MXPA98003098A - Packaging for anethole based beverage - Google Patents

Abstract

The invention concerns a long-lasting unilayer or multilayer packaging containing an alcoholic or non-alcoholic anethole based beverage, characterised in that the layer in contact with said beverage is made of a polymer containing condensed aromatic patterns. The polymer is in particular naphtalate polyethylene (PEN) with a crystalline rate higher than 20%. The invention also concerns a method for limiting the degradation of anethole based beverages using such a polymer.

Description

CONTAINER FOR A DRINK MADE OF ANETOL DESCRIPTIVE MEMORY The present invention relates to a new container containing an aqueous alcoholic or non-alcoholic beverage made from anethole. It also relates to a process with which it is intended to limit the penetrate of anethole present in an optional alcohol solution that makes contact with the polymer wall of a container, and the use of a polymer film for the production of a container that makes contact with optionally alcoholic anethole solutions, to limit the loss of the anethole that makes contact with the container wall. Anise-flavored drinks contain anethole or para-propenylmethoxybenzene, predominantly in trans form, (greater than 96-97%). Anethole has the special property of being very poorly soluble in water (<50 mg / l) and soluble in alcohol. In the presence of water the anethole becomes opaque, while in a water / alcohol solution of high alcohol content (of the order of 45% by volume) the anethole remains in the dissolved state (2 g / 1. alcohol-free beverages or with a little alcohol (4-9 vol.%) an emulsifier is used because the anethole is no longer soluble.When anise-flavored drinks are stored, considerable degradation occurs with the course of the time, especially under the effect of: - light (cis-trans isomerization), - oxidation in the presence of light, interaction between anethole and the packaging material. Although, with the help of containers that are opaque to ultraviolet light and that act as a barrier to gases, it has been possible to overcome the first two disadvantages mentioned above, not the case of the third point that refers to the loss of anethole that makes contact with the packaging material. In fact, in the case of containers made of polyethylene (polyethylene, oylpropylene, polyvinyl chloride, polyethylene terephthalate) that are conventionally used, a very large loss of flavor (up to 100%) is observed in the course of time. the drink is in contact with the polymer walls and this prevents the anise-flavored drinks from being marketed in plastic containers. This problem is even more serious in the case of alcohol-free or low-alcohol drinks that are made of anethole, in which case, the loss that comes from being in contact with the polymer is even faster. Anethole has a low solubility coefficient in water but has a high solubility coefficient in polymers. This phenomenon is proportionally more important in the case of beverages that contain little or no alcohol they contain alcohol. This produces a considerable electrostatic interaction with the surface of the polymer and the adsorption of the anethole present therein. In addition, the affinity of anethole with the polymers is such that an absorption phenomenon occurs due to the insertion of this compound between the polymer chains. Therefore, this implies a dynamic phenomenon of abso rción / adso rción. On the other hand, anethole shows a strong tendency to polymerize in polyanetol. This polymerization of cationic type is promoted by the highly nucleophilic nature of the methoxy group. This phenomenon occurs especially in the case of polymers derived from styrene, maleic anhydride or acrylonitrile, which are commonly used as a beverage container. This is due to the fact that anethole reacts with the molecular chains of these polymers. However, anethole can also react with the residual monomers, given the well known copolymerization reaction with styrene (T. Higashimura et al., Journal of Polymer Science: part A. 1, vol 10, 85-93, 1972). or terpolymerization with maleic anhydride and acrylic monomers such as acrylonitrile (T. Kobuko et al., Macromolecules, vol.3, No. 5, Sept.-Oct., 1970; 518-523). For all these reasons, until now there is no known plastic container for beverages made with anethole. That's why currently flavored drinks to anise are packaged in glass bottles. Accordingly, it is desirable to propose a new container made of polymer material which makes it possible to achieve the inertia capacity of the glass or to approach it. After conducting systematic research, the applicant company has developed a new container to contain anise-flavored drinks optionally alcoholic, which exhibits satisfactory characteristics, especially as regards the lack of anethole sorption. In fact, it has been found that, unlike polyethylene terephthalate, which shows a very strong absorption with respect to anethole, polymers containing condensed aromatic units show, on the contrary, a very weak absorption with respect to anethole. This is the reason why the subject matter of the invention is firstly a container for an optionally alcoholic beverage including apetol, characterized in that the layer of said packaging which makes contact with said beverage is formed