EP0912422B1 - Long-lasting packaging for anethole-based beverage - Google Patents

Long-lasting packaging for anethole-based beverage Download PDF

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Publication number
EP0912422B1
EP0912422B1 EP97930555A EP97930555A EP0912422B1 EP 0912422 B1 EP0912422 B1 EP 0912422B1 EP 97930555 A EP97930555 A EP 97930555A EP 97930555 A EP97930555 A EP 97930555A EP 0912422 B1 EP0912422 B1 EP 0912422B1
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EP
European Patent Office
Prior art keywords
packaging
terpolymer
anethole
alcoholic
acrylonitrile
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EP97930555A
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German (de)
French (fr)
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EP0912422A1 (en
Inventor
Patrice Robichon
Philippe Noble
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Pernod Ricard SA
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Pernod Ricard SA
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D1/00—Containers having bodies formed in one piece, e.g. by casting metallic material, by moulding plastics, by blowing vitreous material, by throwing ceramic material, by moulding pulped fibrous material, by deep-drawing operations performed on sheet material
    • B65D1/02—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents
    • B65D1/0207—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents characterised by material, e.g. composition, physical features
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D85/00—Containers, packaging elements or packages, specially adapted for particular articles or materials
    • B65D85/70—Containers, packaging elements or packages, specially adapted for particular articles or materials for materials not otherwise provided for
    • B65D85/72—Containers, packaging elements or packages, specially adapted for particular articles or materials for materials not otherwise provided for for edible or potable liquids, semiliquids, or plastic or pasty materials
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]

