EP2001759B1 - Diffusion-reducing cork coating - Google Patents

Diffusion-reducing cork coating Download PDF

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Publication number
EP2001759B1
EP2001759B1 EP07711466A EP07711466A EP2001759B1 EP 2001759 B1 EP2001759 B1 EP 2001759B1 EP 07711466 A EP07711466 A EP 07711466A EP 07711466 A EP07711466 A EP 07711466A EP 2001759 B1 EP2001759 B1 EP 2001759B1
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EP
European Patent Office
Prior art keywords
coating
cork
stopper
layer
hydrophobic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Not-in-force
Application number
EP07711466A
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German (de)
French (fr)
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EP2001759A1 (en
Inventor
Andreas Schmidt
Mustapha Benomar
Carsten Friese
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Publication of EP2001759A1 publication Critical patent/EP2001759A1/en
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D39/00—Closures arranged within necks or pouring openings or in discharge apertures, e.g. stoppers
    • B65D39/0005—Closures arranged within necks or pouring openings or in discharge apertures, e.g. stoppers made in one piece
    • B65D39/0011—Closures arranged within necks or pouring openings or in discharge apertures, e.g. stoppers made in one piece from natural or synthetic cork, e.g. for wine bottles or the like
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B67—OPENING, CLOSING OR CLEANING BOTTLES, JARS OR SIMILAR CONTAINERS; LIQUID HANDLING
    • B67B—APPLYING CLOSURE MEMBERS TO BOTTLES JARS, OR SIMILAR CONTAINERS; OPENING CLOSED CONTAINERS
    • B67B1/00—Closing bottles, jars or similar containers by applying stoppers
    • B67B1/03—Pretreatment of stoppers, e.g. cleaning, steaming, heating, impregnating or coating; Applying resilient rings to stoppers