from a polymer film containing units. condensed aromatics. "Container" shall mean any container capable of containing said beverage, whether in the form of a bottle, can or other equivalent closed systems, including wineskins and wineskins. In the context of the present invention, the packaging concept also extends to the closure and test means of filtration of the various containers referred to above. The present invention relates in particular to the closure means for any container with which it is intended to contain a beverage made from anethole. Such a closure means is advantageously provided with an inner metallic foil formed from a polymer film containing condensed aromatic units, which is placed over the opening of said container. In particular, it may consist of a cylindrical cap inside which there is a metal foil formed from a polymer film containing condensed aromatic units, which is placed over the opening of said container. Condensed aromatic units refer in particular to bivalent or tri-fused divalent aromatic systems, such as the bivalent units of naphthalene or anthracene. These units are present, in particular, alternating with aliphatic units, these two types of units being united by groups of well-known chemical functional esters, of the amide or urethane type. Therefore, in many cases there is involvement of copolymers, in fact. It is understood that these polymers are linear and, therefore, thermoplastic. A second important characteristic of these polymers is their degree of crystallinity. In fact, it has it has been discovered that a particularly low sorption is observed when the polymers have a degree of crystallinity greater than or equal to 20%, with between 20 and 45% being preferable, 20 or 30% being more advantageous. Very briefly, it is known that crystallinity is related to the increase in order within the chains of the polymer, due especially to the alignment of the latter, one with respect to another. Processes are known which make it possible to increase the crystallinity, by virtue of a relaxation of the stresses by a temper greater than 20% and even up to 45%. This is especially the case with polyethylene naphthalate. These procedures include those developed by Sidel, known as SRF or SRCF. The tempering can be carried out by means of various techniques, especially using the hot mold technique or by softening the biaxially extracted product. The SRCF process is a particular embodiment of the general process, in which, to increase the crystallinity of the aromatic esters, the polyester in polymerized form is first extracted biaxially and then softened to relax the stresses caused by the biaxial extraction and then, and only Then, give it the final form. The SRCF procedure, which derives from the cold procedure or two-stage procedure, starts with a pre-form manufactured in an independent press. The procedure includes four stages subsequently: 1) the body of the pre-form is heated; 2) a first bottle of exaggerated size with biaxial orientation is inflated; 3) this bottle goes to an infrared oven called "recovery oven"; two things happen: on the one hand the ring crystallizes and turns white; on the other, under the effect of temperature, 200 ° C for about 1 minute 30 seconds, the body of the bottle contracts; the stresses caused during the biaxial extraction stages have relaxed, the bottle then takes a "sword-like" shape, the density of the PEN that makes up the body of the article has increased considerably, from now on the PAN is crystalline and has turned resistant to heat; 4) the product is finished inflating a second occasion with biaxial orientation, adopting the bottle then its final shape. Among the polymers according to the invention, those selected advantageously are polyesters obtained by polycondensation of ethylene or, more generally, of alkylene glycol and of bi- or tri-fused aromatic diacids, especially naphthalic or anthracic acid. Among these, preference is given to polyester of ethylene glycol and naphthalic acid (PEN). The container to result be particularly profitable in the case of non-alcoholic drinks or those containing little alcohol whose alcohol content is preferably less than 10% by volume, preferably between 3 and 9%. In a known manner, the aqueous alcoholic beverage includes 0.01 to 2 g / 1 of anethole, with 0.02 g / 1 or more of anethole being preferable. In concentrates that must be diluted, such as the beverage known under the name "Pastis", the anethole concentration is of the order of 2 g / 1. In ready-to-drink alcoholic beverages it is of the order of 200 to 400 mg / l. In the case of anise-flavored drinks it is of the order of 10 to 50 mg / l. It should be remembered that in the case of alcoholic beverages with a strength of 45% by volume, anethole dissolves completely, while in the case of alcohol-free or low alcohol-containing beverages (4-9% by volume) an emulsifier is used to maintain the anethole in the stable emulsion form. Generally, in addition to the characteristics of a barrier for the anethole, the container according to the invention must show a sufficient impermeability to carbon dioxide. It must also show a resistance to tearing and a modulus of elasticity sufficient for the use considered. The container must be in the form of a layer or in the multilayer form.