Definitions

  • the present invention relates to packaging monolayer or multilayer, long-lived, containing a drink aqueous, alcoholic or not, based on anethole.
  • It also relates to a method intended to limit the loss of anethole contained in an optionally alcoholic solution in contact with the wall of a packaging, as well as the use of a film polymer for producing a packaging in contact with possibly alcoholic anethole solutions, in order to limit the loss anethole in contact with the packaging wall.
  • Anise drinks contain anethole or para propenyl methoxy benzene, in majority trans form (greater than 96-97%).
  • Anethole has the distinction of being very sparingly soluble in water ( ⁇ 50 mg / l) and soluble in alcohol. In the presence of water, the anethole becomes cloudy, so than in a water / alcohol solution with a high alcohol content (around 45% by volume), the anethole remains in the solubilized state.
  • an emulsifier is used because the anethole is no longer soluble.
  • Anethole has a low coefficient of solubility in water but a high solubility coefficient in alcohols. This phenomenon is all the more important for drinks with little or no alcohol. This induces significant electrostatic interaction with the polymer surface and adsorption of anethole thereon.
  • the affinity of anethole for polymers is such that there is an absorption phenomenon, by insertion of this compound between the polymer chains. It is therefore a dynamic phenomenon adsorption / absorption.
  • Anethole also reveals a strong propensity to polymerize in polyanethole.
  • This cationic type polymerization is favored by the very electron-donating character of the methoxy group. This phenomenon occurs produced in particular in the case of polymers derived from styrene, from anhydride maleic or acrylonitrile commonly used as packaging for beverages. This is due to the fact that anethole reacts with the molecular chains of these polymers.
  • anethole can also react with monomers residual 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 (TK. Kobuko et al, Macromolecules, vol. 3, n ° 5, Sept-Oct. 1970,518-523).
  • the applicant company has point a new packaging intended to contain aniseed drinks possibly alcoholic which have satisfactory characteristics, particularly with regard to the absence of sorption of anethole while with the qualities of transparency and low manufacturing cost required.
  • the invention firstly relates to a long-lasting single-layer or multi-layer packaging containing a possibly anethole alcoholic drink, characterized by that the layer in contact with said drink is formed of a terpolymer methyl acrylate-acrylonitrile-butadiene.
  • Packaging means any packaging likely to contain said drink, whether in the form of a bottle, box or other equivalent closed systems, including bottles and pouches.
  • long shelf life is meant that the shelf life is at least 6 months.
  • the present invention relates in particular to the means closure for any packaging intended to contain a beverage based anethole.
  • Such a sealing means is advantageously provided with a internal film formed from a film of methyl acrylate-acrylonitrile-butadiene terpolymer coming into application on the opening of said conditioning.
  • It can in particular consist of a cylindrical capsule with inside which is housed an internal film formed of a film of methyl acrylate-acrylonitrile-butadiene terpolymer coming in application on the opening of said packaging.
  • the packaging was particularly interesting in the case of non-alcoholic or low-alcoholic drinks whose content alcohol is preferably less than or equal to 10% by volume, preferably between 3 and 9%.
  • the aqueous alcoholic or non-alcoholic drink comprises from 0.01 to 2 g / l of anethole, preferably 0.02 g / l or more of anethole.
  • the anethole concentration is around 2 g / l.
  • ready-to-drink alcoholic beverages it is around 200 to 400 mg / l.
  • anise flavored drinks it is in the range of 10 to 50 mg / l.
  • terpolymers suitable in the context of the present invention preference will be given to those having an oxygen permeability of less than 0.8 cm 3 .mm / m 2 .day.bar at 23 ° C, at a relative humidity of 100 %.
  • the terpolymer has a level of butadiene between 8 and 20%.
  • the terpolymer is chosen from the group consisting of the terpolymer with a butadiene content of approximately 10% or the terpolymer, the butadiene content of which is approximately 18%.
  • Barex 210® polymer has an oxygen permeability of 0.3 cm 3 .mm / m 2 .day.bar at 23 ° C.
  • Barex 218® polymer has an oxygen permeability of 0.6 cm 3 .mm / m 2 .day.bar at 23 ° C.
  • EP-A-433 097 describes a similar resin container to that described in the present invention for packaging beverages such as water, tea, coffee, fruit juices, grape juices. This document does not describe or suggest the use of this resin for packaging anethole drink.
  • films formed of a methyl acrylate-acrylonitrile-butadiene terpolymer must have sufficient impermeability towards carbon dioxide. They must also have resistance to tear and a modulus of elasticity sufficient for the application considered.
  • the packaging may be in the form of a monolayer or in multilayer form.
  • the inner layer is formed from a film of methyl acrylate-acrylonitrile-butadiene terpolymer.
  • the film is associated with a structural material, itself possibly multilayer (metal, cardboard, mono or multilayer material polymeric).
  • the thickness of the terpolymer layer may vary so notable depending on whether the packaging is monolayer or multilayer. She will preferably be between 200 and 500 ⁇ m, advantageously between 300 and 400 ⁇ m, but can go down to 50 ⁇ m for films and go up to 1 mm or more for large packages (drums, for example).
  • the processing of such polymers is carried out on a machine usual extrusion blow molding, such as that used for PVC with or without bi-orientation.
  • the packaging therefore takes the form of a monolayer or multilayer material obtained by extrusion.
  • the packaging according to the invention can retain a anethole-based drink, in particular low or non-alcoholic, in same conditions as a glass bottle, i.e. without degradation substantial organoleptic qualities.
  • the invention also relates to a sealing means for said packages provided with an internal film formed of a film of methyl acrylate-acrylonitrile-butadiene terpolymer coming in application on the opening of said packages.
  • This sealing means is in particular a cylindrical capsule with inside which is housed an internal film of a polymer such as defined above.
  • Figure 1 There is shown in Figure 1 attached a bottle, seen in longitudinal section, in which the bottle 1 formed from a body 2 cylindrical, a neck 3 and a bottom 4 is made of a material polymer in methyl acrylate-acrylonitrile-butadiene terpolymer.
  • the bottle has a thickness of 0.2 mm at body level cylindrical and 0.6 mm at the bottom.
  • the capsule 5 is formed of a cylindrical body 6 and a base circular 7. Inside the capsule 5 is housed a disc 8 formed of a methyl acrylate-acrylonitrile-butadiene terpolymer layer 8 applied to the inside of the base and a terpolymer layer methyl acrylate-acrylonitrile-butadiene 9 bearing on the neck 3.
  • the invention also relates to the use of a terpolymer methyl acrylate-acrylonitrile-butadiene, as described above for the realization of a monolayer or multilayer packaging, intended to contain anethole-based drinks which may be alcoholic in order to limit the degradation of these, said terpolymer forming the diaper in contact with said drinks.
  • It also relates to a method intended to limit the degradation of anethole-based drinks, especially weakly or not alcoholic, characterized in that said drinks are stored in a long-lasting single-layer or multi-layer packaging, the layer of which in contact with said drinks consists of an acrylate terpolymer of methyl-acrylonitrile-butadiene as defined above.
  • the bottles are cold filled in the presence of a bacteriostatic, non-alcoholic anise solution containing 400 mg / l anethole, then left for 12 months at 20 ° C,
  • the loss of anethole is evaluated periodically. We aknowledge that after 9 months, the loss in anethole is 25% and that after one year, it is 28%. We therefore observe a plateau from 9 months, the loss of anethole having little changed since that term.
  • Bottles formed from polyethylene terephthalate are filled of the same solution as that of Example 1 and are left for 12 months at 20 ° C.
  • the loss of anethole is evaluated periodically. We aknowledge that after 6 months, the loss is 92% and 100% after 12 months.
  • FIG. 2 shows the percentage of loss of anethole in months (Barex 218® - ⁇ -, PET -oulez-). Month 0 3 6 9 12 Barex®% 0 18 21 25 28 PET% 0 65 92 97 100
  • Example 2 An example similar to Example 1 was carried out with polyethylene bottles sold by Pampryl (France) for fruit juices and with polypropylene bottles.
  • Example 3 An example similar to Example 3 with a PVC bottle is realized .

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  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Laminated Bodies (AREA)
  • Wrappers (AREA)
  • Packages (AREA)
  • Food Preservation Except Freezing, Refrigeration, And Drying (AREA)
  • Packging For Living Organisms, Food Or Medicinal Products That Are Sensitive To Environmental Conditiond (AREA)
  • Thermally Insulated Containers For Foods (AREA)
  • Distillation Of Fermentation Liquor, Processing Of Alcohols, Vinegar And Beer (AREA)
  • Tea And Coffee (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention relates to a monolayer or multilayer long-life packaging containing an anethole-based alcoholic or non-alcoholic drink, characterized in that the layer in contact with the said drink is formed of a methyl acrylate/acrylonitrile/butadiene terpolymer. The invention also relates to a process intended to limit the degradation of an anethole-based alcoholic or non-alcoholic drink, in particular one which is low in alcohol or alcohol-free, characterized in that the said drinks are stored in a monolayer or multilayer long-life packaging whose layer in contact with the said drinks consists of a methyl acrylate/acrylonitrile/butadiene terpolymer.

