Bioactive Packages and Package Closures

Abstract

The invention relates to an active package and/or an active package closure having different formats, made of metal and/or synthetic and/or natural associated or not materials. According to said invention, at least one element and/or component of said packages contains and distributes one or several dietary additives and complements and/or ingredients and technological auxiliaries used for producing foods an cosmetics. The inventive bioactive packages and closures are provided with novel specific functions such as additive and/or technical and/or antimicrobial functions with respect to a packed product. Said bioactive packages and closures confer to packed products sanitary, organoleptic and nutritional characteristics and are used for controllingly preserving the products during packaging, storage, transportation and distribution thereof.

Description

This invention relates to the arrangement, production and industrial applications of new packaging materials represented by devices such as bioactive stoppers, lid seals, seals, caps, lids, plugs and valves designed to close bottles, flasks, jars, boxes, cans, barrels, tanks and other containers used to package and store food and dietary products and cosmetic products.

These new so-called bioactive packages are constituted, alone or in combination, by metal and/or cellulosic and/or synthetic materials, and are characterised by the fact that at least one of their elements and/or constituents incorporates, and/or contains, and/or diffuses biochemical and/or biological substances that confer new functional properties on these packages. A package is generally defined as an assembly of materials designed to receive, contain and protect a good intended to be stored, transported and sold. In particular, a food package must, by virtue of its intrinsic properties, enable optimal preservation of the food contents throughout its lifetime, from production to consumption. It must protect the food from external germs, offer selective gas barrier properties, withstand changes related to temperature or hygrometry of the environment during storage, sale and use by the consumer and comply with regulations.

The packages currently used provide passive functions of receiving, packaging, physical containment and mechanical protection of foods from the environmental factors encountered during the steps of production, storage, transport and sale. The European regulations on packages in contact with food are designed to protect the consumer's health. The European directive 89/109/EC stipulates that the materials and objects intended to come into contact with foods must satisfy the principle of inertial. The materials and objects intended to come into contact with foodstuffs, products and drinks for consumption must not, under the normal or expected conditions of use, transfer constituents to these foodstuffs in an amount that could present a health hazard or lead to an unacceptable change in the composition of the foodstuffs. This directive therefore does not allow the use of active packages that satisfy the following definition according to Wagner (1989): “An active package provides more than simple production. It interacts with the product and in some cases responds to changes in the environment or the product itself”.

A new European regulation has modified the directive 89/109/EC and now takes into account the concept of “active” packages, which authorises the principle of “deliberate transfer or absorption of compounds to or from the food in order to maintain or enhance the conditions of preservation of the product”.

The packaging materials can therefore modify the composition of the foodstuffs only if the modifications comply with the community provisions applicable to foodstuffs, as defined in the directive 89/107/CEE relating to food additives.

Substances such as food additives deliberately incorporated into certain active materials intended to come into contact with foodstuffs so as to be released into the packaged foodstuffs can be allowed. According to Gontard, these active packages can be classified into three main categories:

1) Interactive packages that act in a controlled manner on the food so as to enhance and preserve its quality over the course of the distribution chain. The activity of these packages is intended to control the risks of food deterioration associated with various mechanisms of lipid oxidation, tissue browning, vitamin destruction or microbial contamination. Numerous products are available on the market in the form of oxygen-absorbing bags or carbon dioxide-absorbing bags, produced by Mitsubishi Gas Chemical (Japan), Multiform Dessicant (United States), Bioka (Finland) and Standa (France).

2) Indicator packages that react with the properties of the food and the preservation conditions so as to inform the consumer of said conditions. The devices generally used are Weather/Temperature indicators based on enzymatic- or polymerisation-type reactions. They are produced by various companies: 3M Monitor (Great Britain), Trigon Industries (Great Britain), Lifelines Technology (United States), Pillsbury Co. (United States), Marupfroid (France). Coloured indicators of gas concentration of pH in the package are also sold by Mitsubishi Gas Chemical Co. and Toppan Printing Co. (Japan) and by Trigon Industries (Great Britain).

3) Preparatory packages that make it possible to modify the properties of the food so as to facilitate its consumption. These are essentially self-heating or self-cooling packages proposed by Print Pak Inc. (United States), Baritalia (Italy) and Bréger (France).

In addition, some packaging devices used temporarily during the food production steps are considered to be technological packages. The new bioactive stoppers, caps, lids, lid seals, valves and seals according to the invention differ from the active packages that already exist by virtue of their specific arrangements, their biochemical or biological contents and by their new functional activities. These new packages or package closures are arranged so as to adapt to various types of containers, such as bottles, flasks, boxes, brick cartons, jars, terrines, cans, jugs, barrels, casks, tanks and cisterns, and are characterised by the fact that they comprise at least one element or one constituent capable of producing and/or diffusing at least one non-hydrating substance constituted, in a pure or combined form, by biochemical and/or biological compounds, belonging to the additives and dietary supplements and/or ingredients and processing aids used in the production of foodstuffs and cosmetic products, which substance is in particular a colouring agent, and/or an antioxidant, and/or a preservative, and/or a flavouring agent, and/or a sweetener, and/or an acidulant, and/or an emulsifier, and/or a thickener, and/or a stabiliser, and/or a flavour enhancer, and/or a gas and/or a bioactive ingredient.

The chemical and/or biological compounds can in particular be:

• • chemical elements (oxygenated free radicals, mineral salts, etc.);
  • nitrogenated, chlorinated, iodized, bromated, sulphated, phosphated molecules, etc.;
  • biochemical elements (carbohydrates, fats, proteins, metabolites, etc.);
  • biological elements (flavourings, vitamins, enzymes, immunoglobulins, etc.);
  • microbiological elements (bacteria, yeast and fungi, etc.).

In particular, they can be:

• • gas (carbon dioxide, sulphur dioxide, nitrogen, etc.);
  • salts (sodium, potassium, calcium, magnesium, iron or zinc salts, sodium or potassium phosphates, sodium or potassium thiocyanates, sodium or potassium sulphites, sodium, potassium or magnesium carbonates, sodium or potassium nitrites and nitrates, etc.);
  • vitamins (vitamin A and carotenoids, vitamins B1, B2, B5, B6, B8, B9, B12, vitamins C, D, E, K, PP, etc.);
  • carbohydrates: lactose, saccharose, fructose, glucose, inulin, fructosaccharides;
  • fats: polyunsaturated fatty acids, etc.;
  • proteins: lactoferrin, bioactive peptides, lysozyme, etc.;
  • enzymes: oxidoreductase, beta-galactosidase, glucose-oxidase, xanthine-oxidase, sulphite-oxidase, peroxidase, catalase, etc.;
  • antimicrobial immunoglobulins: antibacterial, antifungal, antiviral, antiparasitic antibodies, etc.;
  • microorganisms: lactic bacteria (Lactobacillus, Lactococcus, etc.), yeast (Saccharomyces, etc.), fungi (Penicillium, Streptomyces, etc.).