Definitions

  • the invention relates to a method for producing a multiple coating on cork stoppers intended to reduce diffusion of undesirable components through the cork surface. Furthermore, the invention relates to cork stoppers for closing bottles, which are provided with a multiple coating.
  • cork as a stopper for closing beverage bottles has long been known.
  • the drinks may be alcoholic or non-alcoholic.
  • cork stoppers are used in bottle-shaped containers. During storage, it can not be ruled out that the liquid will come into contact with the side of the cork stopper facing the inside of the bottle for a longer period of time. As a problem may occur that unwanted components from the cork can migrate into the drink, which have toxic properties there, change the composition or can significantly affect the taste of the drink.
  • TCA trichloroanisole
  • WO 00/64649 there is described a method of producing a coating on a cork to prevent flavor-active or odor-active ingredients from diffusing, using a copolymer which must have a flexible ingredient and a component retaining the active ingredient.
  • the restrained ingredient should bind the active substance.
  • Various coatings of aqueous solutions of silanes are described, wherein the solvent evaporates by heating and cross-linking the polymeric component.
  • the lamination of cork is mentioned with plastic films. Creating a double coating with different coatings is not described.
  • WO 00/64647 For example, a method is described for producing a coating on a substrate which has the task of preventing the diffusion of taste or odor-active compounds.
  • the polymer present in the coating should prevent migration of the components.
  • the polymers are listed here without mentioning the particular requirements necessary to impart this desired property to the coating.
  • the US 6,348,243 It is known to describe a method of applying a thin surface coating to a cork to prevent contamination from the cork from migrating out of the molding, the coating comprising a thin layer of silicone rubber.
  • the rubber is dispersed in a solvent and is intended to be ultrasonicated be distributed to the surface.
  • the coating should have a thickness of 20 microns or less.
  • the coatings must also have additional properties; in particular, they must be flexible in order not to be destroyed when the compressible cork is applied to the bottle. In addition, they are said to have a friction-reducing effect to facilitate removal of the cork stopper from the bottle.
  • the prior art coating processes are in need of improvement.
  • Bonding with foils is technically complex.
  • the different requirements for a coating limit the choice of polymers.
  • the object is achieved by a method according to claim 1.
  • the plug is provided with two different coatings based on liquid coating agents.
  • cork stoppers As a substrate from which the cork stoppers can be made, natural cork is known, ie the plug is made of a piece of cork bark. Furthermore, it is known to glue cork granules with adhesives in the form of plates or strands and then make these up in a plug shape. It may be agglomerated or microagglomerated cork. Such substrates have on the surface next to each other cork parts and small amounts of adhesive. Furthermore, cork materials are known, which may consist of cork granules and portions of plastic granules, which are glued together. Likewise, synthetic cork materials are known, which are based on polymers or polymer foams.
  • a particularly distinctive aroma-active component TCA is known. This can occur in natural cork materials and even with small amounts of a significant deterioration of the taste of the food. However, it may also contain derivatives or similar compounds. In synthetic cork, such substances are not included. However, it may contain other aroma-active substances that change the taste of the food or should not get into the liquid for food law reasons.
  • cork stoppers which are already packaged for use in bottles as a shaped body, provided with a dual coating. It should consist of a coating of film-forming substances having substantially hydrophilic properties.
  • the second coating should consist of film-forming substances which have substantially hydrophobic properties. Possibly. it is also possible to apply additional layers to this two-layer coating.
  • the order of the layers can be selected according to the substance to be hindered in the migration. It can be seen from the direction of the substrate surface, first a coating with hydrophilic properties are applied and then a coating with hydrophobic properties. Likewise, a reverse procedure is possible. However, a coating which has a hydrophilic coating on the cork substrate and a hydrophobic coating on the contents is preferred.
  • the corresponding polymers of the coating compositions should be liquid at the application temperature, they may be soluble, they may be present in the form of a dispersion.
  • polymers are also understood low molecular weight oligomers, as long as they still have film-forming properties as a coating or can crosslink to give polymers.
  • They can be reactive compounds or unreactive polymers or oligomers can be used. However, these should no longer contain volatile components as a coating.
  • organic solvent-based coating agents are possible. However, preference is given to using aqueous dispersions or solvent-free coating compositions.
  • the hydrophilic coating agent contains at least one hydrophilic polymer.
  • hydrophilic polymers are natural or synthetic polymers, such as polysaccharides, e.g. As starch, dextrins, cellulose, proteins, polyvinyl alcohol, polyvinylpyrrolidone, poly (meth) acrylic acid, higher molecular weight polyethylene glycols or polyols and derivatives thereof.
  • Examples of natural polymers are polysaccharides, ie polymeric compounds based on repeating sugar units.
  • Polysaccharides which are suitable in the context of the present invention are, for example, those based on cellulose or starch.
  • a suitable polymer according to the invention may be, for example, a polysaccharide, as it is present in natural form.
  • polysaccharides which have been prepared synthetically or derivatives of natural or synthetic polysaccharides Such derivatives of starch and / or cellulose may, for example, be modified by oxidation, esterification, etherification, acid degradation.
  • the alkyl and / or (ar) alkyl groups preferably additionally nonionic, anionic or cationic groups.
  • Such reactions and corresponding polymers are known to the person skilled in the art.
  • the individual molecules are usually substituted differently, so that their degree of substitution is an average.
  • Examples of such hydrophilic polymers are hydroxyalkyl ether starches, hydroxyalkyl celluloses, carboxyalkyl celluloses, carboxyalkyl ether starches; Dextrins or hydroxyalkyldextrins. These can be used individually or in a mixture.
  • polypeptides is gelatin, which may have a molecular weight of 15,000 to more than 250,000 g / mol. It is a product produced by hydrolysis of the collagen contained in the skin and bones of animals.
  • the amino acid composition of gelatin is similar to that of the collagen from which it was obtained.
  • polystyrene resin Suitable are synthetic polymers containing many polar groups, such as polyvinylpyrrolidone, polyvinyl alcohols or polycarboxylic acids, such as poly (meth) acrylic acid, optionally as a copolymer with optionally OH-bearing esters of (meth) acrylic acid.
  • Such hydrophilic polymers can optionally be modified on the functional groups or react with crosslinking constituents.
  • polyalkylene glycols are polyalkylene glycols. These are, for example, polyethylene glycols, polypropylene glycols or polytetrahydrofurans, or else mixed copolymers in random or block copolymeric form. In particular, portions of ethylene oxide building blocks are necessary to ensure sufficient hydrophilicity.
  • di- or polyfunctional polyalkylene glycols have a molecular weight of between 600 and 30,000 (as measured by GPC). They can be liquid or they are highly viscous or solid substances. Possibly. it is possible to add to these polymers of the coating agent crosslinking substances which lead to polymerization under the application conditions or cause crosslinking of the polymer after application of the coating composition. Examples of such crosslinkers are polyisocyanates or polyepoxides which give crosslinked polymer layers on heating and / or under catalysis.
  • Preferred polymers are either liquid or dissolved or dispersed in solvents, especially in water.
  • coating compositions may contain additives to influence processing properties of the dispersion or film properties of the coating.
  • Additives are, for example, antioxidants, rheology aids, viscosity regulators, adhesion promoters, pH regulators, leveling agents, degassing agents, defoaming agents, emulsifiers.
  • the viscosity of the coating agent is adapted to the application method.
  • the coating agents are applied to the substrate and adhere to form ionic and covalent forces on the surface. Possibly. it is also possible that crosslinking substances are contained in the coating agent, which can react with the substrate.
  • the second coating agent should contain hydrophobic polymers as an essential ingredient.
  • Polymers with hydrophobic properties are known.
  • these may be silicone oils or silicone compounds, polymers based on perfluorinated compounds, polymers based on polyolefins, waxes, polyamides or similar polymers.
  • These polymers should be liquid at the application temperature, they may be dissolved or they may be dispersed in solvents.
  • a known group of hydrophobic polymers suitable according to the invention are silicone polymers or oligomers. They may be polysiloxanes which are liquid or solid, they may have crosslinking groups or they may be inert. They may have functional groups. Rubbery, non-flowable polymers are less suitable. Examples of such compounds are silicone oils, polysiloxanes or optionally substituted alkoxysilanes.
  • Waxes can be natural waxes, chemically modified waxes or synthetic waxes.
  • Natural waxes include, for example, vegetable waxes such as carnauba wax, sugar cane wax, montan wax, beeswax, shellac wax, lanolin, mineral waxes or petrochemical waxes such as petrolatum, paraffin waxes or microwaxes.
  • Synthetic waxes are generally understood as meaning polyalkylene waxes or polyalkylene glycol waxes. Also suitable are synthetically produced waxes from carboxylic acids and fatty alcohols or fatty acid amides. Also to the waxes, for example, so-called wax alcohols are counted, i. higher molecular weight, water-insoluble fatty alcohols having usually about 22 to 40 carbon atoms. Such products are known to the person skilled in the art.
  • hydrophobic components are vegetable oils, such as sunflower oil, soybean oil, rapeseed oil, wheat germ oil, and the liquid portions of coconut oil, or fatty acid and fatty alcohol esters, such as monoesters of the fatty acids with alcohols having 3 to 24 carbon atoms. These can be liquid or highly viscous or they are solid at room temperature.
  • liquid or solid paraffins can be used as constituent of the hydrophobic coating agent, such as unbranched paraffin hydrocarbons, in particular C 12-24 alkanes, or isoparaffins
  • hydrophobic substances are perfluorinated compounds such as perfluorinated fatty acids, esters of carboxylic acids with perfluorinated alcohols, perfluorinated olefin (co) polymers.
  • a particularly suitable group of compounds are alkyl siloxanes which have OH groups and / or NH groups, in particular those which contain hydroxyl groups, hydroxycarboxylic acid groups and / or mono- / disaccharides in the main chain or in the side chain.
  • they are substituted aminoalkylsiloxanes and / or higher alkyl-modified amidoaminosiloxanes containing from 10 to 1500 silicon atoms.
  • substituents are hydrogen atoms, monovalent, optionally fluorine-, chlorine- or bromine-substituted C 1 - to C 18 -hydrocarbon radicals, C 1 - to C 12 -alkoxy or hydroxy radicals, hydroxycarboxylic acids, mono- and disaccharides, alkyl glycol radicals and / or primary or secondary amino groups or amido groups.
  • Such compounds are for example in the EP 1081272 or the DE 10214982 described.
  • Such polymers can be converted into the water phase, for example, by means of suitable emulsifiers.
  • the hydrophobic coating agent or coating made therefrom may contain one or more of the above-mentioned hydrophobic polymers or oligomers. It may be present in the coating agent polymer substances which have a total of hydrophobic properties. However, it may also be low molecular weight oligomers which under the application conditions, for. B. in the aqueous phase, can be crosslinked as a coated layer after film formation to polymers. The corresponding higher molecular weight polymers of the coating film should then have the hydrophobic properties.
  • the hydrophobic coating agent may be inert, it may be self-crosslinking, or crosslinkers may additionally be present in the coating composition.
  • various additives and auxiliaries may be contained in the coating agent, which facilitate the processing of the coating agent or influence the properties of the coating. It can work to be the same classes of substances that are to be present as additives in the hydrophilic coating compositions.
  • emulsifiers or other dispersing aids it must be ensured that these additives do not impair the essential character of the coating as a hydrophobic coating.
  • the two coatings are applied successively to the substrate. It is possible that the cork stopper is evenly coated on all surfaces. However, it may be sufficient to coat only the side facing the content and the side facing the edge of the bottle. Possibly. It is also possible to coat a correspondingly small Korkform redesign and glue it to an uncoated cork stopper on the liquid side facing.
  • the coating compositions should be liquid at the application temperature. This may preferably be between 15 and 70 ° C., preferably between 20 and 40 ° C. or at the usual room temperature.
  • both coatings produce a dense coating on the cork stopper. Since the cork stopper may possibly have pores and imperfections on the surface, it may be necessary to apply a correspondingly increased amount of the coating agent.
  • the coating should be applied from both layers in an amount between 1 mg / cm 2 of the surface up to 300 mg / cm 2 , in particular between 2 mg / cm 2 up to 150 mg / cm 2 . It is possible that both polymer layers have approximately the same application weight. However, it is also possible that they have different order weight. It is particularly preferred if the hydrophobic coating is at least 50%, in particular at least 70%, of the layer weight.
  • Another object of the invention is a method for coating cork substrates in plug shape, wherein at least two layers are applied. It is possible that the finished molded cork stopper is ground if necessary, and then optionally subjected to a cleaning on the surface. Further pretreatment is usually not necessary. It is also possible to print on the cork stopper.
  • the first coating agent is then applied to the corresponding cork stopper in a highly viscous or highly viscous form, preferably an aqueous solution containing at least one hydrophilic polymer.
  • the coating agent should be liquid at the application temperature. The viscosity of the coating agent can also be reduced by increased temperatures during application. However, it is preferable to operate at room temperature, i. usually between 20 to 40 ° C.
  • the cork stopper may be heated to allow evaporation of the volatiles, especially water, from the coating agent. In this case, a crosslinking reaction can be initiated. In addition, a film formation of the polymer is supported.
  • the application of the coating agent can be done by the known application method, for example by spraying, dipping, roller coating or coating in a drum. If the coated cork stoppers are moved afterwards, it is important to ensure that the integrity of the surface coating is not destroyed as much as possible.
  • the second coating step with the second coating agent preferably the hydrophobic coating agent, can be carried out.
  • the same application methods mentioned above can be used. In this case, too, it is possible to process the coating agent under heating or to perform a drying step and / or a crosslinking step after the coating step. It should be ensured in this case, a film formation.
  • One embodiment operates such that, after the first coating, the second coating is applied without further heating or crosslinking or after brief flash off of volatile constituents, if appropriate by compressed air and / or heating. Thereafter, a common drying step may be performed. In the process, possible solvents are removed and a film formation of the polymers is supported.
  • the drying of the coated cork stoppers can be carried out by known methods. This solvent, water or other volatile components can be removed. Furthermore, it is possible by heating, for. B. by the IR radiation, by passing heated gases or by heating in an oven to remove volatile components from the coating.
  • the temperatures can be between 20 ° C up to 130 ° C, in particular between 30 ° C up to 90 ° C.
  • the heating time can be between 30 seconds and 12 hours. Care must be taken that the substrate material does not undergo any negative changes at this temperature. Discolouration of the substrate material should also be avoided.
  • additional layers can be applied as needed. These can serve, for example, to protect the cork stopper during storage or application.
  • a cork stopper is obtained which has completely or partially on the surface at least a double coating.
  • This at least double coating reduces migration either as diffusion or as extraction from the cork substrate into the food. Since the polymers form a dense layer, possibly highly viscous or crosslinked, migration of aroma-active substances, in particular TCA, is markedly reduced. Even in the event that possibly pores may be present in a coating, the second coating will nevertheless reduce migration of such components.
  • the coatings should be flexible. Since in the application of a cork stopper this is compressed and then brought to its destination, the coatings according to the invention should only be crosslinked so far that a deformation is either elastic or permanently possible.
  • the polymers must not be so brittle or so cross-linked that cracks and breaks in the coating can occur. Particularly suitable are those polymers in the coatings that still have cold flow properties and can close any defects.
  • the polymers can be chosen so that they have separate performance properties.
  • the side facing the substrate is particularly suitable for reducing migration of the aroma-active constituents.
  • the side facing the liquid should avoid intensive contact of the liquid with the cork surface.
  • the polymer of this layer may be selected to allow a sliding action of the cork stopper in the neck of the bottle.
  • Cork which has a TCA content determined by blank.
  • a granulate is coated and extracted.
  • a 2% aqueous solution of hydroxyethylcellulose (Natrosol LR 250, Hercules GmbH) is prepared by stirring in water. The result is a clear thin-viscous solution ( ⁇ 200 mPas, 20 ° C).
  • An approximately 30% aqueous solution of an amido-amino siloxane is used (Tubingal FAM, CHT Beitlich GmbH), which contains about 10% of a fatty alcohol ethoxylate as emulsifier.
  • the solution is a thin viscous emulsion ( ⁇ 400 mPas, 20 ° C, Brookfield RVT, spindle 2, 50 rpm).
  • a cork granulate having a particle size of 2 to 8 mm together with 20 ml of a coating agent 1 or 2 ml of a coating agent 2 are combined and rolled in a drum. After 30 minutes, the coated cork granules are removed and dried at 80 ° C. for 7 hours. The cork granules are weighed and the weight gain indicates the amounts of coating absorbed.
  • the other coating is applied according to the same procedure.
  • the coated cork granules are placed in a beaker and treated with a 12% solution of ethanol in water. The amount is chosen so that 67 ml of aqueous solution is used on 5 g of cork granules. The material is kept below the liquid surface.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Closures For Containers (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Chemical And Physical Treatments For Wood And The Like (AREA)

Abstract

A method for coating cork stoppers is described, wherein a stopper which has optionally been cleaned and printed on the surface is provided with two coatings one after another, wherein a coating medium having a hydrophobic polymer is used and a further coating medium having hydrophilic polymers is used, and a cork stopper having an anti-diffusion two-layer coating is also described.

