Closure, membrane seal and cover assembly for closing e.g. bottle of water, has head extended by main body including inner space provided with container that rests on o-ring seal

i

The present invention relates to the arrangement, manufacture and industrial applications of new packaging materials represented by devices such as stoppers and / or bio-active lids and / or lids intended for closing bottles, flasks. , jars, cans, boxes and containers used in the packaging and storage of food products.

These new packaging qualified as bio-active consist, individually or in combination, of metallic and / or cellulosic and / or synthetic materials, and they are characterized by the fact that at least one of their elements and / or their constituents contains, and / or incorporates and / or comprises and / or releases, and / or diffuses bio-chemical and / or biological substances which confer new functional properties to these packaging. Packaging is generally defined as an assembly of materials designed to receive, contain and protect goods intended to be stored, transported and marketed. In particular, the packaging of food intended for humans must, by virtue of its intrinsic properties, allow optimal conservation of the food content throughout its life cycle, from its manufacture to its consumption. It must protect the food from external germs, offer selective gas barrier properties, withstand changes related to the temperature or humidity of the environment during storage, marketing and use by the consumer and, “in fine”, to comply with regulations.

- Until now, the packaging generally used provides passive functions of collection, packaging, physical containment and mechanical protection of food against environmental factors encountered during the successive phases of manufacture, storage, transport and sale .

European regulations dealing with packaging in contact with food aim to protect the health of the consumer. It is stipulated in the European framework directive 89/109 / EC that materials and articles intended to come into contact with food must comply with the principle of inertia: "Materials and articles intended to come into contact with foodstuffs, products and drinks for human consumption must not, under normal or foreseeable conditions of use, give these foodstuffs constituents in a quantity liable to present a danger to human health or cause an unacceptable change in the composition of foodstuffs ”. This directive therefore did not authorize the use of active packaging which meets the following definition according to Wagner (1989): “Active packaging offers more than just protection. It interacts with the product and in some cases responds to changes in the surrounding environment or in the product itself. "

A new European regulation has amended Directive 89/109 / EC and now takes into account the concept of "active" packaging which allows the principle of "transfer or deliberate absorption of compounds to or from food for the purpose of to maintain or improve the conditions of conservation of the product ”. “Materials can modify the composition of food only if the modifications comply with Community provisions applicable to food, such as the provisions of Directive 89/107 / EEC relating to food additives. Substances such as food additives deliberately incorporated in certain active materials intended to come into contact with food with a view to being released into packaged food should be allowed ”. According to Gontard, active packaging can be classified into three main categories:

- interactive packaging which acts in a controlled manner on the food to improve and preserve its quality throughout the distribution chain. The activity of these packaging aims to control the risks of food deterioration linked to the various mechanisms of lipid oxidation, tissue browning, vitamin degradation or microbial contamination. Many products are offered on the market in the form of oxygen absorber sachets; or carbon dioxide absorber sachets, manufactured by Mitsubishi Gas Chemical (Japan), by Multiform Dessicant (United States), by Bioka (Finland) and by Sanda (France).

- indicator packaging which reacts to the characteristics of the food and to the storage conditions in order to inform the consumer. The devices generally used are the Time / Temperature indicators based on reactions of the enzymatic or polymerization type. They are produced by different companies: 3M Monitor (Great Britain), Tr igon Industries (Great Britain), Lifelines Technology (United States), Pillsbury Co. (United States),

Marupfroid (France). Color indicators of gas concentration or pH in the package are available from Mitsubishi Gas Chemical Co. and Toppan Printing Cri. (Japan) and by Trigon Industries (Great Britain).

- preparatory packaging which makes it possible to modify the characteristics of the food to facilitate its consumption. These are essentially self-heating or self-cooling packaging offered by Print pak Inc. (United States), by Baritalia (Italy) and by Bréger (France). It should be noted that certain packaging devices used transiently during The successive stages of food manufacturing are rather qualified as technological packaging. The new models of bioactive stoppers, lids and lids according to the invention differ from already existing active packaging by their specific formats, by their biological contents and by their new functional activities. These new models of caps, lids and lids are developed for different formats of containers such as bottles, flasks, boxes, bricks, jars, terrines, cans, demijohns, barrels, barrels, vats, tanks and they are characterized by the that at least one of their elements and / or their constituents acts as a reservoir which receives, contains, produces and diffuses various chemical and / or biological compounds such as:

- chemical elements (oxygenated free radicals, mineral salts, ...)

- nitrogen, chlorine, iodine, brominated, sulfur, phosphate, etc. molecules,

- biochemical elements (carbohydrates, lipids, proteins, metabolites, ...)

- biological elements (flavors, vitamins, enzymes, immunoglobulins, ...)

- microbiological elements (bacteria, yeasts and fungi, ...).

The bioactive stoppers, lids and lids, objects of the invention, are characterized by the fact that they allow, during the stoppering of the container, to obtain, individually and / or in combination:

- the addition and diffusion, immediate and / or deferred, of the various compounds and their interaction products present in the reservoir (s) of the caps, lids and lids, towards and in the packaged products.

- aromatic and / or nutritional enrichment, health protection and prolonged storage of liquid food products (milk, wines, champagnes, beers, fruit juices, etc.), semi-liquids (egg products, vegetable soups, vegetable purees , fruit compotes and jams, sauces, ready meals, etc.) and solids (fruits and vegetables, etc.) contained in the packaging containers thus closed.