The bioactive stoppers, caps, lid seals, seals, valves and lids according to the invention are characterised by the fact that they make it possible, when closing the container, to obtain, alone and/or in combination:

• • the addition and diffusion, immediate and/or delayed, of various compounds and their interaction products contained in the constituents and/or in the elements of the closures to and in the packaged products;
  • flavour and/or nutritional enrichment, sanitary protection and prolonged preservation of packaged liquid products (milks, wines, champagnes, ciders, beers, fruit juices, waters, lotions, etc.), semi-liquid products (milk products, vegetable soups, vegetable purees, compotes, jams, creams, sauces, prepared foods, pomades, ointments, etc.) and solid products (fruits and vegetables, powders, grains, etc.).

The type, the mode of assembly and the arrangement of the structural elements, the formulation of the bioactive compounds, the new functional properties and the industrial applications of new packages and package closures (stopper, lid seal, lid, seal, plug, valve, etc.) are the subject of this invention described above, according to five different models provided by way of a non-limiting indication, shown respectively in FIGS. 1 to 5.

These figures are side cross-section views of these various models.

Cap, Lid Seal and Lid with Additive Function According to FIG. 1

According to a first general preferred but not exclusive embodiment of the packaging devices according to the invention, the cap, lid seal or lid model according to FIG. 1 is characterised by its additive function, which consists of containing and diffusing food additives and/or ingredients and processing aids, previously included, to the packaged product. The cap, lid seal and lid are constituted by different materials, associated or not, such as metal compounds (aluminium, iron, tin, etc.), and/or synthetic plastic materials (polyethylene, polypropylene, etc.).

The cap, lid seal and lid models according to FIG. 1 comprise a head 1, which is provided with an internal thread 3 enabling it to be screwed onto the neck of the container 8, and which is extended by a hollow cylindrical body 2 of various dimensions. The body 2 has an internal cavity 4 that comprises at least one of the two elements constituted respectively by the part 5 and/or by the O-ring 6, structured in one or more superimposed layers (6a, 6b, etc.). The part 5, with a cellular and spongy structure, is advantageously constituted by the assembly arranged with different expanded materials, associated or not, such as plastic materials (polyethylene, polypropylene, polyvinyl, polysulphone, polyurethane, etc.), or natural polymerised materials (starch, cellulose, agarose, casein, chitosan, lactic acid, etc.). The part 5 is formed by one or more superimposed layers and it constitutes a container of which the dimensions and arrangement vary with the size of the container to be closed and with the amount of additives and ingredients to be filled.

By way of an indicative but non-limiting example, the part 5, composed of low-density and spongy polyethylene, is arranged in an elastic and compressible disk. The part 5 then receives a predetermined filler, in the form of a powder or a solution, of food additives and/or processing aids, pure or combined, represented by preservatives (lactic, acetic, peracetic and tartaric acids, sodium and potassium sulphites, sodium and potassium nitrites, sodium and potassium bicarbonate, hydroxy-8 quinoline, oxygenated water and peroxy salts, ethanol, sodium hypochlorite, nisin and bacteriocins, essential plant oils, etc.), and/or by antioxidants (carbon gas, nitrogen, argon, natural phenolic compounds, etc.) and/or by vitamins (vitamins A, C, E), and/or by sweeteners (polyols, acesulphame, aspartame, cyclamate, thaumatin, neohesperidin, etc.), and/or by flavour enhancers (glutamates, ribonucleotides, ethylmaltol, etc.), and/or by active proteins and peptides (lysozyme, reduced lactoferrin and transferrin, glucose-oxidase, catalase, lacto-peroxidase, glutathion, etc.), and/or by flavourings (eugenol, vanillin, pinene, limonene, geranial). The O-ring seal 6, structured in one or more superimposed layers (6a, 6b, etc.) comprises one or more pores 7 allowing solutions located at 5 to pass toward space 4.

By way of an indicative but non-limiting example, the first layer 6a, made of expanded polyethylene, is filled with a given volume of liquid-phase additives. The layer 6b, joined to layer 6a, is constituted by an aluminium film with a thickness of 0.5 mm, with a barrier effect and impermeable to water and gas (oxygen, nitrogen, carbon gas), which serves as a lid seal after screwing. The placement of the cap on the neck of the container 8 creates a vertical circular pressure on the seal 6 and on the disk 5, which will then release, through the opening 7, most of their respective contents into the packaged product in 8. The residual additives in 5 and 6a then continue their slow diffusion toward the packaged foodstuff in 8, over the course of the storage period. The model according to FIG. 1a, which has two distinct containers 5 and 6, allows for the separate and sequential filling and diffusion of compounds that are relatively or totally incompatible with one another. The characteristic advantage of this cap, lid seal and lid model with an additive function according to FIG. 1 of the invention lies in the fact that the diffusion of the active compounds occurs sequentially, first when the container is closed and then throughout the storage of the foodstuff. This characteristic involves in an increased production time as well as a prolonged period of diffusion of the active compounds into the product thus packaged.

According to a first preferred but not exclusive example of the industrial production and application according to the invention, the cap according to FIG. 1, made of polypropylene, is arranged so as to close a 1-litre formula milk bottle, with a wide neck 4 cm in diameter. The cap comprises, in its internal cavity 4, two distinct containers represented respectively by the disk 5 and the seal 6. The production of the active capsule, intended for packaging the formula milk, is performed as possible: the disk 5, constituted by a polymerised and expanded cellulose matrix, receives a filler of vitamins and food ingredients combined in an original formulation satisfying the dietetic properties required for packaged formula milk. The seal 6a is filled by two millilitres (2 ml) of a mixture of vitamins (vitamins A, D, E), emulsifiers (lecithin), and fatty acids, according to the formulation indicated below by way of indication:

• • vitamin A (E160a): 400 mg
  • vitamin D3: 12.5 mg
  • vitamin E (E306): 6.6 g
  • linoleic acid: 40 g
  • linolenic acid: 50 g
  • carnitine: 80 g
  • taurine: 3.5 g
  • lecithin (E322): 30 g
  • water, q.s.f. 1000 ml.