Description

Die Erfindung betrifft ein Verfahren zum Herstellen einer Mehrfachbeschichtung auf Kork-stopfen, die eine Diffusion von unerwünschten Bestandteilen durch die Korkoberfläche vermindern soll. Weiterhin betrifft die Erfindung Korkstopfen zum Verschließen von Flaschen, die mit einer mehrfachen Beschichtung versehen sind.The invention relates to a method for producing a multiple coating on cork stoppers intended to reduce diffusion of undesirable components through the cork surface. Furthermore, the invention relates to cork stoppers for closing bottles, which are provided with a multiple coating.

Die Verwendung von Kork als Stopfen zum Verschließen von Getränkeflaschen ist seit langem bekannt. Bei den Getränken kann es sich um alkoholische Getränke oder um nichtalkoholische Getränke handeln. Üblicherweise werden solche Korkstopfen in flaschenförmigen Behältern angewendet. Während der Lagerung ist es nicht auszuschließen, dass die Flüssigkeit längere Zeit mit der der Innenseite der Flasche zugewandten Seite des Kork-stopfens in Berührung kommt. Als Problem kann dabei auftreten, dass unerwünschte Bestandteile aus dem Kork in das Getränk migrieren können, die dort toxische Eigenschaften aufweisen, die Zusammensetzung verändern oder deutlich den Geschmack des Getränks beeinflussen können.The use of cork as a stopper for closing beverage bottles has long been known. The drinks may be alcoholic or non-alcoholic. Usually, such cork stoppers are used in bottle-shaped containers. During storage, it can not be ruled out that the liquid will come into contact with the side of the cork stopper facing the inside of the bottle for a longer period of time. As a problem may occur that unwanted components from the cork can migrate into the drink, which have toxic properties there, change the composition or can significantly affect the taste of the drink.

Solche Probleme sind insbesondere bei der Verwendung von Korkstopfen zum Verschließen von Weinflaschen bekannt. Eine bekannte Verbindung, die den Inhalt der Flasche negativ beeinträchtigt, ist TCA (Trichloranisol). Diese Verbindung kann in natürlichem Korkmaterial in geringen Spuren enthalten sein. Aber schon die Migration von geringsten Spuren TCA in den Wein gibt einen negativen Geschmack, der deutlich zu spüren ist und das Produkt ungenießbar macht. Eine Diffusion oder Extraktion von aromaschädlichen Substanzen, beispielsweise TCA, soll unter den üblichen Lagerbedingungen aus dem Korkstopfen in ein Lebensmittel deshalb verhindert werden.Such problems are particularly known in the use of cork stoppers for closing wine bottles. One known compound that adversely affects the contents of the bottle is TCA (trichloroanisole). This compound may be present in natural cork material in small amounts. But even the migration of the slightest traces TCA into the wine gives a negative taste, which is clearly felt and makes the product inedible. Diffusion or extraction of aroma-damaging substances, for example TCA, should therefore be prevented under the usual storage conditions from the cork stopper into a foodstuff.

Eine Lösung für solche Probleme ist in der US 2004/01 66 345 vorgeschlagen worden.One solution to such problems is in the US 2004/01 66 345 been proposed.

Es sind schon Verfahren beschrieben, aus natürlichem Korkmaterial solche geschmacksstörenden Stoffe, insbesondere TCA, durch Extraktion zu entfernen. Das kann beispielsweise durch Extraktion mit Lösemitteln oder flüssigem CO2 geschehen. Weiterhin sind Verfahren bekannt, Korkstopfen mit einer Polymerschicht zu versehen, um die Migration von störenden Bestandteilen aus dem Kork in das Lebensmittel zu verhindern.Methods have already been described for removing such taste-disturbing substances, in particular TCA, from extraction by natural cork material. This can be done for example by extraction with solvents or liquid CO 2 . Furthermore, methods are known to provide cork stoppers with a polymer layer to prevent the migration of interfering components from the cork into the food.

In der WO 00/64649 ist ein Verfahren beschrieben, einen Überzug auf einen Korken zu erzeugen, um geschmacksaktive oder geruchsaktive Bestandteile an einer Diffusion zu hindern, wobei ein Copolymer eingesetzt wird, das einen flexiblen Bestandteil und einen die aktive Komponente zurückhaltenden Bestandteil aufweisen muss. Dabei soll der zurückhaltende Bestandteil die aktive Substanz binden. Es werden verschiedene Beschichtungen aus wässrigen Lösungen von Silanen beschrieben, wobei durch Erwärmen das Lösemittel verdampft und die polymere Komponente vernetzt. Weiterhin wird das Kaschieren von Kork mit Kunststofffilmen erwähnt. Ein Erzeugen einer doppelten Beschichtung mit unterschiedlichen Beschichtungen wird nicht beschrieben.In the WO 00/64649 there is described a method of producing a coating on a cork to prevent flavor-active or odor-active ingredients from diffusing, using a copolymer which must have a flexible ingredient and a component retaining the active ingredient. The restrained ingredient should bind the active substance. Various coatings of aqueous solutions of silanes are described, wherein the solvent evaporates by heating and cross-linking the polymeric component. Furthermore, the lamination of cork is mentioned with plastic films. Creating a double coating with different coatings is not described.

In der WO 00/64647 wird ein Verfahren beschrieben, um auf einem Substrat eine Beschichtung zu erzeugen, die die Aufgabe hat, die Diffusion von geschmacks- oder geruchsaktiven Verbindungen zu verhindern. Das in dem Überzug vorhandene Polymer soll die Migration der Bestandteile verhindern. Dabei werden die Polymere in einer Liste aufgezählt, ohne die besonderen Anforderungen zu erwähnen, die notwendig sind, um diese gewünschte Eigenschaft der Beschichtung zu verleihen.In the WO 00/64647 For example, a method is described for producing a coating on a substrate which has the task of preventing the diffusion of taste or odor-active compounds. The polymer present in the coating should prevent migration of the components. The polymers are listed here without mentioning the particular requirements necessary to impart this desired property to the coating.

Weiterhin ist die US 6,348,243 bekannt, in der ein Verfahren zum Aufbringen einer dünnen Oberflächenbeschichtung auf einen Korken beschrieben wird, um Verunreinigungen aus dem Kork an der Migration aus dem Formkörper zu verhindern, wobei die Beschichtung eine dünne Schicht eines Silikonkautschuks umfasst. Der Kautschuk ist in einem Lösemittel dispergiert und soll mit Ultraschall auf der Oberfläche verteilt werden. Die Beschichtung soll eine Stärke von 20 µm oder weniger aufweisen.Furthermore, the US 6,348,243 It is known to describe a method of applying a thin surface coating to a cork to prevent contamination from the cork from migrating out of the molding, the coating comprising a thin layer of silicone rubber. The rubber is dispersed in a solvent and is intended to be ultrasonicated be distributed to the surface. The coating should have a thickness of 20 microns or less.

Aus der WO 2004/060764 ist ebenfalls bekannt, Korken zu beschichten. Dabei wird ein Polymerfilm als Barriereschicht mit einer Klebstoffschicht mit dem Korkstopfen verklebt. Eine Beschichtung mit zwei flüssigen Beschichtungsmitteln ist nicht beschrieben.From the WO 2004/060764 is also known to coat corks. In this case, a polymer film is glued as a barrier layer with an adhesive layer with the cork stopper. A coating with two liquid coating agents is not described.

Die Beschichtungen müssen neben der Schutzfunktion noch weitere Eigenschaften aufweisen, insbesondere müssen Sie flexibel sein, um bei der Applikation des kompressiblen Korks in die Flasche nicht zerstört zu werden. Außerdem sollen sie einen reibungsvermindernden Effekt aufweisen, um ein Entfernen des Korkstopfens aus der Flasche zu erleichtern Die Verfahren zum Beschichten gemäß dem Stand der Technik sind noch verbesserungsbedürftig.In addition to the protective function, the coatings must also have additional properties; in particular, they must be flexible in order not to be destroyed when the compressible cork is applied to the bottle. In addition, they are said to have a friction-reducing effect to facilitate removal of the cork stopper from the bottle. The prior art coating processes are in need of improvement.

Ein Verkleben mit Folien ist verfahrenstechnisch aufwändig. Die unterschiedlichen Anforderungen an eine Beschichtung schränken die Auswahl der Polymeren ein.Bonding with foils is technically complex. The different requirements for a coating limit the choice of polymers.

Aufgabe der vorliegenden Erfindung ist es deswegen, eine Beschichtung zur Verfügung zu stellen, bei der Korkstopfen an der Oberfläche mit einer Beschichtung versehen werden, die für längere Zeit die Migration von aromaschädlichen Substanzen bei Kontakt mit einer Gasphase oder in Kontakt mit einer wässrigen Flüssigkeit verhindert, die eine technisch einfache Herstellung der Stopfen gestattet und die die applikationstechnischen Anforderungen an solche Stopfen erfüllt.It is therefore an object of the present invention to provide a coating in which cork stoppers are provided on the surface with a coating which prevents the migration of aroma-damaging substances on contact with a gas phase or in contact with an aqueous liquid for a long time, which allows a technically simple production of the plug and meets the application requirements for such plugs.

Die Aufgabe wird durch ein Verfahren gemäß Anspruch 1 gelöst. Dabei wird der Stopfen mit zwei unterschiedlichen Beschichtungen auf Basis von flüssigen Beschichtungsmitteln versehen.The object is achieved by a method according to claim 1. The plug is provided with two different coatings based on liquid coating agents.

