not based on anethole.

It also relates to a process intended to limit the loss of anethole contained in an optionally alcoholic solution in contact with the wall of a packaging made of polymer material as well as the use of a polymer film for producing a packaging in contact with possibly alcoholic anethole solutions in order to limit the loss of anethole in contact with the wall of the packaging. Anise drinks contain anethole or para propenyl methoxy benzene, in the majority trans form (greater than 96-97%).

Anethole has the distinction of being very slightly soluble in water (<50 mg / l) and soluble in alcohol. In the presence of water, the anethole becomes cloudy, whereas in a water / alcohol solution with a high alcohol content (of the order of 45% by volume), the anethole remains in the solubilized state.

In the case of non-alcoholic or low-alcoholic drinks (4-9% vol), an emulsifier is used because the anethole is no longer soluble.

When preserving aniseed-flavored drinks, significant degradation appears over time, in particular under the action of: - light (cis-trans isomerization),

- oxidation in the presence of light,

- the interaction between the anethole and the packaging material.

If we were able to overcome the first two disadvantages mentioned above using opaque ultra-violet packaging and having a gas barrier effect, it is not the same with regard to the third point relating to the loss of anethole on contact with packaging material.

In fact, in the case of polymer packaging conventionally used (polyethylene, polypropylene, polyvinyl chloride, polyethylene terephthalate), a very significant loss of aroma is observed over time (up to 100%) in contact with the polymer walls. , what prevents the marketing of aniseed drinks in plastic packaging.

This problem is even more sensitive in the case of non-alcoholic or low-alcohol drinks based on anethole for which the loss on contact with the polymer is even faster.

Several scientific observations illustrate the particular behavior of this compound:

Anethole has a low coefficient of solubility in water but a high coefficient of solubility in polymers. This phenomenon is all the more important for drinks with little or no alcohol. This induces a significant electrostatic interaction with the surface of the polymer and the adsorption of anethole thereon.

Furthermore, the affinity of anethole for polymers is such that an absorption phenomenon occurs, by insertion of this compound between the chains of the polymer. It is therefore a dynamic phenomenon of adsorption / absorption.

Anethole also reveals a strong propensity to polymerize into polyanethole. This cationic type polymerization is favored by the very electron-donating nature of the methoxy group. This phenomenon occurs in particular in the case of polymers derived from styrene, maleic anhydride or acrylonitrile commonly used as packaging for beverages. This is due to the fact that anethole reacts with the molecular chains of these polymers. However, anethole can also react with residual monomers, given the well-known copolymerization reaction with styrene (T. Higashimura et al, Journal of Polymer Science: part A. l, vol. 10.85-93 (1972)) or terpolymerization with maleic anhydride and acrylic monomers such as acrylonitrile (T. Kobuko et al, Macromolecules, vol.3, n ° 5, Sept-Oct. 1970,518-523).

For all these reasons, we do not know, at present, plastic packaging for anethole-based drinks. It has been well described in the abstract Derwent AN-9231951 1 (39) a bottle formed of a crushable aromatic polyamide, but this document simply indicates that the bottle may contain beer, carbonated drinks or juices. This bottle is also assimilated to PET bottles which, as we know, cannot be used in the case of anethole-based drinks.

This is why currently aniseed drinks are packaged in glass bottles.

It is therefore desirable to propose new packaging in polymer material making it possible to reach or approach the inertial performance of glass.

After systematic research, the applicant company has developed a new packaging intended to contain aniseed drinks, possibly alcoholic, which have satisfactory characteristics, in particular as regards the absence of sorption of anethole.

This is why, the invention firstly relates to a packaging for an optionally alcoholic drink comprising anethole, characterized in that the internal layer of said packaging is formed of a polyamide film comprising aromatic units. By "packaging" is meant any monolayer or multilayer packaging, capable of containing said drink, whether in the form of a bottle, box or other equivalent closed systems, including bottles and pouches.

The packaging has been found to be particularly advantageous in the case of non-alcoholic or low-alcoholic drinks whose alcohol content is preferably less than 10% by volume, preferably between 3 and 9%.