The disk 5 is filled by one millilitre (1 ml) of a mixture of water-soluble vitamins (vitamins B, C, PP, etc.), proteins (lactoferrin, lactoperoxidase, lysozyme, antimicrobial antibodies, etc.), mineral salts and oligo-elements, according to the formulation provided below by way of indication:

• • vitamin B1: 400 mg
  • vitamin B2: 1.5 g
  • vitamin B5: 3 g
  • vitamin B6: 0.6 g
  • vitamin B9: 90 mg
  • vitamin B12: 2 g;
  • vitamin C (E300-E301-E302): 60 g
  • vitamin P: 600 mg
  • calcium orthophosphate (E341): 75 g
  • magnesium carbonate (E504): 10 g
  • zinc: 8 g
  • sodium iodide (E010): 150 mg
  • bovine ferrin: 0.5 g
  • bovine lactoperoxidase: 0.5 g
  • ozyme (E1105): 0.5 g
  • antiviral lactic immunoglobulins: 50 g
  • water: q.s.f. 1000 ml.

The disk 5b and the seal 6a thus filled are inserted on the interior base of the head 1 of the cap. The cap is then attached by its screw thread 2 on the neck 8 of the container. The screwing of the capsule causes the migration and diffusion of the vitamins, salts, fatty acids and proteins contained in 5 and 6a into the milk packaged in 8. The formula milk preparations currently available comprise vitamin-enriched formulations. Some of these vitamins (in particular B vitamins), are heat-sensitive and are destroyed by the heat sterilisation procedures applied to the milk before the packaging thereof. The use of an active cap according to the invention enables the vitamins, and in particular heat-sensitive vitamins, to be added after sterilisation and packaging, thus making it possible to protect the molecular integrity and the biological activity of these vitamins in the formula milk. A characteristic of the active cap according to the invention thus consists of maintaining the nutritional properties of this dietetic milk during its period of storage, transport and distribution.

A second example of an application according to FIG. 1, provided below by way of a non-limiting indication, is represented by an active cap used to package fresh milk. The constituents of the fresh milk, in particular fats and certain vitamins, are sensitive to the atmospheric oxygen and are altered by oxidation during storage. The production of an anti-oxygen capsule intended for packaging fresh milk is performed as follows: the disk 5 is filled by one millilitre (1 ml) of a solution of ascorbic acid (E300) or ascorbates (E301 or E302 or E304), at 30 g per litre, and the seal 6 receives 1 g of tocopherols (E306) in emulsion. The disk 5 and the seal 6 thus filled are inserted into the space 4 and bonded to the interior base of the head 1. The active cap is then screwed onto the neck 8 of the container. The screwing causes the diffusion of the ascorbic acid and the tocopherols toward the milk packaged in 8. The properties of the active cap according to the invention allow for prolonged preservation of the organoleptic properties of the milk and its cheese derivatives, and they constitute an important competitive advantage in their marketing.

A third example of an application according to FIG. 1, provided below by way of a non-limiting indication, is represented by an active cap intended for packaging food oils. In this application, the disk 5 receives for one millilitre (1 ml), a filler of one gram (1 g) of tocopherols (E306) emulsified in a solution of fatty acid esters (E471) at 5 g per litre. The seal 6a is filled by one millilitre (1 ml) of a liquid mixture with 10% ascorbic acid (E300) and 10% propyl gallate (E310). The specific functions of the cap according to FIG. 1 are characterised by nutritional enrichment and by the protection against oxidation of high-fat foodstuffs such as food oils, margarines, fats and essential plant oils, fresh milks, industrial milks, dietetic milks and cheese products (fermented milk, butter, cottage cheese and yogurt).

A fourth indicative and non-limiting example of an application is represented by a cap arranged according to FIG. 1 and intended to close bottles, flasks, brick cartons and boxes receiving wine. The metal or synthetic cap comprises a head 1 with a diameter of 3 cm extended by a body 3, 6 cm long. During the production of the active cap, the space 4 receives the circular part 5 constituted by viscose fibre sheets superimposed in a seal according to FIG. 6 and filled with sulphites (potassium metabisulphite) (E228, for example), with doses capable of ranging from 25 mg to 100 mg, in the form of powders or grains. The part 5 is then attached by bonding to the interior base of the cap. After closing the bottle 8, the sulphite filler comes into contact with the wine and is progressively diffused therein, providing prolonged protection from oxidation and from the growth of microbial contaminants present. In this specific application for packaging wine, the active cap according to FIG. 1 can be arranged and sized in various ways according to the size of the container receiving the wine.

According to the invention, the arrangements and dimensions used for the cap according to FIG. 1 can involve the production of a barrel and/or cask plug, or a tank valve lid or “cubitainer” for preservative functions.

A fifth example of an application of the stopper according to FIG. 1, provided by way of a non-limiting indication, concerns a metal capsule arranged and filled for closing beer bottles and/or flasks of infusion concentrations and/or jars containing jams and marmalades. To this end, the disk 5 made of expanded polypropylene, receives a filler of 1 ml of a solution with 200 mg/litre of potassium sorbate (E202), and the seal 6 receives a filler of 1 ml of a sodium benzoate solution (E211) with 150 mg/litre. These additives released after plugging the container provide protection against oxidation as well as prolonged preservation of the organoleptic properties of the packaged foodstuffs.

A sixth example of an application according to FIG. 1, provided by way of a non-limiting indication, is a synthetic lid seal arranged and filled for closing containers (bottles, flasks, boxes, etc.) receiving fruit juices or flavoured waters or specific dietetic drinks. To this end, the disk 5, made of woven polyethylene, receives a filler of 1 ml of a solution containing 100 mg/litre of ascorbic acid (E300) and 100 mg/litre of citric acid (E330). The seal 6a receives a filler of 0.5 ml of a flavouring solution comprising, for 1 litre:

1 mg of vanillin+1 mg of isoeugenol+10 g of tannin+0.25 mg of guanylic acid (E626)+0.25 mg of inosinic acid (E630)+20 mg of asparatame (PS 200). These additives released after plugging the container 8 make it possible to preserve the flavouring, dietetic and gustatory properties of the packaged drinks.