Description

La présente invention concerne un conditionnement monocouche ou multicouche, de longue durée, contenant une boisson aqueuse, alcoolisée ou non, à base d'anéthole.The present invention relates to packaging monolayer or multilayer, long-lived, containing a drink aqueous, alcoholic or not, based on anethole.

Elle concerne également un procédé destiné à limiter la déperdition d'anéthole contenu dans une solution éventuellement alcoolisée au contact de la paroi d'un conditionnement, ainsi que l'utilisation d'un film polymère pour la réalisation d'un conditionnement en contact avec des solutions d'anéthole éventuellement alcoolisées, afin de limiter la déperdition d'anéthole au contact de la paroi du conditionnement.It also relates to a method intended to limit the loss of anethole contained in an optionally alcoholic solution in contact with the wall of a packaging, as well as the use of a film polymer for producing a packaging in contact with possibly alcoholic anethole solutions, in order to limit the loss anethole in contact with the packaging wall.

Les boissons anisées contiennent de l'anéthole ou para propényl méthoxy benzène, sous forme majoritaire trans (supérieure à 96-97 %). L'anéthole présente la particularité d'être très peu soluble dans l'eau (< 50 mg/l) et soluble dans l'alcool. En présence d'eau, l'anéthole se trouble, alors que dans une solution eau/alcool à forte teneur en alcool (de l'ordre de 45 % en volume), l'anéthole reste à l'état solubilisé.Anise drinks contain anethole or para propenyl methoxy benzene, in majority trans form (greater than 96-97%). Anethole has the distinction of being very sparingly soluble in water (<50 mg / l) and soluble in alcohol. In the presence of water, the anethole becomes cloudy, so than in a water / alcohol solution with a high alcohol content (around 45% by volume), the anethole remains in the solubilized state.

Dans le cas des boissons sans alcool ou faiblement alcoolisées (4-9 % vol), on a recours à un émulsifiant car l'anéthole n'est plus soluble.In the case of alcohol-free or low-alcohol drinks (4-9 % vol), an emulsifier is used because the anethole is no longer soluble.

Lors de la conservation de boissons anisées, des dégradations importantes apparaissent au cours du temps, notamment sous l'action de :

  • la lumière (isomérisation cis-trans),
  • l'oxydation en présence de lumière,
  • l'interaction entre l'anéthole et le matériau de conditionnement.
During the conservation of aniseed drinks, significant degradations appear 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.

Si on a pu pallier les deux premiers inconvénients précités à l'aide d'emballages opaques aux ultra-violet et présentant un effet barrière aux gaz, il n'en n'est pas de même en ce qui concerne le troisième point relatif à la déperdition d'anéthole au contact du matériau de conditionnement.If we were able to overcome the first two disadvantages mentioned above using opaque ultraviolet packaging with 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.

De fait, dans le cas des conditionnements en polymère utilisés classiquement (polyéthylène, polypropylène, polychlorure de vinyle, polyéthylènetérephtalate), on observe au cours du temps une perte très importante d'arôme, (jusqu'à 100 %) au contact des parois polymères, ce qui empêche de commercialiser les boissons anisées dans des emballages plastiques. In fact, in the case of the polymer packaging used conventionally (polyethylene, polypropylene, polyvinyl chloride, polyethylene terephthalate), we observe over time a very significant aroma (up to 100%) in contact with the polymer walls, which prevents marketing aniseed beverages in packaging plastics.

Le document Ernährung/nutrition, vol. 3 n° 1, 1979 illustre au tableau de la page 35 le fait que les matériaux plastiques tels que le polyéthylène ne conviennent pas pour le conditionnement des boissons à base d'anéthole.The document Ernährung / nutrition, vol. 3 n ° 1, 1979 illustrates at table on page 35 the fact that plastic materials such as polyethylene are not suitable for the packaging of beverages anethole base.

Ce problème est encore plus sensible dans le cas des boissons sans alcool ou faiblement alcoolisées à base d'anéthole pour lesquelles la déperdition au contact du polymère est encore plus rapide.This problem is even more significant in the case of drinks without alcohol or low alcohol content based on anethole for which the loss on contact with the polymer is even faster.

Plusieurs observations scientifiques illustrent le comportement particulier de ce composé.Several scientific observations illustrate the behavior particular of this compound.

L'anéthole présente un faible coefficient de solubililé dans l'eau mais un coefficient de solubilité élevé dans les alcools. Ce phénomène est d'autant plus important pour les boissons peu ou pas alcoolisées. Cela induit une interaction électrostatique importante avec la surface du polymère et l'adsorption de l'anéthole sur celle-ci.Anethole has a low coefficient of solubility in water but a high solubility coefficient in alcohols. This phenomenon is all the more important for drinks with little or no alcohol. This induces significant electrostatic interaction with the polymer surface and adsorption of anethole thereon.

Par ailleurs, l'affinité de l'anéthole pour les polymères est telle qu'il se produit un phénomène d'absorption, par insertion de ce composé entre les chaínes du polymère. Il s'agit donc d'un phénomène dynamique d'adsorption/absorption.Furthermore, the affinity of anethole for polymers is such that there is an absorption phenomenon, by insertion of this compound between the polymer chains. It is therefore a dynamic phenomenon adsorption / absorption.