Als Substrat, aus der die Korkstopfen gefertigt sein können, ist natürlicher Kork bekannt, d. h. der Stopfen ist aus einem Stück Korkrinde gefertigt. Weiterhin ist es bekannt, Korkgranulate mit Klebstoffen in Form von Platten oder Strängen zu verkleben und diese dann in Stopfenform zu konfektionieren. Es kann sich dabei um agglomerierten oder mikroagglomerierten Kork handeln. Solche Substrate haben an der Oberfläche nebeneinander Korkanteile und geringe Klebstoffanteile. Weiterhin sind Korkmaterialien bekannt, wobei diese aus Korkgranulat und Anteilen von Kunststoffgranulat bestehen können, die miteinander verklebt werden. Ebenso sind synthetische Korkmaterialien bekannt, die auf Basis von Polymeren oder Polymerschäumen aufgebaut sind.As a substrate from which the cork stoppers can be made, natural cork is known, ie the plug is made of a piece of cork bark. Furthermore, it is known to glue cork granules with adhesives in the form of plates or strands and then make these up in a plug shape. It may be agglomerated or microagglomerated cork. Such substrates have on the surface next to each other cork parts and small amounts of adhesive. Furthermore, cork materials are known, which may consist of cork granules and portions of plastic granules, which are glued together. Likewise, synthetic cork materials are known, which are based on polymers or polymer foams.

Als besonders markante aromaaktive Komponente ist TCA bekannt. Dieses kann in natürlichen Korkmaterialien auftreten und gibt schon bei geringen Mengen eine deutliche Verschlechterung des Geschmacks des Lebensmittels. Es können aber auch Derivate oder ähnliche Verbindungen enthalten sein. In synthetischem Kork sind solche Substanzen nicht enthalten. Es können aber andere aromaaktive Substanzen enthalten sein, die den Geschmack des Lebensmittels verändern oder die aus lebensmittelrechtlichen Gründen nicht in die Flüssigkeit gelangen sollen.A particularly distinctive aroma-active component TCA is known. This can occur in natural cork materials and even with small amounts of a significant deterioration of the taste of the food. However, it may also contain derivatives or similar compounds. In synthetic cork, such substances are not included. However, it may contain other aroma-active substances that change the taste of the food or should not get into the liquid for food law reasons.

Erfindungsgemäß werden Korkstopfen, die zur Verwendung in Flaschen bereits als Formkörper konfektioniert sind, mit einer zweifachen Beschichtung versehen. Dabei soll eine Beschichtung aus filmbildenden Substanzen bestehen, die im wesentlichen hydrophile Eigenschaften aufweisen. Die zweite Beschichtung soll aus filmbildenden Substanzen bestehen, die im wesentlichen hydrophobe Eigenschaften aufweisen. Ggf. ist es auch möglich, zusätzliche Schichten auf diesen Zweischichtüberzug aufzubringen.According to the invention cork stoppers, which are already packaged for use in bottles as a shaped body, provided with a dual coating. It should consist of a coating of film-forming substances having substantially hydrophilic properties. The second coating should consist of film-forming substances which have substantially hydrophobic properties. Possibly. it is also possible to apply additional layers to this two-layer coating.

Die Reihenfolge der Schichten kann entsprechend der in der Migration zu behindernden Substanz ausgewählt werden. Es kann aus Richtung der Substratoberfläche gesehen, zuerst eine Beschichtung mit hydrophilen Eigenschaften aufgetragen werden und anschließend eine Beschichtung mit hydrophoben Eigenschaften. Ebenso ist eine umgekehrte Verfahrensweise möglich. Bevorzugt ist jedoch eine Beschichtung, die auf das Korksubstrat zuerst eine hydrophile Beschichtung und gegen den Inhalt eine hydrophobe Beschichtung aufweist.The order of the layers can be selected according to the substance to be hindered in the migration. It can be seen from the direction of the substrate surface, first a coating with hydrophilic properties are applied and then a coating with hydrophobic properties. Likewise, a reverse procedure is possible. However, a coating which has a hydrophilic coating on the cork substrate and a hydrophobic coating on the contents is preferred.

Die entsprechenden Polymere der Beschichtungsmittel sollen bei der Applikationstemperatur flüssig sein, sie können löslich sein, sie können in Form einer Dispersion vorliegen. Unter Polymeren sollen auch niedermolekulare Oligomere verstanden werden, soweit diese als Beschichtung noch filmbildende Eigenschaften aufweisen oder zu Polymeren vernetzen können. Es kann sich um reaktive Verbindungen handeln oder es können nichtreaktive Polymere oder Oligomere eingesetzt werden. Diese sollen aber als Beschichtung keine flüchtigen Anteile mehr enthalten. Im Prinzip sind auch organische lösemittelhaltige Beschichtungsmittel möglich. Bevorzugt werden jedoch wässrige Dispersionen eingesetzt oder lösemittelfreie Beschichtungsmittel.The corresponding polymers of the coating compositions should be liquid at the application temperature, they may be soluble, they may be present in the form of a dispersion. By polymers are also understood low molecular weight oligomers, as long as they still have film-forming properties as a coating or can crosslink to give polymers. They can be reactive compounds or unreactive polymers or oligomers can be used. However, these should no longer contain volatile components as a coating. In principle, organic solvent-based coating agents are possible. However, preference is given to using aqueous dispersions or solvent-free coating compositions.

Da eine Verwendung zur Verpackung von Lebensmitteln vorgesehen ist, ist es zweckmäßig, entsprechende lebensmittelrechtlich zugelassene Rohstoffe zu verwenden.Since it is intended to be used for packaging foodstuffs, it is expedient to use corresponding raw materials approved in accordance with food law.

Das hydrophile Beschichtungsmittel enthält mindestens ein hydrophiles Polymer. Beispiele für solche Polymere sind natürliche oder synthetische Polymere, wie Polysaccharide, z. B. Stärke, Dextrine, Cellulose, Proteine, Polyvinylalkohol, Polyvinylpyrrolidon, Poly(meth)-acrylsäure, höhermolekulare Polyethylenglykole oder Polyole und Derivate davon.The hydrophilic coating agent contains at least one hydrophilic polymer. Examples of such polymers are natural or synthetic polymers, such as polysaccharides, e.g. As starch, dextrins, cellulose, proteins, polyvinyl alcohol, polyvinylpyrrolidone, poly (meth) acrylic acid, higher molecular weight polyethylene glycols or polyols and derivatives thereof.

Beispiele für natürliche Polymere sind Polysaccharide, d.h. polymere Verbindungen auf Basis sich wiederholender Zuckereinheiten. Im Rahmen der vorliegenden Erfindung geeignete Polysaccharide sind beispielsweise solche auf Basis von Cellulose oder Stärke. Ein erfindungsgemäß geeignetes Polymeres kann beispielsweise ein Polysaccharid sein, wie es in natürlicher Form vorliegt. Es ist jedoch im Rahmen der vorliegenden Erfindung ebenso möglich Polysaccharide einzusetzen, die synthetisch hergestellt wurden oder Derivate von natürlichen oder synthetischen Polysacchariden. Solche Derivate von Stärke und/oder Cellulose können beispielsweise modifiziert sein durch Oxidation, Veresterung, Veretherung, sauren Abbau. Die Alkyl- und/oder (Ar)alkyl-Gruppen tragen vorzugsweise zusätzlich nichtionische, anionische oder kationische Gruppen. Solche Umsetzungen und entsprechende Polymere sind dem Fachmann bekannt. Dabei sind die Einzelmoleküle in der Regel unterschiedlich substituiert, so dass ihr Substitutionsgrad ein Mittelwert ist. Beispiele für solche hydrophilen Polymere sind Hydroxyalkyletherstärken, Hydroxyalkylcellulosen, Carboxyalkylcellulosen, Carboxyalkyletherstärken; Dextrine oder Hydroxyalkyldextrine. Diese können einzeln oder im Gemisch eingesetzt werden.Examples of natural polymers are polysaccharides, ie polymeric compounds based on repeating sugar units. Polysaccharides which are suitable in the context of the present invention are, for example, those based on cellulose or starch. A suitable polymer according to the invention may be, for example, a polysaccharide, as it is present in natural form. However, it is within the scope of the present invention also possible to use polysaccharides which have been prepared synthetically or derivatives of natural or synthetic polysaccharides. Such derivatives of starch and / or cellulose may, for example, be modified by oxidation, esterification, etherification, acid degradation. The alkyl and / or (ar) alkyl groups preferably additionally nonionic, anionic or cationic groups. Such reactions and corresponding polymers are known to the person skilled in the art. The individual molecules are usually substituted differently, so that their degree of substitution is an average. Examples of such hydrophilic polymers are hydroxyalkyl ether starches, hydroxyalkyl celluloses, carboxyalkyl celluloses, carboxyalkyl ether starches; Dextrins or hydroxyalkyldextrins. These can be used individually or in a mixture.

Ein Beispiel für Polypeptide ist Gelatine, die eine Molmasse von 15.000 bis größer 250.000 g/mol aufweisen kann. Es handelt sich dabei um ein durch Hydrolyse des in Haut und Knochen von Tieren enthaltenen Kollagens entstandenes Produkt. Die Aminosäuren-Zusammensetzung der Gelatine entspricht weitgehend der des Kollagens, aus dem sie gewonnen wurde.An example of polypeptides is gelatin, which may have a molecular weight of 15,000 to more than 250,000 g / mol. It is a product produced by hydrolysis of the collagen contained in the skin and bones of animals. The amino acid composition of gelatin is similar to that of the collagen from which it was obtained.