The nature, the mode of assembly and the formatting of the structural elements, the formulation of the bioactive compounds, the new functional properties and the industrial applications of the new models of caps, lids and lids are the subject of the present document. invention described below, by way of indication but not by way of limitation, according to five different models.

1) Stoppers, lids and lids with additive function according to figure 1.

- According to a first general preferred but not exclusive embodiment of the 5 packaging devices according to the invention, the cap, lid or cover model according to FIG. 1 is characterized by its additive function which consists in containing, in release and diffuse food additives and / or processing aids, previously included in its reservoir, to the packaged food product. The stopper, the cap and the cover are made of different materials, associated or not, such as metal compounds (aluminum, iron, etc.), and / or such as synthetic plastics (polyethylene, polypropylene, etc. ), and / or such as natural materials (cellulose, cork, etc.). The stopper and lid models; and cover comprise a head (1) which is provided with an internal thread (2) allowing screwing on the neck of the container (8), and which is extended by a hollow cylindrical body (3) of variable dimensions. The body (3) has an internal cavity (4) which comprises at least one of the two elements constituted respectively by the part (5) and / or by the O-ring (6). The part (5), of honeycomb and spongy structure, is advantageously made up of the formatted assembly of different expanded materials, associated or not, such as plastics (polyethylene, polypropylene, polystyrene, polysulfone, polyurethane, etc.), or polymerized natural materials (starch, cellulose, agarose, casein, chitosan, lactic acid ...). The part (5) is structured in one or more spongy layers and it constitutes a reservoir whose dimensions and format vary with the size of the container to be closed and with the nature and quantity of food additives and / or technological aids to be loaded.

- By way of indicative but non-limiting example, the part (5) is formatted as a disc with a spongy, elastic and compressible structure, which acts as a reservoir.

During its manufacture, the reservoir (5) is loaded with a determined quantity, in the form of powder or solution, with food additives and / or technological aids, pure or associated, intended for nutrient enrichment, and / or aromatic, and / or organoleptic of food, and represented by preservatives (chlorides, phosphates, nitrites and nitrates, sulfur dioxide and sulphites, organic acids), and / or anti-oxidants (carbon dioxide, nitrogen, argon, natural phenolic compounds, ...) and / or vitamins (Vitamin A, Vitamin C, vitamin E), and / or sweeteners (polyols, acesulfame, aspartame, cyclamate, thaumatin, neohesperidin), and / or flavor enhancers (glutamates, ribonucleotides, ethylmaltol), and / or peptides and active proteins (Iyzozyme, reduced lactoferrin and transferrin, glucose-oxidase, catalase, lacto-peroxidase, glutathione, etc.), flavorings (eugenols, vanillin, pinenes, limonéne, geranial).

Depending on the case, the reservoir (5) can also receive a determined quantity, in powder or solution form, of different antimicrobial molecules, associated or not, such as lactic acid, acetic and peracetic acids, tartaric acid. , sodium disulphite or potassium disulphite, sodium or potassium nitrites, 8-hydroxyquinoline, hydrogen peroxide and persalts, ethanol, sodium hypochlorite, nisin, bacteriocins, essential oils.

The sealing O-ring (6) is structured, as necessary, in one or more annular layers (6a, 6b, ...) comprising one or more transverse channels (7) allowing the passage of the solutions contained in (5) towards space (4).

- By way of indicative but non-limiting example, the first layer (6a), of expanded polyethylene, serves as a reservoir for various compounds. The second layer (6b) is a metallic film, with a barrier effect, impermeable to water and to gases (oxygen, nitrogen, carbon dioxide), which serves as a physical support for the previous layer (6a) and as a cover. sealing after screwing. The installation of the stopper or the cover on the container (8) produces a vertical circular pressure on the seal (6) and on the disc (5) which will then release, through the channel (7), the major part of their respective contents in the product packaged in (8). The residual additives in (5) and (6a) then continue their diffusion towards the food packaged in (8) throughout the storage period. The model according to FIG. 1, which presents two distinct reservoirs (5) and (6), allows the separate and sequential loading and diffusion of compounds which are hardly or not compatible with one another. The characteristic advantage of this model of stopper, cap and cover with additive function according to FIG. 1 of the invention consists in the fact that the diffusion of the active compounds takes place at the time of packaging and throughout the storage of the product. 'food. This characteristic induces a saving in manufacturing time as well as an extension of the period of diffusion of the active compounds in the food thus conditioned.

- According to a first preferred but non-exclusive example of industrial production and application according to the invention, the stopper according to FIG. 1, composed of polyethylene, is formatted to close bottles of infant formula of 1 liter, with a wide neck of 4 cm in diameter. The plug comprises in its internal cavity (4) two separate reservoirs represented respectively by the disc (5) and by the O-ring (6). During the manufacture of the active stopper according to the invention, the disc (5), consisting of a frame of polymerized and expanded caseins, can receive a load of different formulations, alone or in combination, of additives and food auxiliaries which meet the properties required for the final packaged food.

For example, the manufacture of an active cap intended for a one liter container used in the packaging of infant formulas for young children is carried out as indicated below. The seal (6a) is loaded with two milliters (2ml) of a mixture of vitamins (vitamins A, D, E,), emulsifiers (lecithins), fatty acids, according to the formulation established below and provided for information:

- Vitamin A (E160a): 400 mg -Vitamin D3: 12.5 mg -Vitamin E (E306): 6.6g- Linoleic acid: 40g -Linolenic acid: 50g-Camitine: 80g-Taurine: 3.5 gr- Lecithins (E 322): 30 gr.