L'anéthole révèle en outre une forte propension à polymériser en polyanéthole. Cette polymérisation de type cationique est favorisée par le caractère très donneur d'électrons du groupement méthoxy. Ce phénomène se produit notamment dans le cas des polymères dérivés du styrène, d'anhydride maléique ou d'acrylonitrile couramment utilises en tant que conditionnements pour boissons. Ceci est du au fait que l'anéthole réagit avec les chaínes moléculaires de ces polymères.Anethole also reveals a strong propensity to polymerize in polyanethole. This cationic type polymerization is favored by the very electron-donating character of the methoxy group. This phenomenon occurs produced in particular in the case of polymers derived from styrene, from anhydride maleic or acrylonitrile commonly used as packaging for beverages. This is due to the fact that anethole reacts with the molecular chains of these polymers.

Mais l'anéthole peut également réagir avec les monomères résiduels étant donné la réaction de copolymérisation bien connue avec le styrène (T. Higashimura et al, Journal of Polymer Science: part A.1, vol.10,85-93 (1972)) ou la terpolymérisation avec l'anhydride maléique et les monomères acryliques tels que l'acrylonitrile (TK. Kobuko et al, Macromolecules, vol. 3, n° 5, Sept-Oct. 1970,518-523).But anethole can also react with monomers residual 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 (TK. Kobuko et al, Macromolecules, vol. 3, n ° 5, Sept-Oct. 1970,518-523).

De fait, à l'heure actuelle les seuls conditionnements acceptables pour les boissons à base d'anéthole sont les conditionnements de verre et les conditionnements en polymère utilisés classiquement conduisent au cours du temps à une perte très importante d'arôme (jusqu'à 100 %) au contact de parois polymères ce qui empêche de commercialiser les boissons anisées dans des emballages plastiques. In fact, at present the only acceptable packaging for anethole-based drinks are the glass containers and the polymer packaging conventionally used lead during the time to a very significant loss of aroma (up to 100%) on contact with polymer walls which prevents the marketing of aniseed drinks in plastic packaging.

C'est pourquoi actuellement les boissons anisées sont conditionnées dans des bouteilles en verre.This is why currently aniseed drinks are packaged in glass bottles.

Il est donc souhaitable de proposer de nouveaux conditionnements permettant d'atteindre ou d'approcher les performances d'inertie du verre.It is therefore desirable to propose new packaging allowing to reach or approach the inertia performance of the glass.

Après des recherches systèmatiques, la société déposante a mis au point un nouveau conditionnement destiné à contenir des boissons anisées éventuellement alcoolisées qui présentent des caractéristiques satisfaisantes, notamment en ce qui concerne l'absence de sorption de l'anéthole tout en possédant les qualités de transparence et de faible coût de fabrication requis.After systematic research, the applicant company has point a new packaging intended to contain aniseed drinks possibly alcoholic which have satisfactory characteristics, particularly with regard to the absence of sorption of anethole while with the qualities of transparency and low manufacturing cost required.

C'est pourquoi, l'invention a en premier lieu pour objet un conditionnement de longue durée monocouche ou multicouche contenant une boisson éventuellement alcoolisée à base d'anéthole, caractérisé en ce que la couche en contact avec ladite boisson est formée d'un terpolymère acrylate de méthyle-acrylonitrile-butadiène.This is why, the invention firstly relates to a long-lasting single-layer or multi-layer packaging containing a possibly anethole alcoholic drink, characterized by that the layer in contact with said drink is formed of a terpolymer methyl acrylate-acrylonitrile-butadiene.

Par "conditionnement", on entendra tout emballage susceptible de contenir ladite boisson, que ce soit sous forme de bouteille, de boíte ou d'autres systèmes fermés équivalents, y compris les outres et poches."Packaging" means any packaging likely to contain said drink, whether in the form of a bottle, box or other equivalent closed systems, including bottles and pouches.

Par "longue durée", on entend que la durée de conservation est d'au moins 6 mois.By "long shelf life" is meant that the shelf life is at least 6 months.

Dans le cadre de la présente invention la notion de conditionnement s'étend également aux moyens d'obturation et d'étanchéité des différents contenants rappelés ci-dessus.In the context of the present invention the concept of packaging also extends to sealing and sealing means of the different containers mentioned above.

La présente invention concerne en particulier les moyens d'obturation pour tout conditionnement destiné à contenir une boisson à base d'anéthole.The present invention relates in particular to the means closure for any packaging intended to contain a beverage based anethole.

Un tel moyen d'obturation est avantageusement pourvu d'une pellicule interne formée d'un film de terpolymère acrylate de méthyle-acrylonitrile-butadiène venant en application sur l'ouverture dudit conditionnement.Such a sealing means is advantageously provided with a internal film formed from a film of methyl acrylate-acrylonitrile-butadiene terpolymer coming into application on the opening of said conditioning.

Il peut en particulier être constitué d'une capsule cylindrique à l'intérieur de laquelle est logée une pellicule interne formée d'un film de terpolymère acrylate de méthyle-acrylonitrile-butadiène venant en application sur l'ouverture dudit conditionnement.It can in particular consist of a cylindrical capsule with inside which is housed an internal film formed of a film of methyl acrylate-acrylonitrile-butadiene terpolymer coming in application on the opening of said packaging.

Le conditionnement s'est révélé particulièrement intéressant dans le cas des boissons non alcoolisées ou faiblement alcoolisées dont la teneur en alcool est de préférence inférieure ou égale à 10 % en volume, de préférence entre 3 et 9 %. The packaging was particularly interesting in the case of non-alcoholic or low-alcoholic drinks whose content alcohol is preferably less than or equal to 10% by volume, preferably between 3 and 9%.