In known manner, the aqueous alcoholic drink comprises from 0.01 to 2 g / l of anethole, preferably 0.02 g / l or more of anethole. In concentrates to be diluted such as the drink known under the name "Pastis", the anethole concentration is of the order of 2 g / l.

In ready-to-drink alcoholic beverages, it is around 200 to 400 mg / l. In the case of anise flavored drinks, it is of the order of 10 to 50 mg / l.

It will be recalled that for alcoholic drinks at 45% by volume, the anethole is completely dissolved, while for non-alcoholic or low-alcoholic drinks (4-9% by volume), an emulsifier is used in order to maintain the anethole as a stable emulsion.

Preferably, the polyamide film is such that the water absorption measured according to ATSM D570 is less than 8% and the water uptake measured according to ASTM D570 is less than 5%. Preferably, the polyamide film is such that the oxygen permeation speed (cc-20 μ / m ² day, atm) at 20 ° C. and at

0% RH is less than 4.

These polyamide polymers are obtained by polycondensation of a dialcohol with a diamine, one of the monomers being aromatic.

Advantageously, the polyamide polymers are obtained by polycondensation of an aliphatic dialcohol with an aromatic diamine in

C ₅ (phenyl).

Among the polyamide polymers suitable in the context of the present invention, advantageously may be mentioned those obtained by polycondensation of meta-xylylenediamine with adipic acid such as Nylon-MXD6 sold by the company SOLVAY or SELAR® PA sold by the company DU BRIDGE OF NEMOURS.

These resins were already known to form a barrier layer to oxygen, carbon dioxide and humidity and were therefore already recommended for the packaging of various food products. It should be noted, however, that no publication or commercial brochure from the manufacturers suggests the particularly remarkable properties of these resins with respect to anethole.

It should also be noted that in the 1992 publication published in

Journal of Food Science, vol. 57, pages 490 to 492, the authors study the absorption of aromatic esters or aldehydes by various polymers, the

Nylon-6 or polyethylene terephthalate and that these have concluded that polyethylene terephthalate constitutes a remarkable "barrier" film vis-à-vis esters and aldehydes or alcohols comparable to polyamide. However, it is surprising to note that polyethylene terephthalate is not acceptable in the case of packaging for drinks containing anethole, in particular in the case of low alcoholic drinks, while the polyamides according to the invention reveal remarkable qualities making possible industrial implementation of packaging.

In general, in addition to the barrier characteristics with respect to anethole, the polyamide films with aromatic units must have sufficient impermeability with respect to carbon dioxide. They must also have a tear strength and a modulus of elasticity sufficient for the application considered, whether it is the packaging proper, the sealing means or the seal, monolayer or multilayer.

Preferably, the thickness of the polyamide film is between 10 and 100 micrometers, in general between 20 and 80 micrometers and advantageously of the order of 50 micrometers.

The invention relates in particular to a two-layer packaging comprising an external layer of structure and an internal film formed from a polyamide film comprising aromatic units. By external structural layer is meant a material having sufficient tear strength in the context of the use considered, in particular polymer, metal or cardboard.

Preferably, the outer layer will have sufficient rigidity for bottle shaping and will be advantageously chosen from the group consisting of polyesters such as polyethylene terephthalate (PET) or polyolefins such as polypropylene (PP) or polyethylene (PE ).

According to a preferred embodiment, the polyamide film is co-extruded with the associated layer or layers under conditions of temperature and pressure well known in the art considered. Extrusion temperatures are usually between 200 and 320 ° C. The co-extrusion operation can be followed by a bi-axial orientation. Preferably, the packaging is in the form of a three-layer material obtained by co-extrusion comprising an intermediate layer of a binder ensuring cohesion between the internal layer and the external layer. The different thicknesses of the layers constituting such a material are generally between the following intervals (in μm). Outer layer 50 to 1000

Intermediate layer 5 to 50

Inner layer (polyamide film) 20 to 100 The outer layer generally has a thickness of between 200 and 600 μm but can go down to 50 μm for films and go up to 1 mm or more for large packages (drums. ..).

The invention also relates to a means for closing off said packages provided with an internal film formed from a polyamide film comprising aromatic patterns coming into application on said packages.