Ebenfalls geeignet sind synthetische Polymere, die viele polare Gruppen enthalten, wie Polyvinylpyrrolidon, Polyvinylalkohole oder Polycarbonsäuren, wie Poly(meth)acrylsäure, gegebenenfalls als Copolymerisat mit gegebenenfalls OH-Gruppen tragenden Estern der (Meth)acrylsäure. Solche hydrophilen Polymere können ggf. an den funktionellen Gruppen modifiziert werden oder mit vernetzenden Bestandteilen reagieren.Also suitable are synthetic polymers containing many polar groups, such as polyvinylpyrrolidone, polyvinyl alcohols or polycarboxylic acids, such as poly (meth) acrylic acid, optionally as a copolymer with optionally OH-bearing esters of (meth) acrylic acid. Such hydrophilic polymers can optionally be modified on the functional groups or react with crosslinking constituents.

Eine weitere Gruppe von geeigneten hydrophilen Polymeren sind Polyalkylenglykole. Es handelt sich dabei beispielsweise um Polyethylenglycole, Polypropylenglycole oder Polytetrahydrofurane, oder auch um gemischte Copolymere in statistischer oder blockcopolymerer Form. Insbesondere sind Anteile von Ethylenoxid-Bausteinen notwendig, um eine ausreichende Hydrophilie sicherzustellen. Solche di- oder polyfunktionellen Polyalkylenglykole weisen ein Molekulargewicht zwischen 600 und 30000 auf ( wie über GPC messbar ). Sie können flüssig sein oder es handelt sich um hochviskose oder feste Substanzen. Ggf. ist es möglich, diesen Polymeren des Beschichtungsmittels vernetzende Substanzen zuzusetzen, die unter den Applikationsbedingungen zu einer Polymerisation führen oder nach dem Auftragen des Beschichtungsmittels eine Vernetzung des Polymeren bewirken. Beispiele für solche Vernetzer sind Polyisocyanate oder Polyepoxide, die bei Erwärmung und/oder unter Katalyse vernetzte Polymerschichten ergeben.Another group of suitable hydrophilic polymers are polyalkylene glycols. These are, for example, polyethylene glycols, polypropylene glycols or polytetrahydrofurans, or else mixed copolymers in random or block copolymeric form. In particular, portions of ethylene oxide building blocks are necessary to ensure sufficient hydrophilicity. Such di- or polyfunctional polyalkylene glycols have a molecular weight of between 600 and 30,000 (as measured by GPC). They can be liquid or they are highly viscous or solid substances. Possibly. it is possible to add to these polymers of the coating agent crosslinking substances which lead to polymerization under the application conditions or cause crosslinking of the polymer after application of the coating composition. Examples of such crosslinkers are polyisocyanates or polyepoxides which give crosslinked polymer layers on heating and / or under catalysis.

Insbesondere bevorzugt sind jedoch natürliche Polymere, wie Cellulose und Cellulosederivate.However, particular preference is given to natural polymers, such as cellulose and cellulose derivatives.

Bevorzugte Polymere sind entweder flüssig oder in Lösemitteln, insbesondere in Wasser gelöst oder dispergiert. Weiterhin können solche Beschichtungsmittel Additive enthalten, um Verarbeitungseigenschaften der Dispersion oder Filmeigenschaften der Beschichtung zu beeinflussen. Additive sind beispielsweise Antioxidantien, Rheologiehilfsmittel, Viskositätsregler, Haftvermittler, pH-Regler, Verlaufsmittel, Entgasungsmittel, Entschäumungsmittel, Emulgatoren. Die Viskosität des Beschichtungsmittels wird dem Applikationsverfahren angepasst.Preferred polymers are either liquid or dissolved or dispersed in solvents, especially in water. Furthermore, such coating compositions may contain additives to influence processing properties of the dispersion or film properties of the coating. Additives are, for example, antioxidants, rheology aids, viscosity regulators, adhesion promoters, pH regulators, leveling agents, degassing agents, defoaming agents, emulsifiers. The viscosity of the coating agent is adapted to the application method.

Üblicherweise werden die Beschichtungsmittel auf das Substrat aufgetragen und haften unter Bildung von ionischen und kovalenten Kräften auf der Oberfläche. Ggf. ist es auch möglich, dass vernetzende Substanzen in dem Beschichtungsmittel enthalten sind, die mit dem Substrat reagieren können.Typically, the coating agents are applied to the substrate and adhere to form ionic and covalent forces on the surface. Possibly. it is also possible that crosslinking substances are contained in the coating agent, which can react with the substrate.

Das zweite Beschichtungsmittel soll als wesentlichen Bestandteil hydrophobe Polymere enthalten. Polymere mit hydrophoben Eigenschaften sind bekannt. Beispielsweise kann es sich um Silikonöle oder Silikonverbindungen handeln, Polymere auf Basis von perfluorierten Verbindungen, Polymere auf Basis von Polyolefinen, Wachse, Polyamide oder ähnliche Polymere. Diese Polymere sollen bei der Applikationstemperatur flüssig sein, sie können gelöst sein oder sie können in Lösemitteln dispergiert werden. Auch im Falle dieser Beschichtungsmittel ist es zweckmäßig, aus Gründen der späteren Verwendung des Korkstopfens, solche Lösemittel einzusetzen, die lebensmittelrechtlich unbedenklich sind. Im wesentlichen sollen organische Lösemittel vermieden werden, ggf. kann das Beschichtungsmittel Wasser oder Ethanol als Dispersionsmedium enthalten sein.The second coating agent should contain hydrophobic polymers as an essential ingredient. Polymers with hydrophobic properties are known. For example, these may be silicone oils or silicone compounds, polymers based on perfluorinated compounds, polymers based on polyolefins, waxes, polyamides or similar polymers. These polymers should be liquid at the application temperature, they may be dissolved or they may be dispersed in solvents. Also in the case of these coating compositions, it is expedient, for reasons of later use of Korkstopfens, to use such solvents that are harmless under food law. In essence, organic solvents should be avoided, if necessary, the coating agent may be water or ethanol contained as a dispersion medium.

Eine bekannte Gruppe von erfindungsgemäß geeigneten hydrophoben Polymeren sind Siliconpolymere oder Oligomere. Es kann sich um Polysiloxane handeln, die flüssig oder fest sind, sie können vernetzende Gruppen aufweisen oder sie sind inert. Sie können funktionelle Gruppen aufweisen. Kautschukartige, nicht verfließende Polymere sind weniger geeignet. Beispiele für solche Verbindungen sind Siliconöle, Polysiloxane oder ggf. substituierte Alk-oxysilane.A known group of hydrophobic polymers suitable according to the invention are silicone polymers or oligomers. They may be polysiloxanes which are liquid or solid, they may have crosslinking groups or they may be inert. They may have functional groups. Rubbery, non-flowable polymers are less suitable. Examples of such compounds are silicone oils, polysiloxanes or optionally substituted alkoxysilanes.

Wachse können natürliche Wachse, chemisch modifizierte Wachse oder synthetische Wachse sein. Zu den natürlichen Wachsen zählen beispielsweise pflanzliche Wachse wie Carnaubawachs, Zuckerrohrwachs, Montanwachs, Bienenwachs, Schellackwachs, Lanolin, zu den Mineralwachsen oder petrochemischen Wachsen beispielsweise Petrolatum, Paraffinwachse oder Mikrowachse. Unter synthetischen Wachsen werden in der Regel Polyalkylenwachse oder Polyalkylenglycolwachse verstanden. Geeignet sind auch synthetisch hergestellte Wachse aus Carbonsäuren und Fettalkoholen oder Fettsäureamiden. Ebenfalls zu den Wachsen werden beispielsweise sogenannte Wachsalkohole gezählt, d.h. höhermolekulare, wasserunlösliche Fettalkohole mit in der Regel etwa 22 bis 40 Kohlenstoffatomen. Solche Produkte sind dem Fachmann bekannt.Waxes can be natural waxes, chemically modified waxes or synthetic waxes. Natural waxes include, for example, vegetable waxes such as carnauba wax, sugar cane wax, montan wax, beeswax, shellac wax, lanolin, mineral waxes or petrochemical waxes such as petrolatum, paraffin waxes or microwaxes. Synthetic waxes are generally understood as meaning polyalkylene waxes or polyalkylene glycol waxes. Also suitable are synthetically produced waxes from carboxylic acids and fatty alcohols or fatty acid amides. Also to the waxes, for example, so-called wax alcohols are counted, i. higher molecular weight, water-insoluble fatty alcohols having usually about 22 to 40 carbon atoms. Such products are known to the person skilled in the art.

Eine weitere Gruppe von hydrophoben Komponenten sind pflanzliche Öle, wie beispielsweise Sonnenblumenöl, Sojaöl, Rapsöl, Weizenkeimöl, und die flüssigen Anteile des Kokosöls, oder Fettsäure- und Fettalkoholester, wie Monoester der Fettsäuren mit Alkoholen mit 3 bis 24 C-Atomen. Diese können flüssig oder hochviskos sein oder sie sind bei Raumtemperatur fest.Another group of hydrophobic components are vegetable oils, such as sunflower oil, soybean oil, rapeseed oil, wheat germ oil, and the liquid portions of coconut oil, or fatty acid and fatty alcohol esters, such as monoesters of the fatty acids with alcohols having 3 to 24 carbon atoms. These can be liquid or highly viscous or they are solid at room temperature.