According to a seventh non-exclusive example of an application, a flat screw-on lid of variable dimensions and made of a synthetic material is arranged according to FIG. 1 for the active closure of jars, and/or glass cups, and/or terrines receiving treated or cooked foods. The lid comprises a circular head 1 with a diameter of 8 cm and a height of 2 cm, on which a circular part 5 is attached to the interior face, which circular part 5 is made of woven viscose fibre, 7.8 cm in diameter and 0.5 cm in thickness, and is filled with 100 mg of a mixture of powders in equal volumes of potassium sorbates (E200) and lactates (E270). The packaging of sauces, purees, candied fruits, jams and compotes in containers closed by this type of active lid allows for the dissolution and diffusion of the active principles contained in 5 toward the surface of the distributed foods and allows for their protection and their prolonged preservation until consumption. The cap, lid seal, seal and lid models according to FIG. 1 make it possible, depending on the specific type and formulation of the compounds filled in elements 5 and/or 6, to transfer to the foodstuff distributed in 8, various molecules such as salts, oligoelements, vitamins, amino acids, peptides and proteins, sugars and sweeteners, preservatives, flavourings and fruit, vegetable and various plant extracts. The characteristic additive functions of these bioactive closures according to the invention consist of the addition and the diffusion of food additives and/or processing aids for nutritional enrichment and controlled preservation of packaged products such as foods (milks and milk products, wines, alcohols, spirits, syrups, fruit juices, mineral waters, dietetic drinks, infusions, herbal teas, jams, etc.), and cosmetic preparations (eaux de toilette, lotions, pomades, creams, ointments, etc.).

Stoppers and Lid Seals with Additive and Protective Functions According to FIG. 2

According to a second general preferred but non-exclusive embodiment of the packaging devices according to the invention, the stopper and lid seal models according to FIG. 2 are characterised by their protective function, which consists of containing, releasing and diffusing antimicrobial substances included toward the packaged food. The stoppers and lid seals are constituted by various materials, combined or not, such as natural materials (cellulose, cork, etc.), or plastic materials (polyethylene, polypropylene, etc.), and/or glass.

According to a first indicative but non-limiting example, the stopper according to FIG. 2 is produced to close still or effervescent wine bottles. It comprises a main cylindrical body 1 constituted by agglomerated granulated cork and/or compact cork. The method for producing the active stopper according to the invention consists of treating either the granulated cork before assembly or the cork body 1 using at least one given antiseptic solution so as to impregnate and fill the cork with antimicrobial molecules. For example, and in a non-limiting manner, the body 1 of the stopper is immersed for 7 days at room temperature in a 10% ethanol solution; at the end of this maceration period, the body 1 is dried in a sterile atmosphere, then immersed a second time for 5 days at room temperature in a concentrated sulphur dioxide solution provided in the form of sodium bisulphite (E222) or potassium bisulphite (E228) at 18% (180 g/l of SO2). The stopper is then drained and dried superficially for 5 minutes at 40° C., then packaged in an impermeable plastic bag and sealed until its final use. Two characteristic properties of the cork stopper treated according to the invention are its chemical innocuousness and its microbial sterility, acquired during the process. The treated stopper is free of certain original chemical contaminants such as the trichloroanisols and microorganisms present in the raw cork, and it furthermore preserves its initial physical properties essential for preservation of the organoleptic characteristics of the stopped wines and champagnes.

A third characteristic of the active stopper obtained according to the invention is applied during the stopping of the wine bottles: the active stopper is compressed when it is inserted into the neck and it then releases, at its surface, small amounts of sulphur dioxide, which sanitize the internal and external surfaces of the bottle neck. This characteristic makes it possible to control and manage the risk of subsequent proliferation of microorganisms on the head of the stopper.

A fourth characteristic application of the stopper according to the invention consists of the slow diffusion of the sulphur dioxide impregnated in the body 1 toward the wine in which it will perform its protective activity during storage. In general, the active stopper according to the invention can be subjected, at the time of production, to one or more cycles of impregnation and treatment with antimicrobial agents, used alone or in a mixture, such as antiseptic solutions (sulphites, alcohols, hypochlorites, etc.), and/or gases (formaldehyde) and/or ionising radiation.

According to a second indicative but non-exclusive example of the industrial production and application according to the invention, the stopper according to FIG. 2 is arranged to plug bottles of effervescent alcoholic drinks such as sparkling wines, ciders and champagnes. The stopper, formed by a main cylindrical body 1, made of cork or synthetic polymers, comprises at each of its ends a depression 2 capable of being coated, as needed, with a polyethylene cup 3. The cavity 2 or the cup 3 receives a filler of 100 mg of potassium metabisulphite (E228), then it is closed, by bonding, using a microporous polytetrafluoroethylene lid seal 4 permeable to water and gases. After stopping the container 5, the sulphites in 2 or in 3 diffuse through the membrane 4 and are progressively released into the immediate environment f the stopper, and into the container 5 and its contents. The antimicrobial activity of the sulphur dioxide released by the active stopper makes it possible to control the residual microbial flora (yeast, mould, fermenting bacteria, etc.) of the packaged drinks and to prolong their preservation period.

In general, the type of stopper according to FIG. 2 is characterised by its arrangement and by its formulation of active compounds filled in its constituents and/or 2 and/or 3 and by its capacity to diffuse, toward the product distributed in 5, various additives and processing aids such as salts, oligoelements, vitamins, amino acids, peptides and proteins, fatty acids, flavourings and plant extracts, sugars and preservatives.

Stoppers and Lids with Additive and Protective Functions According to FIG. 3

According to a third general preferred but non-exclusive embodiment of the packaging devices according to the invention, the stopper, lid and lid seal models according to FIG. 3 are characterised by their antioxidant function, which consists of containing and diffusing antioxidant substances included. The stopper and lids, constituted by different materials, combined or not, such as metal compounds (aluminium, iron, tin, etc.), plastic materials (polyethylene, polypropylene, copolymers, etc.), and/or natural materials (cellulose, cork, etc.), comprise a main body 1, superimposed by a head 2 and equipped, in its lower terminal portion, with a hollow cup 3 acting as a container 4, and closed by a microporous lid seal 5 with one or more layers permeable to water and gases.