De façon connue, la boisson aqueuse alcoolisée ou non comprend de 0,01 à 2 g/l d'anéthole, de préférence 0,02 g/l ou plus d'anéthole.In known manner, the aqueous alcoholic or non-alcoholic drink comprises from 0.01 to 2 g / l of anethole, preferably 0.02 g / l or more of anethole.

Dans les concentrés à diluer tels que la boisson connue sous la dénomination "Pastis", la concentration en anéthole est de l'ordre de 2 g/l. Dans les boissons alcoolisées prêtes à boire, elle est de l'ordre de 200 à 400 mg/l. Dans le cas des boissons aromatisées à l'anis, elle est de l'ordre de 10 à 50 mg/l.In concentrates to be diluted such as the drink known as name "Pastis", the anethole concentration is around 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 in the range of 10 to 50 mg / l.

On rappellera que pour les boissons alcoolisées à 45 % en volume, l'anéthole est entièrement solubilisé, tandis que pour les boissons sans alcool ou faiblement alcoolisées (4-9 % en volume), on a recours à un émulsifiant afin de maintenir l'anéthole à l'état solubilisé.It will be recalled that for alcoholic drinks at 45% by volume, the anethole is completely dissolved, while for soft drinks or slightly alcoholic (4-9% by volume), an emulsifier is used to keep the anethole in a solubilized state.

Parmi les terpolymères précités convenant dans le cadre de la présente invention, on préférera ceux présentant une perméabilité à l'oxygène inférieure à 0,8 cm3.mm/m2.jour.bar à 23° C, à une humidité relative de 100 %.Among the aforementioned terpolymers suitable in the context of the present invention, preference will be given to those having an oxygen permeability of less than 0.8 cm 3 .mm / m 2 .day.bar at 23 ° C, at a relative humidity of 100 %.

Ces matériaux sont disponibles sur le marché ou peuvent être obtenus par l'homme du métier de manière connue.These materials are available on the market or can be obtained by a person skilled in the art in a known manner.

De préférence, le terpolymère présente un taux de butadiène compris entre 8 et 20 %.Preferably, the terpolymer has a level of butadiene between 8 and 20%.

Avantageusement, le terpolymère est choisi dans le groupe constitué par le terpolymère dont le taux de butadiène est d'environ 10 % ou le terpolymère dont le taux de butadiène est d'environ 18 %.Advantageously, the terpolymer is chosen from the group consisting of the terpolymer with a butadiene content of approximately 10% or the terpolymer, the butadiene content of which is approximately 18%.

Ces polymères sont commercialisés par la société BP Chemicals sous les noms de marque, respectivement Barex 210® et Barex 218®.These polymers are marketed by the company BP Chemicals under the brand names, respectively Barex 210® and Barex 218®.

Le polymère Barex 210® présente une perméabilité à l'oxygène de 0,3 cm3.mm/m2.jour.bar à 23°C.Barex 210® polymer has an oxygen permeability of 0.3 cm 3 .mm / m 2 .day.bar at 23 ° C.

Le polymère Barex 218® présente une perméabilité à l'oxygène de 0,6 cm3.mm/m2.jour.bar à 23°C.Barex 218® polymer has an oxygen permeability of 0.6 cm 3 .mm / m 2 .day.bar at 23 ° C.

Ces polymères sont déjà utilisés en tant que conditionnement pour différents produits tels que les articles cosmétiques, les produits chimiques domestiques et les articles à usage médical.These polymers are already used as packaging for different products such as cosmetic items, chemicals domestic and medical articles.

Ils sont également utilisés pour certains produits de consommation comme les huiles de table, les huiles essentielles, les épices, les sauces vinaigrette. Cependant, tous les produits qui ont été conditionnés jusqu'à présent par de tels polymères ne possèdent pas les propriétés propres à l'anéthole du fait de la nature chimique et physique particulière de ce composé. They are also used for certain consumer products such as table oils, essential oils, spices, sauces Vinaigrette. However, all products that have been packaged up to present by such polymers do not have the properties specific to anethole due to the particular chemical and physical nature of this compound.

Il ne pouvait donc être évident de déduire de ces informations les performances remarquables de ces matériaux vis-à-vis de l'anéthole.It could not therefore be obvious to deduce from this information the remarkable performance of these materials with respect to anethole.

Le document EP-A-433 097 décrit un container en résine similaire à celle décrite dans la présente invention pour conditionner des boissons telles que l'eau, le thé, le café, les jus de fruits, les jus de raisin. Ce document ne décrit ni ne suggère l'utilisation de cette résine pour le conditionnement de boisson à base d'anéthole.EP-A-433 097 describes a similar resin container to that described in the present invention for packaging beverages such as water, tea, coffee, fruit juices, grape juices. This document does not describe or suggest the use of this resin for packaging anethole drink.

En général, outre les caractéristiques de barrière vis-à-vis de l'anéthole, les films formés d'un terpolymère acrylate de méthyle-acrylonitrile-butadiène doivent présenter une imperméabilité suffisante vis-à-vis du gaz carbonique. Ils doivent également présenter une résistance au déchirement et un module d'élasticité suffisant pour l'application considérée.In general, in addition to the barrier characteristics vis-à-vis anethole, films formed of a methyl acrylate-acrylonitrile-butadiene terpolymer must have sufficient impermeability towards carbon dioxide. They must also have resistance to tear and a modulus of elasticity sufficient for the application considered.