All the variants indicated above relating to the packaging apply to said sealing means.

In particular, the sealing means is a multilayer material whose outer layer is chosen from the group consisting of polyesters such as polyethylene terephthalate (PET) or polyolefins such as polypropylene (PP) or polyethylene (PE).

This sealing means is in particular a cylindrical capsule inside which is housed an internal film as defined above.

Among the numerous packages according to the invention which can be produced, mention may be made of the following applications:

- multilayer plastic bottles of the PP / L / PA type; PET / L / PA.

There is shown in Figure 1 attached such a bottle. This figure is a view in longitudinal section in which the bottle 1 formed of a cylindrical body 2 and a neck 3 consists of an outer layer 4 made of polyethylene terephthalate, an intermediate binder layer 5 and an internal layer 6 of polyamide with aromatic units.

The capsule 7 is formed of a cylindrical body 8 and a circular base 9. Inside the capsule 7 is housed a disc formed of a layer of PE 10 applied to the inner face of the base and a layer of aromatic polyamide 11 bearing on the neck 3.

It is also possible to produce cardboard packaging, the inner face of which is coated with a polyamide film with aromatic patterns such as bricks, but also metal cans comprising such a coating or closure articles (capsules, lids).

The invention also relates to the use of a polyamide comprising aromatic units for the production of packaging intended to come into contact with anethole solutions, in particular weakly alcoholic, in order to limit the loss of anethole in contact with the wall. conditioning.

It also relates to a process intended to limit the loss of anethole contained in alcoholic or non-alcoholic solutions, in particular weakly alcoholic, in contact with the wall of the packaging in polymer material, characterized in that the wall in polymer material in contact with the solution of anethole is a polyamide comprising aromatic units.

The invention also relates to a process for producing a package containing an alcoholic or non-alcoholic drink comprising anethole, characterized in that a package is filled as described above with said drink which is then closed off. this.

The invention is now illustrated by the following examples, given by way of illustration.

Example 1 Bottles consisting of an outer layer of polypropylene and an inner film of a film of polyamide of the SELAR PA® brand are formed by co-extrusion with an adhesion binder. The internal film has an average thickness of 50 micrometers, the outer layer has an average thickness of 520 micrometers and the intermediate layer an average thickness of 44 micrometers.

The bottles are all heat sealed with a PE / ALU / PE seal and are filled cold in the presence of a bacteriostatic agent, an aniseed non-alcoholic solution containing 235 mg / l of anethole, then are left for 12 months at 20 ° C. .

The loss of anethole is evaluated periodically: It is found that after 6 months, the loss of anethole is 12.7% and that after one year it is 14%. We therefore observe a plateau from six months, the loss of anethole having changed little since this term.

Example 2

Bottles consisting of an outer polypropylene layer and an inner film of a SELAR PA® brand polyamide film are formed by co-extrusion with an adhesion binder. The inner film has an average thickness of 50 micrometers, the outer layer has an average thickness of 520 micrometers and the intermediate layer an average thickness of 44 micrometers. The bottles are all heat sealed with a seal

PE / ALU / PE and are filled cold in the presence of a bacteriostatic, an anise solution containing:

- 235 mg / l of anethole,

- 6% alcohol by volume, then left for 12 months at 20 ° C.

The loss of anethole is evaluated periodically:

It is found that after 6 months, the loss of anethole is 11.8% and that after one year it is 13%. We therefore observe a plateau from six months, the loss of anethole having changed little since this term. Example 3

Another test was carried out with identical bottles filled with an aniseed drink containing 2 g / l of anethole and 45% v / v of alcohol.

The bottles are left for 12 months at 20 ° C. The loss of anethole is evaluated periodically:

It is found that after 6 months, the loss of anethole is 5% and that after one year it is 6%. We therefore observe a plateau from six months, the loss of anethole having changed little since this term.

Example 4 (comparative)

Bottles formed of polyethylene terephthalate sold by the company Cusenier (France) for fruit syrups

(Sironimo®) are filled with the same solutions as in Examples 1 and 2 and are left for 12 months at 20 ° C. The loss of anethole is evaluated periodically. We see that after 6 months, the loss is around 90% and 100% after 12 months.