In the case of a multilayer container, the inner metal foil is formed from a polymer film containing condensed aromatic units. The film is attached, by means of an adhesive, for example, to a structural material, which is itself optionally multilayer (metal, cardboard, uni or multilayer polymeric material). The thickness of the inner metallic sheet is between 50 and 200 μm and, in general, it must be sufficient to satisfy the various criteria indicated above. This may be the case, therefore, for cans made of metal, especially aluminum, covered with a metallic sheet of polymer that includes condensed aromatic units. It can also be cardboard boxes, commonly called "cartons", covered inside with a metal sheet of polymer containing condensed aromatic units. More particular mention will be made of the bottles made of an outer layer of polypropylene and an inner metallic sheet of polymer containing condensed aromatic units. These two layers are joined, for example, with the aid of an adhesive or coater. According to a preferred embodiment, the package is in the form of a unicapped polymer containing condensed aromatic units. The thickness of the uni or multilayer bottles is generally from 0.2 to 0.5 mm in the case of the body and 0.5 to 2.5 mm in the case of the lower part, although these thicknesses may vary according to the size of the container. The preparation of such polymers is carried out in a conventional blow molding machine such as that used for PET with or without biaxial orientation, in accordance with conventional one-stage or two-stage processes. Therefore, not requiring the use of a machine that is specific to the product involves relatively inexpensive processing. Accordingly, the package is in the form of a single-layer or multilayer material obtained especially through blow-molding. The package according to the invention can keep a beverage made from anethole, in particular those that are not alcoholic or that contain little alcohol, under the same conditions as a glass bottle; that is, without substantial degradation of the organoleptic properties. Furthermore, they are transparent in the case of single-layer packaging or multilayer packaging in which the structural layers are transparent, easy to transform and economical. The invention also relates to a closure means, especially for the aforementioned package, provided with an inner metallic sheet made of material impermeable to anethole; in particular a polymer that contains aromatic units condensed, which is placed on said container. All the alternative forms indicated above and related to the container correspond to said closure means. This closure means is in particular a cylindrical cap having an inner metal foil of a polymer, as described above. In figure 1, attached, a bottle seen in longitudinal section is shown, in which the bottle 1, formed by a cylindrical body 2, a neck 3 and a lower part 4, consists of a polymer material made of polyethylene naphthalate . The bottle has a thickness of 0.2 mm in the cylindrical body and 0.6 mm in the lower part. The cover 5 is formed by a cylindrical body 6 and a circular base 7. Inside the cover 5 there is a disc 8 formed from a layer of PEN 8 applied to the internal face of the base and a layer of PEN 9 on the neck 3. The invention also relates to the use of a polymer containing condensed aromatic units for the production of a single-ply or pulticapa container for beverages made from anethole, in particular with little alcohol, to limit the loss of the anethole which makes contact with the container wall, said polymer forming the layer that contacts said beverages. Also, the invention relates to a process with which it is intended to limit the degradation of beverages made on the basis of of anethole, especially those that do not contain alcohol or contain little; further characterized in that said beverages are stored in a single-layer or multi-layer durable packaging in which the layer contacting said beverages consists of a polymer containing condensed aromatic units. The examples presented below, by way of illustration, exemplify the invention.