-Water qsp .............: 1000ml.

The disc (5) is loaded with one milliliter (1ml) of a mixture of soluble vitamins (Vitamins B, C, PP, ..), proteins (lactoferrin, lactoperoxidase, lysozyme, antimicrobial antibodies,), mineral salts and trace elements, according to the formulation established below and provided as an indication but not limiting: -Vitamin B1: 400 mg -Vitamin B2: 1.5 g -Vitamin B5: 3 gr-Vitamin B6: 0.6 gr -Vitamin B9: 90 mg -Vitamin B12: 2gr -Vitamin C (E 300-E 301-E 302): 60 gr-Vitamin PP: 600 mg.

- Calcium orthophosphates (E341): 75gr.

-Magnesium carbonate (E 504): 10 gr.

- Zinc: 8 gr - Sodium iodide (EOlO): 150 mg.

-Bovine lacto-ferrin: 0.5 gr.

-Bovine lacto-peroxidase: 0.5 gr.

-Lysozyme (E1105): 0.5gr.

- Antiviral lactic immunoglobulins: 50gr.

-Water qsp ...................................... 1000 ml.

The disc (5b) and the seal (6a) thus loaded are inserted on the inner bottom of the head (l) of the stopper. The stopper is then fixed by its thread (2) on the neck of the container (8). Screwing on the cap causes migration and diffusion of vitamins, salts, fatty acids and proteins contained in (5) and (6a) in the milk packaged in (8). enriched with specific vitamins and nutrients. Some of these vitamins, (B vitamins), are heat sensitive and are altered or destroyed by heat sterilization procedures applied to milk prior to packaging. The use of an active stopper according to the invention results in the addition of vitamins, and in particular heat-sensitive vitamins, after heating and conditioning, thus making it possible to maintain the molecular integrity and the biological activity of these vitamins. in the food. One characteristic of the active stopper according to the invention thus consists in maintaining the nutritional properties of the food throughout its period of storage, transport and distribution.

- A second example of application of the cap according to Figure 1, provided below by way of indication but not limiting, is represented by an active cap intended for packaging fresh milk. The constituents of fresh milk, in particular fats and certain vitamins, are sensitive to atmospheric oxygen and are altered by oxidation over time. The manufacture of an active antioxidant plug, intended for packaging fresh milk, is carried out as follows: the disc (5) is loaded with one milliliter (1ml), with a solution of ascorbic acid (E 300) or with ascorbates (E 301, or E302, or E304), at 30gr. per liter and the seal (6) receives lgr. of tocopherols (E 306). The active stopper, comprising the disc (5) and the seal (6a), is then screwed onto the neck of the container (8). Screwing on the cap causes the ascorbic acid and tocopherols to diffuse into the milk packaged in (8). The properties of the active stopper according to the invention allow prolonged preservation of the organoleptic characteristics of milk and white cheese curds and they constitute an important competitive advantage for their marketing.

- A third example of application of the stopper according to FIG. 1, provided below by way of indication but not limitation, is represented by an active stopper intended for packaging edible oils. In this application according to the invention, the seal (6a) is loaded with a milliliter (lml), an aqueous solution of 10% ascorbic acid (E300) and 10.% propyl gallate (E310). The disc (5) receives under a milliter (lml), a load of one gram (lgr.) Of tocopherols (E 306) emulsified in a solution of fatty acid esters (E 471) at 10gr. per liter.

The bioactive properties of this stopper according to Figure 1 are applied to the packaging of essential oils, margarines and fats.

The functions of nutrient enrichment and prolonged preservation, characteristic of this stopper according to FIG. 1 of the invention, are applied to various containers receiving foods rich in lipids such as milks of industrial mixtures, and / or fresh milks and / or infant formula and / or dietetic milks and / or specific dairy products (fermented milks, white curds and yogurts) and such as essential oils, and / or fatty liquids.

- A fourth non-limiting example of application according to Figure 1, is represented by a cap formatted to close bottles, flasks, boxes and bricks of: wine. The metal aluminum capsule has a head (l) of 3cm. In diameter extended by a body (3) of 6cm. In length. During the manufacture of the capsule, the disc (5) receives a load of 1 ml. antimicrobial sulfites (sodium sulfites E221, or potassium E228, or calcium E226) in solution at 200gr. per liter and the seal (6a) receives a charge of 0.5ml. of aromatic compounds dissolved according to the following formulation: lmg. of vanillin + lmg. of isoeugenol + 10gr. of tannin + 500mg of a mixture of equal parts of guanylic acid (E 626) and inosinic acid (E 630) in one liter of aqueous solvent. These different charges of active compounds are subsequently released in the wine, sequentially and separately, when the bottle is corked (8) and lead to prolonged protection and enrichment of the physical and organoleptic characteristics of the wine thus conditioned.

The capsule according to Figure 1 can be formatted, sized and activated in various ways depending on the size of the container containing the wine. According to the invention, the format and dimensions adopted for the capsule according to FIG. 1 can thus constitute a barrel and / or barrel bung or a wine vat cover with preservative functions.