According to a first indicative but non-limiting example of the industrial production and application according to the invention, the active stopper according to FIG. 3 is produced so as to close bottles of wines for aging, heated wines and aromatic wines sensitive to oxidation reactions. It is constituted by a main cylindrical body 1 made of cork, superimposed by a round head 2 made of copolymers and equipped in its lower portion with a cup 3 made of polyethylene delimiting a space 4 that receives, during the activation, a filler constituted by a mixture of 50 mg of potassium metabisulphite granules (E222), and 50 mg of sodium bicarbonate powder (E500), (or potassium (E501) or ammonium (E503) or calcium (E001) bicarbonate powder). The cup 4 is closed by a lid seal 5 made of polyvinylidene fluoride (PVDF), which is microporous and permeable to water and gas. The closure of the bottle 6 by this active stopper causes a migration of the water vapour from the drink packaged in 6 toward the container 4 through the lid seal 5. The potassium metabisulphite and the sodium bicarbonate in contact with the water respectively produce sulphur dioxide and carbon dioxide, which migrate through the lid seal 5 and then diffuse in the closed space of the bottle 6. The cumulative antioxidant activities of the sulphur dioxide and the carbon dioxide thus diffused result in the prolonged protection of the organoleptic properties of the packaged drinks.

According to a second indicative but non-exclusive example of the industrial production and application of the invention, the active stopper according to FIG. 3 is produced so as to close bottles of fruit syrups and flavoured non-alcoholic drinks. When the stopper is activated, the space 4 receives 50 mg of sodium metabisulphite granules (E222), and the PVDF lid seal 5 is impregnated with 50 mg of L-ascorbic acid (E300) in solution. The cup 3 is then closed by the lid seal 5, which is permeable to water and gases. After stopping the bottle 6, the ascorbic acid filled in 5 and the sodium bisulphite contained in 4 are progressively released into the drink packaged in 6. The cumulative antioxidant activities of the sulphur dioxide and the ascorbic acid released by the stopper lead to the inhibition of the oxidation phenomena of the packaged drinks and to the preservation of their initial properties during storage.

According to a third indicative but non-exclusive example of the industrial production and application according to the invention, the active closure according to FIG. 3 is arranged in a flat plastic lid, with dimensions suitable either for tubes 6, for packaging butcher and deli means (filets, cutlets, steaks, kebabs, sausages, etc.) or for boxes 6 for distributing fresh vegetables (salads, pickles, aromatic plants, herbal teas, etc.). For example, the lid according to FIG. 3 comprises a synthetic rectangular body 1 and head 2 (20 cm×15 cm), 2 cm in height, and it receives, by bonding on the interior base, a cylindrical multilayer part 3, 5 cm in diameter and 0.5 cm in thickness, defining a volume 4 limited in its lower portion by a membrane 5. The part 3 includes three superimposed layers:

• • the upper sheet 3 made of polyethylene with a cellular and spongy structure, which receives, in a mixture or not, 3 ml of a solution of organic preservative acids (acetic acid (E260), lactic acid (E270), proprionic acid (E280)), and stabilising salts such as sodium (E339), potassium (E340), or calcium (E341) orthophosphates;
  • the space 4, delimited by the sheets 3 and 4, and which receives a powder blend composed of 50 mg of calcium citrate (E333) and 10 mg of chlorophyll-type colouring agents (E140);
  • the lower sheet 5, constituted by a polyamide membrane, which is porous and permeable to water and gases.

According to the type of packaged foodstuff, the sheet 3 and the space 4 may also contain and diffuse certain additives and additional ingredients such as gelling agents (E401, E415, E450a, E516), colouring agents (E120) and preservatives (E202, E325).

After stopping the container 6, the water vapours from the foodstuffs distributed in 6 impregnate and pass through the layer 5 to the container 4 and the sheet 3, where they are solubilised and then activate, by capillarity, the migration and diffusion of the active principles in 3 and 4 toward the meets or vegetables contained in 6.

According to a fourth indicative but non-exclusive example of the industrial production and application according to the invention, the stopper according to FIG. 3 is arranged as a plastic plug for cans intended to store 20 litres of raw or concentrated fruit juices. The plug, which has a cylindrical shape (10 cm in diameter and 5 cm in thickness) includes a head 2 extended by a body 1 that has, on its lower portion, a recess 3 for 20 cc of volume, acting as a vessel 4. It receives a filler of 10 ml of glucose in a 10% solution and is closed by a nylon membrane 5 that is permeable to water and gases, of the PALL-Type Immunodyne ABC brand, activated and carrying glucose-oxidase (E.C. No. 1.1.3.4). The bonding of the enzyme molecules to the membrane to the membrane 5 is achieved by immersion thereof, for 1 hour, in a vat containing 500 ml of a buffer solution with 2 g/litre, per 1 square metre of membrane. The contact between the enzymatic solution and the membrane 5 for 120 minutes at room temperature allows for the stabilised bonding of the proteins to the membrane and the creation of an enzyme layer on the membrane surface (80 □g of proteins per square centimetre). The distribution of dietary liquids in a container closed by the lid according to FIG. 3 is followed by an emission of water vapours that come into contact with the membrane 5, where they cause the activation of the enzymes, which hydrolyse the glucose present in 4, producing gluconic acid and hydrogen peroxide. This production is a function of the initial glucose concentration and the temperature in the plug and, by diffusing in the distributed liquid, it causes an antimicrobial activity associated with the oxygenated water and an antioxidant acidulant activity associated the gluconic acid. The main characteristic of these lids according to the invention consists of their intrinsic capacity to generate, in a quantitatively controlled manner, active metabolites such as organic acids and oxygenated water at low and constant rates, which lead to prolonged protection and preservation of the distributed drinks.

In general, and depending on the intended activity, the membrane 5 of the stoppers, lid seals and lids according to FIG. 3 can be activated, according to a method of adsorption and/or incarceration and/or covalent bonding, by pure or combined enzyme molecules, such as proteases (trypsin, pepsin, papain, carboxypeptidases, etc.), and/or oxidases (amylases, cellulases, mannosidases, galactosidases, fructosidases, glucosidases, etc.) and/or esterases (pectinesterase, polygalacturonase), and/or lipases (triglyceride esterases), and/or oxidoreductases (peroxidases, glucose oxidase, catalase, etc.).

According to the variable modalities of the industrial productions and applications of the invention, the active stoppers, lid seals and lids according to FIG. 3 receive and/or produce and diffuse, in variable volumes, various compounds, pure or mixed, such as antioxidants, colouring agents and preservatives in solid, gaseous and/or liquid forms. These compounds produced or released by the active package provide prolonged protection of the characteristic properties of the packaged foodstuffs.