Weiterhin können als Bestandteil des hydrophoben Beschichtungsmittels flüssige oder feste Paraffine eingesetzt werden, wie unverzweigten Paraffinkohlenwasserstoffen, insbesondere C12-24-Alkanen, oder IsoparaffineFurthermore, liquid or solid paraffins can be used as constituent of the hydrophobic coating agent, such as unbranched paraffin hydrocarbons, in particular C 12-24 alkanes, or isoparaffins

Ebenfalls bekannt als hydrophobe Substanzen sind perfluorierte Verbindungen, wie per-fluorierte Fettsäuren, Ester von Carbonsäuren mit perfluorierten Alkoholen, perfluorierte Olefin(co)polymere.Also known as hydrophobic substances are perfluorinated compounds such as perfluorinated fatty acids, esters of carboxylic acids with perfluorinated alcohols, perfluorinated olefin (co) polymers.

Eine besonders geeignete Gruppe von Verbindungen sind Alkylsiloxane, die OH-Gruppen und /oder NH-Gruppen aufweisen, insbesondere solche, die Hydroxylgruppen, Hydroxycarbonsäuregruppen und/oder Mono- /Disaccharide in der Hauptkette oder in der Seitenkette enthalten. Insbesondere handelt es sich dabei um substituierte Aminoalkylsiloxane und/oder höher alkyl-modifizierte Amidoaminosiloxan , die zwischen 10 bis 1500 Siliciumatome enthalten. Als Substituenten sind beispielsweise Wasserstoffatome, einwertige, gegebenenfalls Fluor-, Chlor- oder Brom-substituierte C1- bis C18-Kohlenwasserstoffreste, C1- bis C12-Alkoxy- oder Hydroxyreste, Hydroxycarbonsäuren, Mono- und Disaccharide, Alkylglykolreste und/oder primäre oder sekundäre Aminogruppen oder Amidogruppenenthalten.A particularly suitable group of compounds are alkyl siloxanes which have OH groups and / or NH groups, in particular those which contain hydroxyl groups, hydroxycarboxylic acid groups and / or mono- / disaccharides in the main chain or in the side chain. In particular, they are substituted aminoalkylsiloxanes and / or higher alkyl-modified amidoaminosiloxanes containing from 10 to 1500 silicon atoms. Examples of suitable substituents are hydrogen atoms, monovalent, optionally fluorine-, chlorine- or bromine-substituted C 1 - to C 18 -hydrocarbon radicals, C 1 - to C 12 -alkoxy or hydroxy radicals, hydroxycarboxylic acids, mono- and disaccharides, alkyl glycol radicals and / or primary or secondary amino groups or amido groups.

Solche Verbindungen sind beispielsweise in der EP 1081272 oder der DE 10214982 beschrieben. Solche Polymere können beispielsweise mittels geeigneter Emulgatoren in die Wasserphase überführt werden.Such compounds are for example in the EP 1081272 or the DE 10214982 described. Such polymers can be converted into the water phase, for example, by means of suitable emulsifiers.

Das hydrophobe Beschichtungsmittel oder die daraus hergestellte Beschichtung kann ein oder mehrere der oben erwähnten hydrophoben Polymere oder Oligomere enthalten. Es können dabei im Beschichtungsmittel Polymersubstanzen vorhanden sein, die insgesamt hydrophobe Eigenschaften haben. Es kann sich jedoch auch um niedermolekulare Oligomere handeln, die unter den Applikationsbedingungen, z. B. in der wässrigen Phase, als aufgetragene Schicht nach der Filmbildung zu Polymeren vernetzt werden können. Die entsprechenden höhermolekularen Polymere des Beschichtungsfilms sollen dann die hydrophoben Eigenschaften aufweisen.The hydrophobic coating agent or coating made therefrom may contain one or more of the above-mentioned hydrophobic polymers or oligomers. It may be present in the coating agent polymer substances which have a total of hydrophobic properties. However, it may also be low molecular weight oligomers which under the application conditions, for. B. in the aqueous phase, can be crosslinked as a coated layer after film formation to polymers. The corresponding higher molecular weight polymers of the coating film should then have the hydrophobic properties.

Das hydrophobe Beschichtungsmittel kann inert sein, es kann selbstvernetzend sein oder es können in dem Beschichtungsmittel zusätzlich Vernetzer enthalten sein. Weiterhin können verschiedene Additive und Hilfsstoffe in dem Beschichtungsmittel enthalten sein, die die Verarbeitung des Beschichtungsmittels erleichtern oder die Eigenschaften der Beschichtung beeinflussen. Es kann sich dabei um die gleichen Substanzklassen handeln, die auch in den hydrophilen Beschichtungsmitteln als Additive vorhanden sein sollen. Insbesondere kann es notwendig sein, wenn ein wässriges Beschichtungsmittel gewählt wird, Emulgatoren oder andere Dispergierhilfsmittel zuzusetzen. Es ist darauf zu achten, dass diese Additive nicht den wesentlichen Charakter der Beschichtung als hydrophobe Beschichtung beeinträchtigen.The hydrophobic coating agent may be inert, it may be self-crosslinking, or crosslinkers may additionally be present in the coating composition. Furthermore, various additives and auxiliaries may be contained in the coating agent, which facilitate the processing of the coating agent or influence the properties of the coating. It can work to be the same classes of substances that are to be present as additives in the hydrophilic coating compositions. In particular, when an aqueous coating agent is selected, it may be necessary to add emulsifiers or other dispersing aids. It must be ensured that these additives do not impair the essential character of the coating as a hydrophobic coating.

Es ist darauf zu achten, dass möglichst geringe Anteile an migrationsfähigen, niedermolekularen Substanzen in den Beschichtungen vorhanden sind. Insbesondere sollen bei einem Kontakt mit dem meist wässrigen Füllgut keine Substanzen aus der zweifachen Beschichtung gelöst werden.It is important to ensure that the lowest possible levels of migratory, low molecular weight substances are present in the coatings. In particular, no substances from the double coating should be dissolved in contact with the mostly aqueous filling material.

Die beiden Beschichtungen werden nacheinander auf das Substrat aufgetragen. Dabei ist es möglich, dass der Korkstopfen auf allen Oberflächen gleichmäßig beschichtet wird. Es ist jedoch ggf. ausreichend, nur die dem Inhalt zugewandte Seite und die dem Flaschenrand zugewandte Seite zu beschichten. Ggf. ist es auch möglich, einen entsprechend kleinen Korkformkörper zu beschichten und diesen auf einen unbeschichteten Korkstopfen auf der der Flüssigkeit zugewandten Seite zu kleben. Die Beschichtungsmittel sollen bei der Applikationstemperatur flüssig sein. Diese kann bevorzugt zwischen 15 bis 70° C liegen, bevorzugt zwischen 20 bis 40° C bzw. bei üblicher Raumtemperatur.The two coatings are applied successively to the substrate. It is possible that the cork stopper is evenly coated on all surfaces. However, it may be sufficient to coat only the side facing the content and the side facing the edge of the bottle. Possibly. It is also possible to coat a correspondingly small Korkformkörper and glue it to an uncoated cork stopper on the liquid side facing. The coating compositions should be liquid at the application temperature. This may preferably be between 15 and 70 ° C., preferably between 20 and 40 ° C. or at the usual room temperature.

Es ist erfindungswesentlich, dass zumindest auf der der Flüssigkeit zugewandten Seite beide Beschichtungen eine dichte Beschichtung auf dem Korkstopfen ergeben. Da der Korkstopfen an der Oberfläche ggf. Poren und Fehlstellen aufweisen kann, kann es notwendig sein, eine entsprechend erhöhte Menge des Beschichtungsmittels aufzubringen. Insgesamt soll die Beschichtung aus beiden Schichten in einer Menge zwischen 1 mg/cm2 der Oberfläche bis zu 300 mg/cm2 aufgebracht werden, insbesondere zwischen 2 mg/cm2 bis zu 150 mg/cm2. Dabei ist es möglich, dass beide Polymerschichten ungefähr das gleiche Auftragsgewicht aufweisen. Es ist jedoch auch möglich, dass sie unterschiedliches Auftragsgewicht haben. Insbesondere bevorzugt ist es, wenn die hydrophobe Beschichtung mindestens 50 %, insbesondere mindestens 70 % des Schichtgewichts beträgt.It is essential to the invention that, at least on the side facing the liquid, both coatings produce a dense coating on the cork stopper. Since the cork stopper may possibly have pores and imperfections on the surface, it may be necessary to apply a correspondingly increased amount of the coating agent. Overall, the coating should be applied from both layers in an amount between 1 mg / cm 2 of the surface up to 300 mg / cm 2 , in particular between 2 mg / cm 2 up to 150 mg / cm 2 . It is possible that both polymer layers have approximately the same application weight. However, it is also possible that they have different order weight. It is particularly preferred if the hydrophobic coating is at least 50%, in particular at least 70%, of the layer weight.