- A fifth example of application of the cap according to Figure 1, provided as an indication but not limiting, relates to a metal cap formatted and loaded to close beer bottles and / or bottles of infiisions concentrates and / or jars containers for jams and marmalades. To this end, the expanded polypropylene disc (5) receives a load of 1 ml of a solution containing 200 mg / liter of potassium sorbate (E 202) and the seal (6) receives a load of 1 ml. of sodium benzoate (E211) at 150mg / liter. These additives released during corking lead to a prolonged preservation of the initial organoleptic properties of the packaged foods.

- A sixth example of application according to Figure 1, provided as an indication but not limiting, is a synthetic cover formatted and loaded to close containers (bottles, flasks, ...) receiving fruit juices, or water flavored or specific diet drinks. To this end, the disc (5), made of expanded polypropylene, receives a load of 1 ml. of a solution containing 100 mgr / liter of ascsorbic acid (E 300) and 100 mgr / liter of citric acid (E330). The joint (6) receives a charge of one milliliter of an aspartame solution (PS 200) at 20 mg. per liter. These additives released after the container (8) has been closed off induce the lasting maintenance of the initial dietetic and taste properties of the packaged drinks.

- According to a seventh example of non-exclusive application, the seal according to Figure 1 is formatted as a flat screw cap, metallic or synthetic in nature and of variable dimensions, and it is intended for closing jars, and / or verrines, and / or terrines receiving processed or cooked foods. The cover according to Figure 1, has a circular head (1), 8cm. diameter and 2cm. height, on which is fixed on its interior base, a circular disc (5) in expanded polyethylene, 7.8cm. diameter and 0.5 cm thick which is loaded with a mixture of equal parts of lactic acid (E270) in 10% solution and sorbic acid (E 200) in 10% solution. The packaging of sauces, purees, candied fruits, jams and compotes in containers closed with the lid according to figure 1, results in the diffusion of the active ingredients contained in the reservoirs (5) and / or (6 ) on the surface of packaged foods and leads to their prolonged protection and preservation during storage and consumption.

The models of caps and lids according to figure 1 allow, depending on the nature and the specific formulation of the compounds loaded in the reservoirs (5) and / or (6), to transfer to the food contained in the receptacle (8) various molecules such as salts, trace elements, vitamins, amino acids, fatty acids, peptides and proteins, sugars and sweeteners, preservatives, flavors and extracts from fruits, vegetables and plants various. The characteristic functions of these stoppers and lids according to the invention consist in the immediate addition during the stoppering, and in the gradual diffusion during their storage and throughout their consumption, of additives and food auxiliaries in the products. conditioned.

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Generally speaking, the additive function of these stoppers and lids according to the invention is implemented for continuous nutritional enrichment, and for the controlled preservation of packaged foods such as milk and dairy products, wines and fruit juices. , mineral water, diet drinks, infusions, herbal teas, jams. These stoppers and lids according to the invention consequently constitute new tools for organoleptic and / or nutritional enrichment and new means of packaging and preserving food.

2) Stopper and lids with additive and protective functions according to figure 2.

- According to a second general preferred but non-exclusive embodiment of the packaging devices according to the invention, the models of caps and lids according to Figure 2 are characterized by their protective function which consists of containing, releasing and diffusing substances anti-microbial bacteria included in the packaged food The caps and lids are made of different materials, associated or not, such as metal compounds (aluminum, iron, etc.), such as synthetic plastics (polyethylene, polypropylene, etc.), and / or such as natural materials (cellulose, cork, etc.).

- According to a first indicative but non-limiting example, the stopper according to FIG. 2 is manufactured to stopper bottles of still or sparkling wines of average conservation, of the order of two to three years.

It comprises a main cylindrical body (1) made up of agglomerated cork granules and / or compact cork. The method of manufacturing the active stopper according to the invention consists in treating the cork granules before assembly and / or the entire cork body (1) using at least one antiseptic solution given so as to impregnate and charge the cork of anti-microbial molecules which, on the one hand, act directly on the material itself and which, on the other hand, then diffuse, from the body (1) of the stopper towards the surrounding environment and towards the food liquid in contact with it. For example, and without limitation, the body (1) of the stopper is immersed for 7 days at room temperature in a solution of 10% ethanol; at the end of this maceration period, the body (1) is dried in a sterile atmosphere, then it is immersed a second time for 5 days at room temperature in a concentrated solution of sulfur dioxide supplied in the form of sodium bisulphite (E 222) or potassium bisulfite (E 228) at 18% (180gr / l of SO2). The stopper is then drained and dried on the surface for 5 minutes at 40 ° C .; it is finally packaged in an impermeable and airtight plastic bag until its final use, which has a shelf life of 3 months. Two characteristic properties of the cork stopper treated according to the invention reside on the one hand in its chemical harmlessness and on the other hand in its microbial sterility which are acquired during this manufacture. The cork treated and sterilized according to the original process described above is in fact free of chemical (Trichloroanisols) and microbial (Fungi) contaminants, possibly present in the initial raw cork. This chemical harmlessness and this acquired microbial sterility represent the specific characteristics of the cork treated according to the invention and they are essential for the subsequent good preservation of the organoleptic and hygienic properties of the wines and champagnes thus corked. A third characteristic property of the active stopper obtained according to the invention occurs during the corking of wine bottles: the active stopper is compressed during its insertion into the neck and it then releases small amounts of sulfur dioxide on its surface which sanitize. the inner and outer surfaces of the bottle neck. This characteristic makes it possible to control and control the subsequent risk of proliferation, on the head of the stopper, of microbial contaminants accidentally included during packaging.