Stoppers and Lids with a Technological Function According to FIG. 4

The stoppers and lids with a technological function according to FIG. 4 are packaging materials characterised by one or more technical activities that are performed during one or more steps of the production process or during storage, and that are involved in obtaining the final characteristics of the foodstuff. The production of stoppers and lids according to FIG. 4 involves various materials, combined or not, such as plastic materials (polyethylene, polypropylene, etc.) and/or metal compounds (iron, aluminium, brass, tin, etc.). The stopper and lid models according to FIG. 4 comprise three additional constituent parts:

• • a hollow tubular body 1, made of plastic or metal material, open and extended in its upper portion by a circular edge for contact on the neck of the container 7. The tubular body 1 comprises, in its lower portion, a multi-openwork and porous wall 2, covered on its internal surface by a synthetic membrane 3 (cellulose esters or nylon or polyethylene), which is microporous (cut-off<0.2 _) and permeable to water, gases (oxygen, carbon dioxide, etc.) and to low-molecular-weight molecules (MW<100,000 D. such as salts, simple sugars, alcohol and metabolites, etc.), but which is impermeable to prokaryotic and eukaryotic cells (bacteria, yeast, fungi and mould, etc.), of high molecular weight (MW>1,000,000 D.). The wall 2 and the membrane 3 that covers it form and limit a container cavity 4;
  • a removable head 5, made of plastic materials, that is attached to and closes the upper opening of the body 1;
  • a notched metal cap 6 that covers the head 5 by attaching it hermetically on the container 7.

According to a first indicative but non-exclusive example of the industrial application and production of the invention, the stopper model according to FIG. 4 receives, in its container 4, an aliquot of 4 mg of active yeast of the Saccharomyces cerevisiae genus in a total number of 20,000,000 CFU, in lyophilized state and coated with 4 g of glucose. The body 1 thus produced is closed by the head 5, and preserved at cold temperature, at +4° C., until its technical use. The characteristics of this technical stopper according to the invention are applied in bottle fermentation that occur during the sparkling wine and champagne production process. To this end, the closed stopper (1+5) is placed on a bottle filled with wine, to which it is attached by clipping on the cap 6. The water and the components of the wine come into contact with the openings 3 of the wall 1, then they pass by capillarity through the pores of the membrane 3 and come into contact with the yeast incarcerated in 4. The activation of the metabolism of the yeast then follows, which, owing to the sugar present in the medium, leads to alcoholic fermentation, producing in particular ethyl alcohol and carbon gas (E290). The micropores of the hydrophilic and permeable membrane 3 enable bilateral transmembrane passages of, on the one hand, the water, salt and sugar molecules contained in the dietary liquid toward the yeast incarcerated in the container, and on the other hand, the fermentation metabolites from the yeast (carbon gas, ethyl alcohol) toward the dietary liquid contained in the container 7. The fermentation process continues until exhaustion of the sugars contained and the final drink obtained is then enriched with ethyl alcohol and effervescent carbon gas.

The device of FIG. 4 according to the invention makes it possible to obtain fermentation and controlled bottle fermentation of fruit juices and wines intended for producing effervescent drinks: sparkling wines, ciders and champagnes. At the end of the fermentation, the disgorging and removal of yeast populations contained in the stopper are greatly facilitated by the extraction of the technical stopper according to FIG. 4. The final stopping of the sparkling drink is also performed advantageously with the stoppers according to FIG. 2 or 3. The use of the bioactive stopper thus makes the various bottle handling operations easier and allows for a substantial savings of time as well as a significant reduction in handling costs in shaking and disgorging operations.

A second preferred but non-exclusive embodiment for industrial production and application of the model according to FIG. 4 consists of the production of a plug with plastic materials, which is intended, according to its arrangement and dimensions, to close bottles, barrels and casks receiving new wine. By way of example, during the production of a plug intended for wine barrels of 2001, the container 4 according to FIG. 4 receives ten millilitres of a composition formed by a mixture of yeast of the Schizosaccharomyces pombe genus at 10×7 cells/ml and lactic bacteria of the Leuconostoc oenos and Lactobacillus plantarum genii at 10×7 cells/ml in suspension in grape juice diluted at 5% with a pH of 4.5. The contact of the stopper with the new packaged wine activates the bacteria contained in the container 4 and leads, owing to the transmembrane exchanges, to the malolactic fermentation of the packaged wine.

This device according to the invention makes it possible to take advantage of the packaging and storage of the new wine so as to activate its malolactic fermentation and promote controlled de-acidification. The device according to the invention can be arranged with greater dimensions and be activated, for example, by a filler of 40 ml of a suspension of yeast and lactic bacteria at 10×7 cells/ml in grape juice diluted at 5% with a pH of 4.5. This device example constitutes a malolactic fermentation plug for a cask storing 900 litres of red wine in production. More generally, the stopper model according to FIG. 4, which is the subject of the invention, has the characteristics of a fermentation bioreactor that enables the treatment of liquids such as fruit juices (grape, pear, peach, apple, orange, lemon, pineapple, grapefruit, tomato, cassis, current juice, etc.), wines, brewer's worts, milks, whey and cell culture media to be metabolised so as to obtain final alcoholic and/or effervescent drinks (sparkling wines and fruit juices, champagnes, beers, etc.), fermented milks (kefir, yogurt, etc.) or microbial biomass (lactic and propionic bacteria, yeast and fungi, etc.). These active package closures according to FIG. 4, produced according to variable arrangements and dimensions and equipped with specific activities constituting new useful industrial tools such as bottle stoppers, plugs for barrels, casks, cans and jugs, and cisterns and tanks.