Ein weiterer Gegenstand der Erfindung ist ein Verfahren zum Beschichten von Korksubstraten in Stopfenform, wobei mindestens zwei Schichten aufgebracht werden. Dabei ist es möglich, dass der fertig geformte Korkstopfen ggf. geschliffen wird, sowie danach ggf. einer Reinigung an der Oberfläche unterzogen wird. Eine weitere Vorbehandlung ist üblicherweise nicht notwendig. Es ist auch möglich, den Korkstopfen zu bedrucken. Auf den entsprechenden Korkstopfen wird dann das erste Beschichtungsmittel aufgebracht in dünnflüssiger oder hochviskoser Form, bevorzugt eine wässrige Lösung enthaltend mindestens ein hydrophiles Polymer. Das Beschichtungsmittel soll bei Applikationstemperatur flüssig sein. Die Viskosität des Beschichtungsmittels kann auch durch erhöhte Temperaturen beim Auftragen vermindert werden. Bevorzugt soll jedoch bei Raumtemperatur gearbeitet werden, d.h. üblicherweise zwischen 20 bis 40° C. Nach dem Beschichten kann der Korkstopfen erwärmt werden, um ein Verdampfen der flüchtigen Bestandteile, insbesondere von Wasser, aus dem Beschichtungsmittel zu ermöglichen. Dabei kann auch eine Vernetzungsreaktion eingeleitet werden. Zusätzlich wird eine Filmbildung des Polymeren unterstützt.Another object of the invention is a method for coating cork substrates in plug shape, wherein at least two layers are applied. It is possible that the finished molded cork stopper is ground if necessary, and then optionally subjected to a cleaning on the surface. Further pretreatment is usually not necessary. It is also possible to print on the cork stopper. The first coating agent is then applied to the corresponding cork stopper in a highly viscous or highly viscous form, preferably an aqueous solution containing at least one hydrophilic polymer. The coating agent should be liquid at the application temperature. The viscosity of the coating agent can also be reduced by increased temperatures during application. However, it is preferable to operate at room temperature, i. usually between 20 to 40 ° C. After coating, the cork stopper may be heated to allow evaporation of the volatiles, especially water, from the coating agent. In this case, a crosslinking reaction can be initiated. In addition, a film formation of the polymer is supported.

Das Auftragen des Beschichtungsmittels kann durch die bekannten Auftragsverfahren geschehen, beispielsweise durch Sprühen, Tauchen, Rollenbeschichtung oder Beschichten in einer Trommel. Wenn die beschichteten Korkstopfen danach bewegt werden, ist darauf zu achten, dass dabei die Integrität der Oberflächenbeschichtung möglichst nicht zerstört wird. Nachdem die erste Beschichtung aufgebracht wurde, kann unmittelbar danach der zweite Beschichtungsschritt mit dem zweiten Beschichtungsmittel, bevorzugt dem hydrophobierenden Beschichtungsmittel, durchgeführt werden. Es können die gleichen oben erwähnten Auftragsverfahren angewendet werden. Dabei ist es auch in diesem Falle möglich, das Beschichtungsmittel unter Erwärmen zu verarbeiten oder nach dem Beschichtungsschritt einen Trocknungsschritt und/oder einen Vernetzungsschritt durchzuführen. Es soll auch in diesem Fall eine Filmbildung sichergestellt werden.The application of the coating agent can be done by the known application method, for example by spraying, dipping, roller coating or coating in a drum. If the coated cork stoppers are moved afterwards, it is important to ensure that the integrity of the surface coating is not destroyed as much as possible. After the first coating has been applied, immediately after the second coating step with the second coating agent, preferably the hydrophobic coating agent, can be carried out. The same application methods mentioned above can be used. In this case, too, it is possible to process the coating agent under heating or to perform a drying step and / or a crosslinking step after the coating step. It should be ensured in this case, a film formation.

Eine Ausführungsform arbeitet so, dass nach der ersten Beschichtung ohne weiteres Erwärmen oder Vernetzung bzw. nach kurzem Abdampfen (flash-off) von flüchtigen Bestandteilen, ggf. durch Druckluft und/oder Erwärmen unterstützt, die zweite Beschichtung aufgetragen wird. Danach kann ein gemeinsamer Trocknungsschritt durchgeführt werden. Dabei werden mögliche Lösemittel entfernt und eine Filmbildung der Polymeren unterstützt.One embodiment operates such that, after the first coating, the second coating is applied without further heating or crosslinking or after brief flash off of volatile constituents, if appropriate by compressed air and / or heating. Thereafter, a common drying step may be performed. In the process, possible solvents are removed and a film formation of the polymers is supported.

Die Trocknung der beschichteten Korkstopfen kann durch bekannte Verfahren durchgeführt werden. Dabei können Lösemittel, Wasser oder andere flüchtige Bestandteile entfernt werden. Weiterhin ist es möglich durch Erwärmen, z. B. durch die IR-Strahlung, durch Überleiten von erwärmten Gasen oder durch Erwärmen in einem Ofen flüchtige Bestandteile aus der Beschichtung zu entfernen. Die Temperaturen können zwischen 20 °C bis zu 130 °C betragen, insbesondere zwischen 30 °C bis zu 90 °C. Die Erwärmungsdauer kann zwischen 30 sec. und 12 Std. betragen. Es ist darauf zu achten, dass das Substratmaterial bei dieser Temperatur keinerlei negative Veränderungen erleidet. Auch Verfärbungen des Substratmaterials sollten vermieden werden.The drying of the coated cork stoppers can be carried out by known methods. This solvent, water or other volatile components can be removed. Furthermore, it is possible by heating, for. B. by the IR radiation, by passing heated gases or by heating in an oven to remove volatile components from the coating. The temperatures can be between 20 ° C up to 130 ° C, in particular between 30 ° C up to 90 ° C. The heating time can be between 30 seconds and 12 hours. Care must be taken that the substrate material does not undergo any negative changes at this temperature. Discolouration of the substrate material should also be avoided.

Nachdem beide Beschichtungen aufgetragen sind, können bei Bedarf weitere Schichten aufgetragen werden. Diese können beispielsweise dazu dienen, den Korkstopfen bei Lagerung oder Applikation zu schützen.After both coatings are applied, additional layers can be applied as needed. These can serve, for example, to protect the cork stopper during storage or application.

Durch die erfindungsgemäße Arbeitsweise wird ein Korkstopfen erhalten, der auf der Oberfläche ganz oder teilweise eine mindestens doppelte Beschichtung aufweist. Diese mindestens doppelte Beschichtung mindert eine Migration entweder als Diffusion oder als Extraktion aus dem Korksubstrat in das Lebensmittel. Da die Polymere eine dichte Schicht bilden, ggf. hochviskos oder vernetzt sind, ist eine Migration von aromaaktiven Substanzen, insbesondere TCA deutlich vermindert. Auch in dem Fall, dass ggf. Poren in einer Beschichtung vorhanden sein können, wird die zweite Beschichtung eine Migration solcher Bestandteile trotzdem vermindern.By means of the procedure according to the invention, a cork stopper is obtained which has completely or partially on the surface at least a double coating. This at least double coating reduces migration either as diffusion or as extraction from the cork substrate into the food. Since the polymers form a dense layer, possibly highly viscous or crosslinked, migration of aroma-active substances, in particular TCA, is markedly reduced. Even in the event that possibly pores may be present in a coating, the second coating will nevertheless reduce migration of such components.

Die Beschichtungen sollen flexibel sein. Da bei der Applikation eines Korkstopfens dieser komprimiert und dann an seinen Bestimmungsort gebracht wird, sollen die erfindungsgemäßen Beschichtungen nur soweit vernetzt werden, dass eine Verformung entweder elastisch oder dauerhaft möglich ist. Die Polymere dürfen nicht so spröde oder so vernetzt sein, dass Risse und Brüche in der Beschichtung auftreten können. Besonders geeignet sind solche Polymere in den Beschichtungen, die noch kaltfließfähige Eigenschaften aufweisen und mögliche Fehlstellen schließen können.The coatings should be flexible. Since in the application of a cork stopper this is compressed and then brought to its destination, the coatings according to the invention should only be crosslinked so far that a deformation is either elastic or permanently possible. The polymers must not be so brittle or so cross-linked that cracks and breaks in the coating can occur. Particularly suitable are those polymers in the coatings that still have cold flow properties and can close any defects.

Durch die mindestens zwei Schichten können die Polymere so gewählt werden, dass sie getrennte Wirkungseigenschaften haben. So ist die dem Substrat zugewandte Seite insbesondere dafür geeignet, eine Migration der aromaaktiven Bestandteile zu vermindern. Die der Flüssigkeit zugewandte Seite soll einen intensiven Kontakt der Flüssigkeit mit der Korkoberfläche vermeiden. Weiterhin kann das Polymer dieser Schicht so ausgewählt werden, dass eine Gleitwirkung des Korkstopfens in dem Flaschenhals ermöglicht wird.Through the at least two layers, the polymers can be chosen so that they have separate performance properties. Thus, the side facing the substrate is particularly suitable for reducing migration of the aroma-active constituents. The side facing the liquid should avoid intensive contact of the liquid with the cork surface. Furthermore, the polymer of this layer may be selected to allow a sliding action of the cork stopper in the neck of the bottle.

Die nachfolgenden Beispiele sollen die Erfindung und die Wirkungsweise der Beschichtung darstellen.The following examples are intended to illustrate the invention and the mode of action of the coating.

BeispieleExamples

Es wird Kork verwendet, der einen TCA-Gehalt aufweist, der durch eine Blindprobe bestimmt wird. Um besser messbare TCA-Werte zu erhalten, wird ein Granulat beschichtet und extrahiert.Cork is used which has a TCA content determined by blank. In order to obtain better measurable TCA values, a granulate is coated and extracted.

Beschichtungsmittel 1:Coating agent 1:

Es wird eine 2 % wässrige Lösung aus Hydroxyethylcellulose (Natrosol LR 250, Hercules GmbH), durch Rühren in Wasser hergestellt. Es entsteht eine klare dünnviskose Lösung
( < 200 mPas , 20 °C ).A 2% aqueous solution of hydroxyethylcellulose (Natrosol LR 250, Hercules GmbH) is prepared by stirring in water. The result is a clear thin-viscous solution
(<200 mPas, 20 ° C).