A fourth characteristic property of the stopper obtained according to the invention consists in the slow and continuous release and diffusion of the sulfur dioxide contained in the body (1) towards the wine in which it will exert a protective and preserving activity during the storage period. In general, the active stopper according to the invention can be the subject, at the time of its manufacture, of one or more unit and / or associated anti-microbial treatment, involving antiseptic solutions (sulphites, alcohols, hypochlorites ...) and / or gases (formaldehyde) and / or ionizing irradiations.

- According to a second indicative but non-exclusive example of industrial production and application according to the invention, the stopper according to Figure 2 is formatted to stopper bottles of still wines and sparkling alcoholic beverages such as sparkling wines, ciders and champagnes from shelf life of over two years The stopper consists of a main cylindrical body (l), in cork and / or synthetic polymers, which comprises, inserted at each of its ends, a hollow polypropylene cup (2), acting as a reservoir (3), and closed by a polytetrafluoroethylene membrane (4), porous and permeable to water and gases. During manufacture, the reservoirs (3) receive and contain, in one milliliter each, a charge of 100 mg. sodium sulphite (E 221).

After plugging the container (5), the sulphite in (3) diffuses through the membrane (4) and is gradually released in the immediate environment of the stopper, on the one hand in the container (5) and its contents, and on the other hand in the head atmosphere above the plug.

The antimicrobial activity of the sulfur dioxide released by the stopper allows, on the one hand, the control and / or the reduction of microbial flora (yeasts and molds, fermentation bacteria, etc.) possibly present in the wine and on the internal walls. the neck (5), and on the other hand induces a prolonged conservation of the drink. In general, the type of plug according to FIG. 2 is characterized by the nature and by the formulation of the compounds loaded into the reservoirs (3) and by its capacity to diffuse and / or to transfer to the product distributed in (5), various additives and technological aids such as salts, trace elements, vitamins, amino acids, peptides and proteins, fatty acids, flavors and plant extracts, sugars and preservatives.

3) Stoppers and lids with additive and protective functions according to Figure 3. - According to a third general preferred but not exclusive embodiment of the packaging devices according to the invention, the models of caps and lids according to Figure 3 are characterized by their antioxidant function which consists of containing, releasing and diffusing the included antioxidant substances to the conditioned food. The caps and lids are made of different materials, associated or not, such as metal compounds (aluminum, iron, etc.), such as synthetic plastics (polyethylene, polypropylene, etc.), and / or such as natural materials (cellulose, cork ...).

The stoppers and lids according to figure 3 comprise a main body (1), in cork or in synthetic polymers, surmounted by a head (2) in synthetic copolymers and provided, in its lower end part, with a polyethylene cup. high density (3) acting as a reservoir (4) closed by a microporous cover (5) made of plastic. Depending on its end use, this cover (5), permeable to water and to gases, comprises one or more successive layers.

- According to a first indicative but non-limiting example of industrial production and application according to the invention, the stopper according to FIG. 3 is manufactured with a view to closing bottles of wines for aging, cooked wines and flavored wines sensitive to reactions oxidation. It consists of a main cylindrical body (1) in cork, and a round head (2) in acrylic. During the manufacture of the active plug according to Figure 3, the reservoir (4) receives 1gr. Of sodium carbonate (E500), or potassium (E501), or ammonium (E503), or calcium (E001) , then it is sealed by a polyvinylidene fluoride membrane (5), porous and permeable to water and gases. The stoppering of the bottle causes a migration of the water vapor from the drink packaged in (6) towards the reservoir (4) through the membrane (5). The contact of the water with the baking soda produced carbon dioxide (E290) which then diffuses to the headspace of the bottle (6). The antioxidant activity of the carbon dioxide thus diffused by the stopper into the container (6) leads to the prolonged preservation of the organoleptic properties of the conditioned wines.

- According to a second indicative but non-exclusive example of industrial production and application of the invention, the stopper according to FIG. 3 is manufactured with a view to plugging bottles of fruit syrups and flavored non-alcoholic drinks. During its manufacture, the stopper is made active by the addition, in the reservoir (4), of 100 mg. of sodium bisulfite (E 222.) and by loading on the cover (5) of 50 mg. L-ascorbic acid (E 300) in solution. After filling, the cup (3) is closed by a cover (5), in low density polyethylene (LDPE), permeable to water. After corking the bottle (6), the ascorbic acid charged in (5) and the: sodium bisulfite contained in (4) are gradually released in the drink packaged in (6). The cumulative antioxidant activities of sulfur dioxide and ascorbic acid released by the stopper lead to the inhibition of the oxidation phenomena of packaged drinks and to the maintenance of their initial taste properties during storage and consumption.

- According to a third indicative but not exclusive example of industrial production and application according to the invention, the stopper according to FIG. 3 is formatted as a flat plastic cover, with dimensions adapted to the size of a jar (6), and intended for the packaging of fresh vegetables such as pickles, olives, aromatic plants and herbal teas. The cover according to Figure 3 comprises a circular head (1) of plastic, 8cm in diameter and 0.5cm. Thick which receives, by gluing in the center of its inner base, a cylindrical polyethylene cup (3), 2 cm in diameter and 0.5 cm in thickness, closed by a multi-layer cover (5). The cover (5) comprises two sheets:

the internal polyethylene sheet (5a), with an alveolar and spongy structure, which receives and contains, mixed or not, solutions of preservative organic acids such as acetic acid (E260) or lactic acid (E270) , or propionic acid (E280), and stabilizing salts such as sodium orthophosphates (E339), or potassium (E340), or calcium (E341).