Stoppers and Lids with Multiple Functions According to FIG. 5

The stoppers and lids with multiple functions according to FIG. 5 are characterised by the fact that they combine the devices described respectively in FIGS. 3 and 4 to form a new device that constitutes an original stopper and/or lid model with two contiguous compartments, separated by membranes with selective permeability. The stoppers and lids according to FIG. 5 are constituted by various materials combined or not, such as synthetic plastic materials (polyethylene, polypropylene, etc.), metal compounds such as iron, brass, etc.) and a lid according to FIG. 5, and comprise three complementary portions:

• • a first hollow tubular body 1, made of high-density plastic materials or metal, terminated in its upper portion by a circular edge for contact 2 on the neck of the container 11. The body 1 is closed in its lower portion by a microporous membrane 3 at the cut-off below 0.2 micron and impermeable to water, gases (oxygen, nitrogen, carbon dioxide, etc.) and to molecules with a molecular weight below 100,000 daltons (salts, simple sugars, alcohols and intermediate metabolites, chemical radicals), but impermeable to microbial cells such as bacteria, yeast and mould. The body 1 and the membrane 3 delimit a cavity 4 that acts as a container.
  • a second hollow cylindrical body 7 having an upper terminal threading 8 that enables the body 7 to be screwed onto the interior base of the head 5, itself provided with an internal screw threading 6 on the neck 11. The internal cavity 10 of the body 7 is limited in its lower portion by a synthetic microporous membrane 9 at the cut-off below 0.2 micron and permeable to water, gases (oxygen, nitrogen, carbon gas, etc.) and to molecules with a molecular weight below 10,000 daltons (salts, simple sugars, alcohol and intermediate metabolites, oxygenated radicals). The final assembly of the closed bodies 1 and 7 comprises a new stopper having two internal compartments 4 and 10, of which the respective contents are separated from the food distributed by two membranes 3 and 9 with defined porosities.

According to a first indicative but non-exclusive example of the production of the invention according to FIG. 5, a high-density polyethylene plug is arranged with the dimensions of a cylinder with a diameter of 5 cm and a height of 10 cm, intended for 20-litre jugs receiving drinking water. The active plug according to the invention is characterised by an antiseptic function that is performed throughout the steps of packaging and storing, thus participating in the sanitary protection and the prolonged food safety of the product contained. The production of the plug according to FIG. 5 comprises the following steps:

• • the container 4 receives 5 ml of a 5% sodium thiocyanate solution;
  • the container 10 receives 10 ml of a sterile 5% glucose solution;
  • the membrane 9 is activated by a glucose-oxidase bond (E.C. No. 1.1.3.4);
  • the membrane 3 is activated by a lactoperoxidase bond (E.C. No. 1.11.1.7).

By way of a non-limiting indication, the enzyme solutions used for the covalent bonds are prepared in a citrate-phosphate buffer 50 mM with a pH of 7.5, as follows:

• • solution at 1 mg/ml of fungal glucose-oxidase (E.C. No. 1.1.3.4) at 40 IU/mg—SIGMA grade II—(St. Louis, United States): glucose-oxidase in the presence of oxygen, hydrolyse the glucose into D-gluconolactone (E575), and oxygenated water;
  • solution at 0.5 mg of bovine lactoperoxidase (E.C. No. 1.11.1.7) at 40 IU/mg—SIGMA grade II—(St. Louis, United States): lactoperoxidase in the presence of oxygenated water (H2O2) catalyses the oxidation of the thiocyanate into oxythiocyanate OSCN—. The bonding of each type of enzyme is performed by immersion, for 60 minutes at room temperature, for 1 square metre of nylon membrane, of the PALL-Type Immunodyne ABC brand, in a vat containing 500 ml of one of the buffer solutions prepared above. The membrane is then rinsed 3 times with 100 ml of a phosphate buffer at pH 7.5, then saturated by immersion in 100 ml of a 2% bovine casein solution in a phosphate buffer at pH 7.5 for 15 minutes at room temperature. After 3 new rinsing steps with 100 ml of phosphate buffer, the membranes 3 and 9 are drained, then dried at −20° C. in a vacuum and stored at +4° C., in a dehydrated atmosphere, until their final insertion by mechanical bonding on the respective lower end pieces of the bodies 1 and 7 of the plug according to FIG. 5. The plug obtained by the final assembly of bodies 1 and 7 is stored in a cold chamber at 4° C. until it is attached to the jug. The stopper of the jug and its storage at room temperature leads to the activation of the enzymatic systems grafted onto the membranes 3 and 9. In the presence of hydrogen peroxide produced by the glucose-oxidase of the two sides of the membrane 9, an oxidation reaction of the thiocyanate ion by the lactoperoxidase occurs in 4 and continues on each side of the membrane 3 with the production and diffusion of acid derivatives oxidised according to the following reactions:

OSCN—+H2O2→O2—SCN—+H2O

Oxythiocyanate+peroxide Superoxythiocyanate

O2SCN—+H2O2→O3—SCN—+H2O

Superoxythiocyanate      Trioxythiocyanate

The free radicals produced as well as the oxidised substrates diffuse through the permeable membrane 3 toward the drinking water of the container 11, in which they interact strongly on any microbes that may be present. The lactoperoxidase (LP) system has strong biocidal and biostatic activities with respect to various microorganisms such as bacteria (Listerias, staphylococci, salmonellae, pseudomonae, mycoplasms, etc.), protozoa (Cryptosporidia), viruses (Bacteriophages). The antimicrobial activity of the oxygenated radicals released by the stopper makes it possible to control and/or reduce the microbial contaminants present in the food and leads to prolonged sanitary quality of the packaged water. The natural LP antimicrobial system, integrated in a packaging device for fragile products, constitutes a new industrial application, which is the subject of the invention. The characteristic properties of the packaging device according to FIG. 5 authorises a practical and repeatable use for treating, asepticising and stabilising, in a prolonged manner, liquid foods such as milks and milk products, mineral waters, flavoured drinking waters and dietetic drinks for various diets for energy and/or therapeutic purposes.

The active packages and package closures according to FIGS. 1, 2, 3, 4 and 5 are characterised by the fact that at least one of their elements and/or their constituents is structured and arranged to receive and/or produce and/or diffuse food additives and processing aids. These new models of bioactive caps, stoppers, lid seals and lids according to the invention differ from the active packages already existing by virtue of their arrangements and their specific biological formulations, and by their functional activities. They have the advantages of technical usefulness, simplicity of use and speed of implementation owing to their suitability for the current distribution machines. Use of the bioactive packages according to the invention leads to an increase in productivity for the industry, a commercial gain for the distributor and an increase in quality for the consumer.

Claims

1. Active package and/or package closure in various arrangements stopper, cap, seal, lid seal, lid, plug and valve, characterised in that they comprise at least one element or one constituent capable of producing and/or diffusing at least one non-hydrating substance constituted, in pure or combined form, by biochemical and/or biological compounds, belonging to the additives and dietary supplements and/or ingredients and processing aids used in the production of foodstuffs and cosmetic products, which substance is in particular a colouring agent, and/or an antioxidant, and/or a preservative, and/or a flavouring agent, and/or a sweetener, and/or an acidulant, and/or an emulsifier, and/or a thickener, and/or a stabiliser, and/or a flavour enhancer, and/or a gas and/or a bioactive ingredient.