EXAMPLE 1 Bottles made of a single-layer polyethylene glycol naphthalate (PEN) with a crystallinity close to 25%, of 1.5 1, with a weight of 59 g, with average thickness of 0.2 mm in the case of the body and 0.6 mm in the case of the lower part, by means of injection blow molding with biaxial orientation and heat fixing in hot molds, using the conventional two-stage process. In the presence of a bacteriostat, the bottles were filled cold with a non-alcoholic anise-flavored solution containing 400 mg / l of anethole, and then left for 12 months at 20 ° C. The loss of anethole was evaluated at regular intervals. It was observed that after 9 months the loss of anethole was 22% and that after one year it was 25%. Therefore, at nine months it was observed that a level of stability began, with a relatively small in the loss of anethole since then, EXAMPLE 2 (COMPARATIVE) With the same solution as in Example 1, bottles made of polyethylene terephthalate having a degree of crystallinity of about 15% were filled and left at 20 ° C for 12 months. The loss of anethole was evaluated at regular intervals. It was observed that after 6 months the loss was 92% and, after 12 months, 100%. The results are summarized in the following table and in the attached figure, where the percentage of anethole loss is shown in months (PEN -, PET - β).

This result is, therefore, completely surprising, keeping in mind the small change in structure (naphthalene instead of benzene).

Claims (18)

NOVELTY OF THE INVENTION CLAIMS

1. Durable multilayer or multilayer container containing an optional alcoholic beverage made of anethole, further characterized in that the layer contacting said beverage is formed from a polymer containing condensed aromatic units.

2. Packaging according to claim 1, further characterized in that the condensed aromatic units are di- or tri-condensed, especially the bivalent units of naphthalene or anthracene.

3. Packaging according to claims 1 and 2, further characterized in that the polymer is a polyester of an alkylene glycol and a condensed aromatic diacid, especially naphthalic acid or anthracic acid.

4. Packaging according to claim 3, further characterized in that the polyester is polyethylene glycol naphthalate (PEN).

5. Packaging according to one of claims 1 to 4, further characterized in that the polymer, which contains condensed aromatic units, has a degree of crystallinity greater than or equal to 20%.

6. Packaging according to claim 5, further characterized in that the polymer, which contains units condensed aromatics, has a degree of crystallinity of between 20 and 45%.

7. Container according to one of claims 1 to 6, further characterized in that it is in the form of a unicap.

8. Packaging according to claim 7, further characterized in that it is in the form of a bottle with a thickness between 0.2 to 0.5 mm, in the case of the body, and 0.5 to 2.5 mm, in the case of the lower part.

9. Packaging according to claim 7 or 8, further characterized in that the bottle is provided with a closure means whose face, which faces the opening of the bottle, is provided with a material impermeable to anethole, especially a polymer containing condensed aromatic units.

10. Packaging according to claim 1, further characterized in that the beverage has no alcohol or has very little.

11. Packaging according to claim 10, further characterized in that the beverage includes up to 10% by volume of alcohol.

12. Packaging according to claim 11, further characterized in that the beverage includes from 3 to 9% by volume of alcohol.

13. Package according to claim 1, 10 to 12, further characterized because the aqueous beverage Alcoholic or non-alcoholic includes 0.01 to 2 g / 1 anethole.

14. Container according to claim 13, further characterized by the aqueous alcoholic or non-alcoholic beverage includes 0.02 to 2 g / 1 of anethole.

15. Closing means for packaging according to one of the preceding claims, provided with an inner metal sheet formed from a polymer film containing condensed aromatic units, which is placed over the opening of said package.

16. Closing means according to claim 15, further characterized in that it consists of a cylindrical cover in which there is a metal sheet formed from a polymer film containing condensed aromatic units, which is placed in the opening of said container.

17. Use of a terpolymer containing condensed aromatic units, as defined in one of claims 1 to 6, for the production of a single-layer or multilayer container for anethole-based nectar drinks, in particular for those containing very little alcohol, to limit the loss of the anethole that makes contact with the container wall, the polymer forming a layer that makes contact with said beverages.

18. Procedure to limit the degradation of beverages made with anethole, in particular those containing very little or no alcohol; further characterized in that said beverages are stored in a single-layer or multi-layer durable package in which the layer contacting said beverages consists of a polymer containing condensed aromatic units, as defined in one of claims 1 to 6.