Beschichtungsmittel 2:Coating agent 2:

Es wird eine ca. 30 % wässrige Lösung eines Amidoaminosiloxans eingesetzt (Tubingal FAM , CHT Beitlich GmbH ), die ca. 10 % eines Fettalkoholethoxylats als Emulgator enthält. Die Lösung ist eine dünnviskose Emulsion ( < 400 mPas , 20 °C ; Brookfield RVT, Spindel 2, 50 U/min. ).An approximately 30% aqueous solution of an amido-amino siloxane is used (Tubingal FAM, CHT Beitlich GmbH), which contains about 10% of a fatty alcohol ethoxylate as emulsifier. The solution is a thin viscous emulsion (<400 mPas, 20 ° C, Brookfield RVT, spindle 2, 50 rpm).

Beschichtungsverfahren 3:Coating method 3:

Es werden 4 g eines Korkgranulats mit einer Teilchengröße zwischen 2 bis 8 mm zusammen mit 20 ml eines Beschichtungsmittels 1 oder 2 ml eines Beschichtungsmittels 2 zusammengegeben und in einer Trommel gewälzt. Nach 30 Min. wird das beschichtete Korkgranulat entnommen und 7 Std. bei 80 °C getrocknet. Das Korkgranulat wird gewogen und die Gewichtszunahme gibt die Mengen der aufgenommenen Beschichtung an.4 g of a cork granulate having a particle size of 2 to 8 mm together with 20 ml of a coating agent 1 or 2 ml of a coating agent 2 are combined and rolled in a drum. After 30 minutes, the coated cork granules are removed and dried at 80 ° C. for 7 hours. The cork granules are weighed and the weight gain indicates the amounts of coating absorbed.

Beschichtungsverfahren 4:Coating method 4:

Es werden 4 g eines Korkgranulats mit einer Teilchengröße zwischen 4 bis 6 mm in einer Trommel bewegt. Durch eine Öffnung werden insgesamt 20 ml eines Beschichtungsmittels 1 in drei Portionen oder 2 ml des Beschichtungsmittels 2 in zwei Portionen in jeweils 10 min Abstand gegeben. Nach 30 Min. wird das beschichtete Korkgranulat entnommen und 7 Std. bei 80 °C getrocknet. Das Korkgranulat wird gewogen und die Gewichtszunahme gibt die Mengen der aufgenommen Beschichtung an.4 g of cork granules with a particle size between 4 and 6 mm are moved in a drum. Through an opening, a total of 20 ml of a coating agent 1 in three portions or 2 ml of the coating composition 2 in two portions in each case 10 minutes distance. After 30 minutes, the coated cork granules are removed and dried at 80 ° C. for 7 hours. The cork granules is weighed and the weight gain indicates the amounts of coating absorbed.

Nach dem Trocken einer Beschichtung wird jeweils die andere Beschichtung nach der gleichen Verfahrensweise aufgetragen.After drying a coating, the other coating is applied according to the same procedure.

Extraktionsverfahren: Extraction method :

In ein Becherglas wird das beschichtete Korkgranulat gegeben und mit einer 12 %-igen Lösung von Ethanol in Wasser versetzt. Die Menge wird so gewählt, dass auf 5 g Korkgranulat 67 ml wässrige Lösung eingesetzt wird. Das Material wird unterhalb der Flüssigkeitsoberfläche gehalten.The coated cork granules are placed in a beaker and treated with a 12% solution of ethanol in water. The amount is chosen so that 67 ml of aqueous solution is used on 5 g of cork granules. The material is kept below the liquid surface.

Nach intensivem Rühren für einen Zeitraum von 48 Std. bei einer Temperatur von 40 °C wird die Flüssigphase abfiltriert und der Gehalt an TCA durch Festphasenextraktion bestimmt. Korkbehandlung TCA Menge (ppt) Korkgranulat unbehandelt 10 Cellulosebeschichtung (0,05 g/g Kork) 6 Siloxanbeschichtung (0,08 g/g Korkgranulat) 7 1. Schicht Cellulose/2. Schicht Siloxan (0,06 g/g Korkgranulat) 2 1. Schicht Siloxan/2. Schicht Cellulose (0,05 g/g Korkgranulat) 4 After intensive stirring for a period of 48 hours at a temperature of 40 ° C, the liquid phase is filtered off and determines the content of TCA by solid phase extraction. Korkbehandlung TCA amount (ppt) Cork granules untreated 10 Cellulose coating (0.05 g / g cork) 6 Siloxane coating (0.08 g / g cork granules) 7 1st layer of cellulose / 2. Layer siloxane (0.06 g / g cork granules) 2 1st layer siloxane / 2. Layer of cellulose (0.05 g / g cork granules) 4

Claims (16)

  1. A method for coating cork stoppers, characterized in that the cork optionally cleaned on the surface is provided successively with at least two coatings, wherein a hydrophilic coating agent is applied as a first layer and a hydrophobic coating agent is applied as a second agent and one or both of the coating agents are liquid at the application temperature.
  2. The method according to claim 1, characterized in that the coating agents are aqueous coating agents.
  3. The method according to any of claims 1 to 2, characterized in that the first coating and/or the second coating is dried and/or subject to a crosslinking step.
  4. The method according to claim 3, characterized in that both coatings are subject together to a drying and/or crosslinking step.
  5. The method according to any of claims 3 or 4, characterized in that the drying and/or crosslinking step is carried out at a high temperature.
  6. The method according to any of claims 1 to 5, characterized in that the weight of both applied coatings together is from 1 to 300 mg/cm2 of substrate surface.
  7. The method according to any of claims 1 to 6, characterized in that before applying the first coating, a cleaning step and/or printing of the cork surface is carried out.
  8. The method according to any of claims 1 to 7, characterized in that the coating agents are applied by immersion, spraying, roll coating, or drum coating.
  9. A cork stopper for closing bottles, characterized in that the surface of the stopper totally or partly has at least two coating layers, the first layer being a hydrophilic layer, the second layer being a hydrophobic layer.
  10. The cork stopper according to claim 9, characterized in that the hydrophilic and/or hydrophobic polymer is a cross-linking polymer.
  11. The cork stopper according to any of claims 9 to 10, characterized in that both coatings have together a basis weight of 1-300 mg/cm2.
  12. The cork stopper according to any of claims 9 to 11, characterized in that the cork is completely coated with two coating layers.
  13. The cork stopper according to any of claims 9 to 12, characterized in that the hydrophilic coating contains at least one polymer based on cellulose, starch or polyvinyl alcohol.
  14. The cork stopper according to any of claims 9 to 13, characterized in that the hydrophobic coating contains at least one polymer based on silicone derivatives.
  15. The cork stopper according to any of claims 9 to 14, characterized in that one or both of the coating layers were applied as an aqueous coating agent.
  16. The cork stopper according to any of claims 9 to 15, characterized in that the stopper consists of cork fragments, molding of cork granulates, or molding of cork granulates with plastic material admixtures.
EP07711466A 2006-03-20 2007-02-08 Diffusion-reducing cork coating Not-in-force EP2001759B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102006013102A DE102006013102A1 (en) 2006-03-20 2006-03-20 Diffusion-reducing cork coating
PCT/EP2007/001057 WO2007107209A1 (en) 2006-03-20 2007-02-08 Diffusion-reducing cork coating

Publications (2)

Publication Number Publication Date
EP2001759A1 EP2001759A1 (en) 2008-12-17
EP2001759B1 true EP2001759B1 (en) 2010-09-29

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EP (1) EP2001759B1 (en)
AT (1) ATE482890T1 (en)
DE (2) DE102006013102A1 (en)
ES (1) ES2355314T3 (en)
PT (1) PT2001759E (en)
WO (1) WO2007107209A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012102631A2 (en) 2011-01-24 2012-08-02 Amorim & Irmãos, S.A. Process for applying polymeric coating on cork stoppers
CN105857879A (en) * 2016-06-17 2016-08-17 河北百林软木制品有限公司 Cork treatment process capable of reducing wine leakage rate of bottled wine

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2956058B1 (en) 2010-02-08 2012-02-03 Jacques Granger TREATMENT OF NATURAL CORK STOP PLUGS AND PLUGS OBTAINED THEREBY

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Publication number Priority date Publication date Assignee Title
DE1103003B (en) * 1960-02-22 1961-03-23 C A Greiner & Soehne K G Process for impregnating corks with thermoplastic synthetic resins
US6022816A (en) * 1994-03-18 2000-02-08 Dewco Investments Pty Ltd. Closure
AUPP989399A0 (en) * 1999-04-22 1999-05-13 Vinpac International Pty Ltd Treated closures 2
NZ529774A (en) * 2001-07-04 2004-10-29 Procork Pty Ltd Container stopper
US20040166345A1 (en) * 2003-02-26 2004-08-26 Wicht Charles A. Processes and articles useful for preventing cork taint in beverages
US7579002B2 (en) * 2003-12-05 2009-08-25 Wisconsin Alumni Research Foundation Method for improving body weight uniformity and increasing carcass yield in animals

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012102631A2 (en) 2011-01-24 2012-08-02 Amorim & Irmãos, S.A. Process for applying polymeric coating on cork stoppers
CN105857879A (en) * 2016-06-17 2016-08-17 河北百林软木制品有限公司 Cork treatment process capable of reducing wine leakage rate of bottled wine

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DE102006013102A1 (en) 2007-09-27
ES2355314T3 (en) 2011-03-24
PT2001759E (en) 2010-10-12
EP2001759A1 (en) 2008-12-17
ATE482890T1 (en) 2010-10-15
DE502007005201D1 (en) 2010-11-11

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