- the sheet (5b) consisting of a synthetic polyamide membrane, porous and permeable to water and gases, and serving as a physical support for the previous layer (5a). During manufacture, the stopper is made active by adding 50 mg to the reservoir (4). of potassium acid sulphite (E 228), and by the respective loadings of 50 mg. of calcium citrate (E 333) on the layer (5a) and lOmg. of chlorophyll type dyes (E 140) on the layer (5b).

After plugging the container (6), the water vapors from the vegetables distributed in (6) come into contact with the layers (5a and 5b) and the reservoir (4), by capillary action, lead to the migration and diffusion of the principles. antioxidants contained in (4) and (5) to the vegetables packaged in (6).

- According to a fourth indicative but non-exclusive example of industrial production and application according to the invention, the stopper according to FIG. 3 is formatted as a plastic bung for cans intended to store 20 liters of raw or concentrated fruit juice. The cylindrical bung (10 cm in diameter by 5 cm in thickness) has on its lower surface a recess of 20 cc in volume acting as a reservoir (4). The latter receives a load of 10 ml. of glucose in 10% solution and it is closed by a nylon membrane (5) permeable to water and gases, brand PALL-Type Immunodyne ABC, activated and carrying glucose-oxidase (ECN ° 1.1.3.4. ) and catalase (ECNo 1.11.1.6). The enzymes are fixed to the membrane (5) by immersing the latter for 1 hour in a tank containing 500 ml. of a mixture, in equal parts, of the two enzymes in buffered solution at 2 gr./liter, for 1 square meter of membrane. Contact between the enzyme solution and the membrane (5) for 120 minutes at room temperature allows the creation of a stable bond between the proteins and the membrane and results in the attachment of an enzyme layer. (80pgr. Of protein per square cm).

After distribution of the food liquids in the containers closed by the lid according to Figure 3, the water vapors from the conditioned liquids come into contact with the membrane (5), and induce an activation of the enzymes which hydrolyze the glucose into acidifying gluconic acid and anti-microbial hydrogen peroxide.

This controlled enzymatic production, which is a function of the initial concentration of glucose in the bung and the storage temperature of the container, induces in the conditioned liquid on the one hand an anti-microbial activity linked to hydrogen peroxide, and of the other has an acidifying and anti-oxidant activity linked to gluconic acid.

The main characteristic of these lids according to the invention consists of their intrinsic capacity to generate, in a controlled quantitative manner, active metabolites such as organic acids and hydrogen peroxide at low and constant rates, which induce protection and conservation. extended distributed drinks. More generally and depending on the targeted activity, the membrane (5) of the stoppers or lids according to FIG. (3) can be activated, according to an adsorption and / or covalent binding reaction, by molecules of enzymes. such as proteases (trypsin, pepsin, papain, carboxypeptidases, ...), and / or osidases (amylases, cellulases, mannosidases, galactosidases, fructosidases, glucosidases, ...) and / or esterases (pectin esterase, polygalacturonase ), and / or lipases (triglyceride esterases,) and / or oxidoreductases, (peroxidases, glucose oxidase, catalase, etc.) In general, and according to varying methods of production and industrial applications of the invention , the caps, lids and lids according to FIG. 3 receive and / or contain and / or produce and diffuse, in variable volumes, different loads of active compounds, pure or mixed, such as antioxidant additives, colorants and preservatives in solid, gaseous and / or liquid forms. These molecules released by the packaging lead to prolonged protection of the organoleptic and hygienic characteristics of the packaged foods.

4) Caps and covers with technological function according to figure 4.

- The technological function caps and lids according to FIG. 4, are packaging materials characterized by one or more technological activities which are carried out during one or more stages of the manufacturing process or during the storage of the food product and which participate in obtaining the final nutritional and taste properties of the food.

The production of stoppers and lids according to FIG. 4, makes use of various materials, whether associated or not, such as synthetic plastics (polyethylene, polypropylene, etc.), and / or such as metal compounds (iron, (aluminum, brass, ...). The models of caps or covers according to figure 4 have three complementary components:

- a hollow tubular body (1), made of hard plastics or of metal, open and extended in its upper part by a circular bearing rim (2) on the neck of the container (9). The tubular body (1) comprises, in its lower distal part, a multi-perforated and porous wall (3), coated on its inner surface with a micro-porous synthetic membrane (4) (cutoff threshold <0.2 μ ), which is permeable: to water, to gases (oxygen, nitrogen, carbon dioxide, etc.) and to molecules of low molecular weight (MW less than 100,000 D .: salts, simple sugars, alcohol and intermediate metabolites, ...) but which is impermeable to prokaryotic and eukaryotic cells (bacteria, yeasts, fungi and molds, ...), of high molecular weights (MW greater than 1,000,000 D. ). The internal wall of (1) and the membrane (4) which covers it, form and limit a reservoir cavity (5).

- a removable head (6), made of plastic, which is fixed and closes the upper orifice of the body (l),

- a notched metal cap (7), which covers the head (6) and fixes it, hermetically, on the container (8).