Example 5 (comparative)

An example similar to Example 4 was carried out with polyethylene bottles sold by the company Pampryl (France) for fruit juices and with polypropylene bottles.

After 6 months there is a loss greater than 90% and 100% after 12 months.

Example 6 (comparative)

An example similar to Example 4 with a PVC bottle is made.

After 6 months there is a loss greater than 90% and 100% after 12 months. Example 7 (comparative)

A test similar to Example 4 with a glass bottle is carried out. There is a loss of about 3% after 6 months and about 6% after 12 months. The diagram in FIG. 2 summarizes the results obtained as a percentage of loss of anethole as a function of the number of months for trials 1,4,5,6 and 7.

We conclude from these experiments: while it was well known that polymers with aromatic units such as PET or polystyrene were not suitable for the reasons explained in the presentation of the invention and that it was the same for polyolefins , the particular combination of aromatic units and amide groups leads to a drastic reduction in the loss of anethole.

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Claims

1. Packaging formed of at least one internal film, containing an optionally alcoholic beverage or not based on anethole, characterized in that the internal film of said packaging is formed of a polyamide film comprising aromatic units.

2. Packaging according to claim 1, characterized in that the polyamide film is such that the water absorption measured according to ASTM D570 is less than 8% and the water uptake measured according to ASTM D570 is less than 5%.

3. Packaging according to claim 1, characterized in that the polyamide film is such that the oxygen permeation rate (cc-20 _μ / m2 day, atm) at 20 ° C and 0% RH is less than 4.

4. Packaging according to one of claims 1 to 3, characterized in that the film is a polyamide resulting from the polycondensation of meta-xylylenediamine with adipic acid.

5. Packaging according to claim 1, characterized in that the drink is non-alcoholic or low-alcoholic.

6. Packaging according to claim 5, characterized in that the drink comprises up to 10% by volume of alcohol.

7. Packaging according to claim 6, characterized in that the drink comprises 3 to 9% by volume of alcohol.

8. Packaging according to claim 1, characterized in that the aqueous alcoholic or non-alcoholic drink comprises 0.01 to 2 g / l of anethole.

9. Packaging according to claim 8, characterized in that the aqueous alcoholic or non-alcoholic drink comprises 0.02 to 2 g / l of anethole.

10. Packaging according to one of the preceding claims, characterized in that the film has a thickness between 10 and 100 micrometers.

11. Packaging according to claim 10, characterized in that the film has a thickness between 20 and 80 micrometers.

12. Packaging according to claim 1, characterized in that it comprises an external structure layer and an internal film formed from a polyamide film comprising aromatic units.

13. Packaging according to claim 12, characterized in that the outer layer is made of polymer.

14. Packaging according to claim 13, characterized in that the outer layer is chosen from the group consisting of polyesters and polyolefins.

15. Packaging according to claim 14, characterized in that the outer layer is chosen from the group consisting of polyethylene terephthalate, polypropylene and polyethylene.

16. Packaging according to claim 12, characterized in that the outer layer is made of metal.

17. Packaging according to claim 12, characterized in that the outer layer is cardboard.

18. Packaging according to one of claims 12 to 17, characterized in that it comprises an intermediate layer of a binder.

19. Packaging according to one of claims 12 to 15 or 18, characterized in that it is in the form of a bottle.

20. sealing means for packaging according to one of the preceding claims, provided with an internal film formed of a polyamide film comprising aromatic patterns coming into application on the opening of said packaging.

21. sealing means according to claim 20, characterized in that it consists of a cylindrical capsule inside which is housed an internal film formed of a polyamide film comprising aromatic units coming into application on the opening of said packaging.

22. Use of a polymer film for the production of a packaging in contact with weakly alcoholic anethole solutions in order to limit the loss of anethole in contact with the wall of the packaging, characterized in that the film is a polyamide comprising aromatic units as described in claims 1 to 3, 10, 11.

23. Method for limiting the loss of anethole contained in solutions with low alcohol content in contact with the walls of a packaging made of polymer material, characterized in that the wall made of polymer material in contact with the solution of anethole is a polyamide as defined in claims 1 to 3, 10, 11.