Le conditionnement peut se présenter sous la forme d'une monocouche ou sous la forme multicouche.The packaging may be in the form of a monolayer or in multilayer form.

Dans le cas d'un conditionnement multicouche, la couche interne est formée d'un film de terpolymère acrylate de méthyle-acrylonitrile-butadiène. Le film est associé à un matériau de structure, lui-même éventuellement multicouche (métal, carton, matériau mono ou multicouche polymérique).In the case of multilayer packaging, the inner layer is formed from a film of methyl acrylate-acrylonitrile-butadiene terpolymer. The film is associated with a structural material, itself possibly multilayer (metal, cardboard, mono or multilayer material polymeric).

L'épaisseur de la couche de terpolymère pourra varier de façon notable selon que le conditionnement est monocouche ou multicouche. Elle sera de préférence comprise entre 200 et 500 µm, avantageusement entre 300 et 400 µm, mais pourra descendre jusqu'à 50 µm pour les films et aller jusqu'à 1 mm ou plus pour les gros emballages (fûts, par exemple).The thickness of the terpolymer layer may vary so notable depending on whether the packaging is monolayer or multilayer. She will preferably be between 200 and 500 μm, advantageously between 300 and 400 µm, but can go down to 50 µm for films and go up to 1 mm or more for large packages (drums, for example).

La mise en oeuvre de tels polymères est effectuée sur une machine d'extrusion soufflage usuelle, telle que celle utilisée pour le PVC avec ou sans bi-orientation.The processing of such polymers is carried out on a machine usual extrusion blow molding, such as that used for PVC with or without bi-orientation.

Il s'agit donc d'une mise en oeuvre peu onéreuse, ne nécessitant pas l'utilisation d'une machine spécifique au produit.It is therefore an inexpensive implementation, not requiring not the use of a product-specific machine.

Les conditionnements se présentent donc sous la forme d'un matériau monocouche ou multicouche obtenu par extrusion.The packaging therefore takes the form of a monolayer or multilayer material obtained by extrusion.

Les conditionnements selon l'invention peuvent conserver une boisson à base d'anéthole notamment faiblement ou non alcoolisée, dans les mêmes conditions qu'une bouteille en verre, c'est-à-dire sans dégradation substantielle des qualités organoleptiques. The packaging according to the invention can retain a anethole-based drink, in particular low or non-alcoholic, in same conditions as a glass bottle, i.e. without degradation substantial organoleptic qualities.

Ils sont de plus transparents dans le cas des conditionnements monocouches ou des conditionnements multicouches où les couches de structure sont transparentes, faciles à transformer et bon marché.They are moreover transparent in the case of packaging. monolayers or multilayer packs where the layers of structure are transparent, easy to transform and inexpensive.

L'invention concerne également un moyen d'obturation pour lesdits conditionnements pourvu d'une pellicule interne formé d'un film de terpolymère acrylate de méthyle-acrylonitrile-butadiène venant en application sur l'ouverture desdits conditionnements.The invention also relates to a sealing means for said packages provided with an internal film formed of a film of methyl acrylate-acrylonitrile-butadiene terpolymer coming in application on the opening of said packages.

Toutes les variantes indiquées ci-dessus relatives aux conditionnements s'appliquent audit moyen d'obturation.All the variants indicated above relating to conditions apply to said sealing means.

Ce moyen d'obturation est notamment une capsule cylindrique à l'intérieur de laquelle est logée une pellicule interne d'un polymère tel que défini ci-dessus.This sealing means is in particular a cylindrical capsule with inside which is housed an internal film of a polymer such as defined above.

On a représenté sur la figure 1 annexée une bouteille, vue en coupe longitudinale, dans laquelle la bouteille 1 formée d'un corps 2 cylindrique, d'un goulot 3 et d'un fond 4 est constituée d'un matériau polymère en terpolymère acrylate de méthyle-acrylonitrile-butadiène.There is shown in Figure 1 attached a bottle, seen in longitudinal section, in which the bottle 1 formed from a body 2 cylindrical, a neck 3 and a bottom 4 is made of a material polymer in methyl acrylate-acrylonitrile-butadiene terpolymer.

La bouteille présente une épaisseur de 0,2 mm au niveau du corps cylindrique et de 0,6 mm au niveau du fond.The bottle has a thickness of 0.2 mm at body level cylindrical and 0.6 mm at the bottom.

La capsule 5 est formée d'un corps cylindrique 6 et d'une base circulaire 7. A l'intérieur de la capsule 5 est logé un disque 8 formé d'une couche en terpolymère acrylate de méthyle-acrylonitrile-butadiène 8 appliquée sur la face intérieure de la base et une couche en terpolymère acrylate de méthyle-acrylonitrile-butadiène 9 venant en appui sur le goulot 3.The capsule 5 is formed of a cylindrical body 6 and a base circular 7. Inside the capsule 5 is housed a disc 8 formed of a methyl acrylate-acrylonitrile-butadiene terpolymer layer 8 applied to the inside of the base and a terpolymer layer methyl acrylate-acrylonitrile-butadiene 9 bearing on the neck 3.