- According to a first indicative but not exclusive example of industrial production and application of the invention, the plug model according to FIG. 4, receives in its reservoir (5), an aliquot of 4 mg. of live yeasts of the genus Saccharomyces cerevisiae in the total number of 20,000,000 CFU, in the lyophilized state and coated in 4 g of glucose. The body (1) thus produced is closed by the head (6) and it is kept cold, at + 4 ° C. until its technical use which includes an expiration period of 12 months. The characteristics of this technological stopper according to the invention are applied more particularly during the second fermentation which occurs during the manufacturing process of sparkling wines and champagnes. To this end, the cork is introduced into the neck of a bottle filled with wine on which it is fixed by clipping the iron cap (7). The water and the components of the wine come into contact with the openings (3) of the wall (1) then pass through the pores of the membrane (4) by capillary action and come into contact with the yeasts imprisoned in (5). This results in an activation of the metabolism of the yeasts which, from the sugars present in the medium, initiate alcoholic fermentation, in particular producing ethyl alcohol and carbon dioxide (E290). The micropores of the hydrophilic and permeable membrane (4) allow bilateral transmembrane passages on the one hand from the molecules of water, salts and sugars contained in the food liquid to the yeasts imprisoned in the reservoir (5) and d 'on the other hand from fermentation metabolites from yeasts (carbon dioxide, ethyl alcohol, etc.) to the liquid food contained in the container (8).

The fermentation process continues until all the sugars contained are used up, and the final drink obtained is then enriched with ethyl alcohol and effervescent carbon dioxide. The device of FIG. 4 according to the invention makes it possible to obtain a controlled fermentation and foaming of fruit juices and wines intended for the production of sparkling drinks: sparkling wines and champagnes. At the end of the fermentation, the manipulations of disgorging and eliminating the populations of yeasts trapped in the stopper are greatly facilitated by the extraction of the technical stopper according to figure 4.

The final closure of the sparkling drink is immediately carried out in an advantageous manner thanks to the caps according to Figures 2 or 3. The use of the bio-active cap thus allows a consequent reduction in the various handling of bottles and it allows a substantial saving of time as well. a significant reduction in handling costs incurred during riddling and disgorging operations.

- A second preferred but non-exclusive embodiment and industrial application of the model according to Figure 4, consists of the manufacture of a plastic bung which is intended, depending on its format and dimensions, for closing bottles, barrels and barrels receiving new wine.

By way of example, during the manufacture of a bung intended for 200 L wine barrels, the reservoir (5) according to FIG. 4 receives ten milliliters of a composition formed from a mixture of yeasts of the genus Schizosaccharomyces pombe at 10x7 cells / ml. and lactic acid bacteria of the genera Leuconostoc oenos and Lactobacillus plantarum at 10x7 cells / ml. suspended in grape juice diluted to 5% and pH. 4.5. Contact of the cork with the conditioned new wine activates the bacteria contained in the reservoir (5) and leads, thanks to the transmembrane exchanges, to malolactic fermentation of the conditioned wine.

This device according to the invention makes it possible to take advantage of the packaging and storage of the new wine to activate its malolactic fermentation and to cause its controlled deacidification. The device according to the invention can be formatted to larger dimensions and be activated, for example, by a 40 ml load of a suspension of yeast and lactic acid bacteria at 10 × 7 cells / ml. in grape juice diluted to 5% and pH. 4.5. This example of a device constitutes a malolactic fermentation bung for a barrel which stores 900 liters of red wine during aging.

More generally, the type of stopper according to FIG. 4 represents a fermentation bioreactor intended for the technological treatment of fermentable food liquids stored in containers. The characteristics of the stopper according to FIG. 4, objects of the invention, allow the controlled technological treatment of food liquids such as fruit juices (grape, pear, peach, apple, orange, lemon juice, etc. pineapple, grapefruit, tomato, blackcurrant, redcurrant, etc ...), wines, brewer's musts and whey, the fermentation of which is sought to obtain final alcoholic drinks and / or effervescent, such as sparkling wines and fruit juices, champagnes, beers, kefir. These models of caps and lids according to figure 4, with variable formats and dimensions depending on the size of the container to be capped, constitute various industrial applications as bottle caps, as active bungs for barrels, barrels, cans. and carboys, and as lids for large capacity vessels.

5) Multiple function caps and covers according to figure 5.

The multi-function caps and lids according to figure 5 are characterized by the fact that they combine the devices described respectively in figures 3 and 4 to form a new device which constitutes an original model of cap and / or lid with two compartments contiguous, separated by membranes with selective permeability. The caps and lids according to figure 5 are made of different materials, whether associated or not, such as synthetic plastics (polyethylene, polypropylene, etc.), metal compounds (iron, brass, and the cover according to figure 5 have three complementary parts:

a first hollow tubular body (1), made of high density plastics or of metal, terminated in its upper part by a circular bearing rim (2) on the neck of the container (11). The body (1) is closed in its lower part by a microporous membrane (3) with a cut-off threshold of less than 0.2 micron and permeable to water, gases (oxygen, nitrogen, carbon dioxide, etc. ) and molecules with molecular weights of less than 100,000 daltons (salts, simple sugars, alcohols and intermediate metabolites, chemical radicals,) but impermeable to microbial cells such as bacteria, yeasts, and molds. The body (l) and the membrane (3) define a cavity (4) which acts as a reservoir.

- a second hollow cylindrical body (7) having an upper terminal thread (8) which allows the screwing of the body (7) on the inner base of the head (5), itself being provided with an internal screw thread ( 6) on the neck (11).