2. Active package and active package closure according to claim 1, characterised in that said substance is composed of molecules, in pure or combined form, such as:

gases (carbon dioxide, sulphur dioxide, nitrogen, etc.);

salts (sodium, potassium, calcium, magnesium, iron or zinc salts, sodium or potassium phosphates, sodium or potassium thiocyanates, sodium or potassium sulphites, sodium, potassium or magnesium carbonates, sodium or potassium nitrites and nitrates, etc.);

vitamins (vitamin A and carotenoids, vitamins B1, B2, B5, B6, B8, B9, B12, vitamins C, D, E, K, PP, etc.);

carbohydrates: lactose, saccharose, fructose, glucose, inulin, fructosaccharides;

fats: polyunsaturated fatty acids, etc.;

proteins: lactoferrin, bioactive peptides, lysozyme, etc.;

enzymes: oxidoreductase, beta-galactosidase, glucose-oxidase, xanthine-oxidase, sulphite-oxidase, peroxidase, catalase, etc.;

antimicrobial immunoglobulins: antibacterial, antifungal, antiviral, antiparasitic antibodies, etc.;

microorganisms: lactic bacteria (Lactobacillus, Lactococcus, etc.), yeast (Saccharomyces, etc.), fungi (Penicillium, Streptomyces, etc.).

3. Active package and active package closure according to claim 1, characterised in that it has a head (1), extended by a main body (2) comprising an internal space (4) equipped with at least one compressible element (5) impregnated with food additives and processing aids in liquid or solid phase, and which rests on a porous and permeable seal (6).

4. Active package and active package closure according to claim 1, characterised in that it has a main body (1) comprising, at each end, a cavity or an integrated cup (3) containing a filler of food additives and processing aids in the form of powders and/or soluble grains (4) and closed by a membrane or by a permeable lid seal (5).

5. Active package and active package closure according to claim 1, characterised in that it has a main body (1) superimposed by a head (2), and equipped in its lower portion with a cavity or an integrated cup (3) containing a filler of food additives and processing aids in the form of powders and/or soluble grains (4) and closed by a membrane or by a permeable lid seal (5).

6. Active package and active package closure according to claim 1, characterised in that it has a main tubular multi-openwork (2) body (1) covered on its surface by a synthetic membrane (3), which is microporous and permeable to water, gases and metabolites, but impermeable bacteria, yeast and fungi; the cavity (4) contains a filler of technological additives such as fermentation microorganisms (bacteria and/or yeast and/or fungi) in the form of soluble grains or powders, and is closed by a lid seal (5) attached by a cap (6) on the container (7).

7. Active package and active package closure according to claim 1, characterised in that it has two complementary tubular bodies (1) and (7) respectively comprising cavities (4) and (10) closed at their lower ends by membranes (3) and (9) permeable to water, gases and metabolites but impermeable to microorganisms (bacteria, yeast, fungi). The cavity (4) contains a filler of food additives and/or processing aids (carbohydrates, salts, proteins, etc.) in soluble powder form and the cavity (10) contains a filler of salts (potassium thiocyanate, etc.) in soluble powder form; the permeable membrane (3) has a layer of enzymes (glucose-oxidase, etc.) attached by covalent bonds and the permeable membrane (9) has a layer of enzymes (peroxidases, etc.) attached by covalent bonds.

8. Active package and active package closure according to claim 1, characterised in that it has new functions applicable to obtaining and/or preserving physicochemical, organoleptic, nutritional, dietetic, sanitary and cosmetic properties of foodstuffs thus packaged such as waters, wines, champagnes, beers, fruit juices, plant oils, milks and milk products, vegetable soups, vegetable purees, herbal teas and plant extracts, jams and compotes, sauces, egg products, meats, fruits, vegetables, salads, spices and condiments, creams, pomades, lotions and eaux de toilette.

9. Active package and active package closure according to claim 2, characterised in that it has a head (1), extended by a main body (2) comprising an internal space (4) equipped with at least one compressible element (5) impregnated with food additives and processing aids in liquid or solid phase, and which rests on a porous and permeable seal (6).

10. Active package and active package closure according to claim 2, characterised in that it has a main body (1) comprising, at each end, a cavity or an integrated cup (3) containing a filler of food additives and processing aids in the form of powders and/or soluble grains (4) and closed by a membrane or by a permeable lid seal (5).

11. Active package and active package closure according to claim 2, characterised in that it has a main body (1) superimposed by a head (2), and equipped in its lower portion with a cavity or an integrated cup (3) containing a filler of food additives and processing aids in the form of powders and/or soluble grains (4) and closed by a membrane or by a permeable lid seal (5).

12. Active package and active package closure according to claim 2, characterised in that it has a main tubular multi-openwork (2) body (1) covered on its surface by a synthetic membrane (3), which is microporous and permeable to water, gases and metabolites, but impermeable bacteria, yeast and fungi; the cavity (4) contains a filler of technological additives such as fermentation microorganisms (bacteria and/or yeast and/or fungi) in the form of soluble grains or powders, and is closed by a lid seal (5) attached by a cap (6) on the container (7).

13. Active package and active package closure according to claim 2, characterised in that it has two complementary tubular bodies (1) and (7) respectively comprising cavities (4) and (10) closed at their lower ends by membranes (3) and (9) permeable to water, gases and metabolites but impermeable to microorganisms (bacteria, yeast, fungi). The cavity (4) contains a filler of food additives and/or processing aids (carbohydrates, salts, proteins, etc.) in soluble powder form and the cavity (10) contains a filler of salts (potassium thiocyanate, etc.) in soluble powder form; the permeable membrane (3) has a layer of enzymes (glucose-oxidase, etc.) attached by covalent bonds and the permeable membrane (9) has a layer of enzymes (peroxidases, etc.) attached by covalent bonds.

14. Active package and active package closure according to claim 2, characterised in that it has new functions applicable to obtaining and/or preserving physicochemical, organoleptic, nutritional, dietetic, sanitary and cosmetic properties of foodstuffs thus packaged such as waters, wines, champagnes, beers, fruit juices, plant oils, milks and milk products, vegetable soups, vegetable purees, herbal teas and plant extracts, jams and compotes, sauces, egg products, meats, fruits, vegetables, salads, spices and condiments, creams, pomades, lotions and eaux de toilette.