L'invention concerne également l'utilisation d'un terpolymère acrylate de méthyle-acrylonitrile-butadiène, tel que décrit précédemment pour la réalisation d'un conditionnement monocouche ou multicouche, destiné à contenir les boissons à base d'anéthole éventuellement alcoolisées afin de limiter la dégradation de celles-ci, ledit terpolymère formant la couche en contact avec lesdites boissons.The invention also relates to the use of a terpolymer methyl acrylate-acrylonitrile-butadiene, as described above for the realization of a monolayer or multilayer packaging, intended to contain anethole-based drinks which may be alcoholic in order to limit the degradation of these, said terpolymer forming the diaper in contact with said drinks.

Elle concerne également un procédé destiné à limiter la dégradation des boissons à base d'anéthole, notamment faiblement ou non alcoolisées, caractérisé en ce que l'on emmagasine lesdites boissons dans un conditionnement de longue durée monocouche ou multicouche dont la couche en contact avec lesdites boissons est constituée d'un terpolymère acrylate de méthyle-acrylonitrile-butadiène tel que défini précédemment. It also relates to a method intended to limit the degradation of anethole-based drinks, especially weakly or not alcoholic, characterized in that said drinks are stored in a long-lasting single-layer or multi-layer packaging, the layer of which in contact with said drinks consists of an acrylate terpolymer of methyl-acrylonitrile-butadiene as defined above.

L'invention est maintenant illustrée par les exemples suivants donnés à titre illustratif.The invention is now illustrated by the following examples given by way of illustration.

Exemple 1Example 1

Des bouteilles constituées d'une monocouche de Barex 218® commercialisé par la société BP Chemicals, d'épaisseur moyenne 350 µm, ont été réalisées par transformation sur une machine d'extrusion bi-orientation soufflage pour PVC.Bottles made of a Barex 218® monolayer marketed by BP Chemicals, with an average thickness of 350 µm, were made by transformation on a bi-orientation extrusion machine blowing for PVC.

Les bouteilles sont remplies à froid en présence d'un bactériostatique, d'une solution anisée non alcoolisée contenant 400 mg/l d'anéthole, puis sont laissées 12 mois à 20°C,The bottles are cold filled in the presence of a bacteriostatic, non-alcoholic anise solution containing 400 mg / l anethole, then left for 12 months at 20 ° C,

On évalue la perte en anéthole périodiquement. On constate qu'après 9 mois, la perte en anéthole est de 25 % et qu'après un an, elle est de 28 %. On observe donc un palier à partir de 9 mois, la perte en anéthole ayant peu évoluée depuis ce terme.The loss of anethole is evaluated periodically. We aknowledge that after 9 months, the loss in anethole is 25% and that after one year, it is 28%. We therefore observe a plateau from 9 months, the loss of anethole having little changed since that term.

Exemple 2 (comparatif) Example 2 (comparative)

Des bouteilles formées en polyéthylènetérephtalate sont remplies de la même solution que celle de l'exemple 1 et sont laissées 12 mois à 20°C.Bottles formed from polyethylene terephthalate are filled of the same solution as that of Example 1 and are left for 12 months at 20 ° C.

On évalue la perte en anéthole périodiquement. On constate qu'après 6 mois, la perte est de 92 % et de 100 % après 12 mois.The loss of anethole is evaluated periodically. We aknowledge that after 6 months, the loss is 92% and 100% after 12 months.

Les résultats sont résumés dans le tableau ci-dessous ainsi que dans la figure 2 annexée où est représenté le pourcentage de perte en anéthole en mois (Barex 218® -▴- , PET -▪-). Mois 0 3 6 9 12 Barex® % 0 18 21 25 28 PET % 0 65 92 97 100 The results are summarized in the table below as well as in the appended FIG. 2 which shows the percentage of loss of anethole in months (Barex 218® -▴-, PET -oulez-). Month 0 3 6 9 12 Barex®% 0 18 21 25 28 PET% 0 65 92 97 100

Exemple 3 (comparatif) Example 3 (comparative)

Un exemple similaire à l'exemple 1 a été effectué avec des bouteilles en polyéthylène commercialisée par la société Pampryl (France) pour des jus de fruits et avec des bouteilles en polypropylène. An example similar to Example 1 was carried out with polyethylene bottles sold by Pampryl (France) for fruit juices and with polypropylene bottles.

On constate après 6 mois une perte supérieure à 90 % et de 100 % après 12 mois.After 6 months there is a loss greater than 90% and 100% after 12 months.

Exemple 4 (comparatif) Example 4 (comparative)

Un exemple similaire à l'exemple 3 avec une bouteille en PVC est réalisé .An example similar to Example 3 with a PVC bottle is realized .

On constate après 6 mois une perte supérieure à 90 % et de 100 % après 12 mois.After 6 months there is a loss greater than 90% and 100% after 12 months.