The internal cavity (10) of the body (7) is limited in its lower part by a microporous synthetic membrane (9) with a cut-off threshold of less than 0.2 μ. And permeable to water, gases (oxygen, nitrogen, carbon dioxide, etc.) and molecules with molecular weights of less than 10,000 daltons (salts, simple sugars, alcohol and intermediate metabolites, oxygenated radicals). The final assembly of the closed bodies (1) and (7) consists of a new cap having two internal compartments (4) and (10), the respective contents of which are separated from the food distributed by two membranes 13) and (9) with defined porosities.

- According to a first indicative but not exclusive example of embodiment of the invention according to Figure 5, a high density polyethylene bung is formatted to the dimensions of a cylinder 5 cm in diameter by 10 cm high, intended for carboys of 20 liters receiving drinking water. The active plug according to the invention is characterized by an antiseptic function which is exerted throughout the packaging and storage steps, thus participating in the health protection and prolonged food safety of the product contained.

The manufacture of the plug according to figure (5) comprises the following steps:

- the reservoir (4) receives 5 ml of a 5% sodium thiocyanate solution.

- the reservoir (10) receives 10ml of a sterile 5% aqueous glucose solution.

- the membrane (9) is activated by binding of glucose oxidase (ECN ° 1.1.3.4.).

- the membrane (3) is activated by binding of lacto-peroxidase (EC N ° ll 1.1.7.).

As an indication and without limitation, the enzyme solutions used for the covalent bindings are prepared in 50 mM citrate-phosphate buffer at pH 7.5 as follows:

- solution at 1 mg / ml of fungal glucose oxidase (EC n ° l. 1.3.4.) at 40 IU / mggrade II of SIGMA- (St Louis - United States): glucose oxidase, in the presence of oxygen, hydrolyzes glucose to D. glucono-lactone (E575), and to hydrogen peroxide.

- 0.5 mg solution of bovine lactoperoxidase (EC N ° 1.11.1.7.) at 40 IU / mg grade II of SIGMA- (St Louis- United States): lacto-peroxidase in the presence of hydrogen peroxide (H2O2 ) catalyzes the oxidation of thiocyanate to oxythiocyanate OSCN-.

Each type of enzyme is fixed by immersion for 60 minutes. at room temperature, 1 square meter of nylon membrane, PALLType Immunodyne ABC- brand, in a container containing 500ml of one of the buffered solutions prepared above. The membrane is then rinsed 3 times with 100 ml of pH 7.5 phosphate buffer and then saturated by immersion in 100 ml of a 2% solution of bovine casein in phosphate buffer pH 7.5 for 15 min at room temperature. After 3 new rinses with 100 ml of phosphate buffer, the membranes (3) and (9) are drained and then dried at -20 ° C. under vacuum and stored at + 4 ° C, in a dehydrated atmosphere, until their final insertion by mechanical fixing and gluing on the respective lower end pieces of the bodies (1) and (7) of 1 bung according to figure (5). bung obtained by the final assembly of the bodies (1) and (7) is stored in a cold room at 4 ° C. until it is fixed on the cylinder. The stoppering of the cylinder and its storage at room temperature causes the activation of the enzymatic systems grafted on the membranes (3) and (9).

In the presence of hydrogen peroxide produced by glucose oxidase on both sides of the membrane (9), an oxidation reaction of the thiocyanate ion by lactoperoxidase begins in (4) and continues on both sides. the other of the membrane (3) with production and diffusion of oxidized acid derivatives according to the following reactions:

OSCN- + H 202 ----------- 02 - SCN- + H2O

Oxythiocyanate + Superoxythiocyanate peroxide

O2SCN- + H 202 ----------------> 03 - SCN- + H2O

Superoxythiocyanate Trioxythiocyanate

The free radicals produced as well as the oxidized substrates diffuse through the permeable membrane (3) towards the drinking water of the container (11), in which they interact strongly with any microbes present.

The lactoperoxidase (LP) system exhibits strong biocidal and biostatic activities with respect to various microorganisms such as bacteria (Listerias, staphylococci, salmonella, pseudomonas, mycoplasmas, etc.), protozoa (Cryptosporidia), viruses (Bacteriophages ). The antimicrobial activity of the oxygen radicals released by the stopper allows the control and / or reduction of the microbial contaminants present in the food and leads to a prolonged sanitary quality of the conditioned water.

The natural anti-microbial system LP, integrated into a packaging device for food products, constitutes a new industrial application, which is the subject of the invention. The characteristic properties of the packaging device according to the invention allow practical and repetitive use for treating, sanitizing and stabilizing, for a prolonged period, liquid foods such as milk and dairy products, mineral water, flavored drinking water and diet drinks from various energy and / or therapeutic diets.

The caps, lids and lids of food packaging according to the models of Figures 1, 2, 3, 4 and 5, characterized by the fact that at least one of their elements and / or their constituents is structured and formatted to be a receptacle and / or a reservoir for food additives and processing aids.

The new models of bioactive caps and lids according to the invention differ from the active packaging already in existence by their specific formats, by their biological formulations and by their functional activities. They have the advantages of technical utility, ease of use and speed of implementation thanks to their suitability for distribution chains.

The use of bioactive packaging according to the invention leads to a gain in productivity for the manufacturer, to a commercial gain for the distributor, and to a gain in quality for the consumer.

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