Claims (17)

  1. Monolayer or multilayer long-life packaging containing an alcoholic or non-alcoholic anethole-based beverage, characterized in that the layer in contact with the said beverage is formed of a methyl acrylate/acrylonitrile/butadiene terpolymer.
  2. Packaging according to Claim 1, characterized in that the methyl acrylate/acrylonitrile/butadiene terpolymer has an oxygen permeability of less than 0.8 cm3.mm/m2.day.bar at 23°C and at a relative humidity of 100%.
  3. Packaging according to either of Claims 1 and 2, characterized in that the terpolymer has a butadiene content of between 8 and 20%.
  4. Packaging according to Claim 3, characterized in that the terpolymer is chosen from the group consisting of the terpolymer whose butadiene content is about 10% and the terpolymer whose butadiene content is about 18%.
  5. Packaging according to one of Claims 1 to 4, characterized in that the terpolymer layer has a thickness of between 50 µm and 1 mm.
  6. Packaging according to one of the preceding claims, characterized in that it is in the form of a multilayer in which the inner layer is formed of a film of methyl acrylate/acrylonitrile/butadiene terpolymer, the said inner layer being combined with a structural material, which may be multilayered.
  7. Packaging according to Claim 6, characterized in that the structural material is chosen from the group consisting of metal, cardboard or a monolayer or multilayer polymer material.
  8. Packaging according to one of Claims 1 to 7, characterized in that it is in the form of a bottle.
  9. Packaging according to Claim 1, characterized in that the beverage is a non-alcoholic or low-alcohol beverage.
  10. Packaging according to Claim 9, characterized in that the beverage comprises up to 10% by volume of alcohol.
  11. Packaging according to Claim 10, characterized in that the beverage comprises 3 to 9% by volume of alcohol.
  12. Packaging according to one of Claims 1 and 9 to 11, characterized in that the alcoholic or non-alcoholic aqueous beverage comprises 0.01 to 2 g/l of anethole.
  13. Packaging according to Claim 12, characterized in that the alcoholic or non-alcoholic aqueous beverage comprises 0.02 to 2 g/l of anethole.
  14. Closure means for packaging according to one of the preceding claims, provided with a thin inner sheet formed of a film of methyl acrylate/acrylonitrile/butadiene terpolymer which is applied over the opening of the said packaging.
  15. Closure means according to Claim 14, characterized in that it consists of a cylindrical cap inside which is housed a thin inner sheet formed of a film of methyl acrylate/acrylonitrile/butadiene terpolymer which is applied over the opening of the said packaging.
  16. Use of a methyl acrylate/acrylonitrile/butadiene terpolymer according to one of Claims 1 to 5, to produce a monolayer or multilayer packaging intended to contain anethole-based beverages, which may be alcoholic, according to one of Claims 1 and 9 to 13, in order to limit the deterioration of these beverages, the said terpolymer forming the layer in contact with the said beverages.
  17. Process intended to limit the deterioration of anethole-based beverages, in particular low-alcohol or non-alcoholic beverages, characterized in that the said beverages are stored in a monolayer or multilayer long-life packaging in which the layer in contact with the said beverages consists of a methyl acrylate/ acrylonitrile/butadiene terpolymer according to one of Claims 1 to 5.
EP97930555A 1996-06-21 1997-06-19 Long-lasting packaging for anethole-based beverage Expired - Lifetime EP0912422B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR9607742 1996-06-21
FR9607742A FR2750116B1 (en) 1996-06-21 1996-06-21 LONG-TERM PACKAGING OF POLYMERIC MATERIAL FOR ANETHOLE-BASED BEVERAGE AND METHOD FOR LIMITING THE LOSS OF ANETHOLE CONTAINED IN A SOLUTION
PCT/FR1997/001102 WO1997049621A1 (en) 1996-06-21 1997-06-19 Packaging for a beverage

Publications (2)

Publication Number Publication Date
EP0912422A1 EP0912422A1 (en) 1999-05-06
EP0912422B1 true EP0912422B1 (en) 2000-08-23

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Application Number Title Priority Date Filing Date
EP97930555A Expired - Lifetime EP0912422B1 (en) 1996-06-21 1997-06-19 Long-lasting packaging for anethole-based beverage

Country Status (13)

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US (1) US5908678A (en)
EP (1) EP0912422B1 (en)
JP (1) JP2000512602A (en)
AT (1) ATE195700T1 (en)
AU (1) AU3446897A (en)
CA (1) CA2259451C (en)
DE (1) DE69702916T2 (en)
DK (1) DK0912422T3 (en)
ES (1) ES2150264T3 (en)
FR (1) FR2750116B1 (en)
GR (1) GR3034878T3 (en)
PT (1) PT912422E (en)
WO (1) WO1997049621A1 (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2752565B1 (en) * 1996-08-21 1998-11-13 Pernod Ricard PACKAGE FOR ANETHOLE-BASED BEVERAGE CONSISTING OF AT LEAST PART OF A POLYMER COMPRISING CONDENSED AROMATIC PATTERNS
US20170252993A1 (en) * 2016-03-03 2017-09-07 Juicero, Inc. Juicer cartridge with coupling

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03187832A (en) * 1989-12-15 1991-08-15 Mitsui Toatsu Chem Inc Transparent container

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US5908678A (en) 1999-06-01
FR2750116B1 (en) 1998-09-11
WO1997049621A1 (en) 1997-12-31
PT912422E (en) 2000-12-29
DE69702916D1 (en) 2000-09-28
DE69702916T2 (en) 2001-03-29
EP0912422A1 (en) 1999-05-06
FR2750116A1 (en) 1997-12-26
CA2259451A1 (en) 1997-12-31
CA2259451C (en) 2007-12-11
ATE195700T1 (en) 2000-09-15
JP2000512602A (en) 2000-09-26
GR3034878T3 (en) 2001-02-28
ES2150264T3 (en) 2000-11-16
DK0912422T3 (en) 2000-12-18
AU3446897A (en) 1998-01-14

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