EP2533957B1 - Bearbeitung von verschlussstopfen aus natürlichem kork und durch diese bearbeitung gewonnene verschlussstopfen - Google Patents

Bearbeitung von verschlussstopfen aus natürlichem kork und durch diese bearbeitung gewonnene verschlussstopfen Download PDF

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EP2533957B1
EP2533957B1 EP11708530.8A EP11708530A EP2533957B1 EP 2533957 B1 EP2533957 B1 EP 2533957B1 EP 11708530 A EP11708530 A EP 11708530A EP 2533957 B1 EP2533957 B1 EP 2533957B1
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Prior art keywords
cork
batch
treatment
liquid composition
corks
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French (fr)
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EP2533957A2 (de
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Jacques Granger
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K7/00—Chemical or physical treatment of cork
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
    • B27K3/02—Processes; Apparatus
    • B27K3/15—Impregnating involving polymerisation including use of polymer-containing impregnating agents

Definitions

  • the invention relates to the field of corking bottles of alcoholic and spirits wines using natural or technical cork stoppers, more specifically a treatment of natural cork stoppers in order to eliminate their disadvantages.
  • cork natural product perfectly suited to the field of corking, can cause disadvantages, particularly because of its heterogeneity and the presence of harmful molecules - typically haloanisoles and halophenols - that can alter the taste of bottled products. As a result, there are no two identical plugs.
  • corks we know natural cork and the different treatments to obtain corks.
  • the plugs are subjected to washing with very hot water to remove small waste and particles of cork or dust, insects, etc.
  • a second superheated steam treatment is generally applied to natural plugs to reduce the content of harmful molecules and reduce the risk of having bottles that are unfit for consumption because they have a "corky taste", expression generally used to designate an unacceptable organoleptic alteration of the bottled liquid due to contamination by the plug.
  • Such a cork taste can be detected from a very low harmful molecule concentration threshold of 2 ng / l (nanograms per liter).
  • clogging treatment is also known in which a mixture of waxes and cork dust is applied to the stopper so as to obtain so-called "clogged" stoppers in order to be able to use a cork which is also rich in cracks.
  • Other heavy treatments have been developed to try to eliminate the harmful molecules, the presence of harmful molecules remaining one of the concerns bottlers, bottlers and consumers.
  • WO2007 / 107209 discloses a cork stopper treatment in which the corks are coated with a hydrophilic polymeric layer, such as a cellulosic layer, based on starch or alcohol polykinetic, and a hydrophobic layer, such as a layer based on a silicone derivative.
  • a hydrophilic polymeric layer such as a cellulosic layer, based on starch or alcohol polykinetic
  • a hydrophobic layer such as a layer based on a silicone derivative
  • WO96 / 28378 discloses a cork plug encapsulated in a layer, preferably PVC or polyurethane, formed for example by molding and heat treatment.
  • international demand WO91 / 04836 discloses a cork stopper treatment comprising a washing step with a solution containing sodium hydroxide, sodium silicate and hydrogen peroxide, followed by a drying step, and a third step of treatment with a solution containing acetic acid, peracetic acid and hydrogen peroxide.
  • the invention aims to transform any batch of corks into natural cork, with its heterogeneity and its variability of intrinsic properties, batch-to-batch variability, and the inside a same lot, in a batch of plugs with homogeneous characteristics, and low variability both from one batch to another and within the same batch.
  • the invention aims to obtain plugs having properties - in particular oxygen permeability - adapted to the liquids to be packaged.
  • the plugs of this batch have on their entire accessible surface, outer surface and inner surface of the cavities or anfractuosities of said plugs, a surface area of cork L, comprising a penetration of said polymeric material P in its mass with an incorporation of said polymeric material P cork, so that said treated plug has the composite skin "L + P".
  • the Applicant has succeeded in impregnating a layer of surface cork or skin with said liquid composition CP.
  • cork or at least its main constituent, the alveolar soft tissue, was able to absorb said CP liquid composition, as has been demonstrated in particular using micrographs with contrast agents.
  • a plug may therefore present locally, particularly at the level of the heterogeneities of the cork or in the anfractuosities of the plug, surface portions having a skin "L + P" of low thickness, or possibly covered with a layer of polymeric material "P".
  • the succession of at least steps a), c) and d) of the treatment is necessary to obtain plugs that solve all the problems posed, at least when the batch of corks stocked is a lot of so-called natural corks.
  • the corks obtained by the treatment according to the invention retain the general appearance of the natural cork stoppers, which would not be the case if the cork was covered with a polymeric or film-forming composition.
  • the treatment according to the invention therefore gives the stopper a composite skin "L + P" based on cork L and polymeric material P, largely intended to be placed in contact with the neck of the container and partly in contact with the conditioned liquid. this skin forming a deformable plastic material which continues, after plugging, to marry, under the effect of the radial compression, then the elastic recovery of the cork, the relief of the inner surface of said neck.
  • the figure 1a is a view of a bottle neck (101) closed by a plug (100) and covered with an overcap (102), this view forming, on the half-right portion of the figure, a half-view of side, and on the half-left part of the figure, an axial half-section in the axial direction (104) of the cap and the neck.
  • FIGs 1b and 1c are cross-sectional portions of the plug, perpendicular to its axial direction, which illustrate said composite skin (204) forming an outer composite skin (301).
  • the figure 1b is a photograph - macrography - of this sectional portion, a black dye tracer having been incorporated into the liquid composition.
  • the figure 1c is the schematic representation of the figure 1 b.
  • the Figures 2a to 2d are cups of plugs (100) obtained according to the invention.
  • a black tracer dye has been added to the liquid composition CP. It is thus very clearly perceived that the crevices such as lenticels, holes, cracks, crevices are impregnated with the liquid composition colored black so as to obtain a visual contrast.
  • the figure 2a is a photograph showing a left half-cut (300b) of a cork.
  • the figure 2b is a diagrammatic representation of a straight half-cut (300a) of the plug of the figure 2a .
  • the Figure 2c is an enlarged photograph of the framed portion A of the figure 2a .
  • the figure 2d is a schematic representation of the Figure 2c .
  • the figure 3 is a diagram relating to plugging and plugging forces, the extraction having been carried out 26 days after capping and storage at room temperature at 15 ° C.
  • the figure 4 is a diagram with the moisture content of the cork after 9 months of stay in the neck of an empty bottle and stored at 15 ° C.
  • the figure 5 shows schematically, in axial section, the device used to measure the oxygen permeability of a bottle portion (600) provided with the plug (100) to be tested.
  • This bottle portion (600) is secured to a metal platen (611) by a bead (612), the platen being provided with gas supply tubes (613) and gas outlet tubes (614), a sealed envelope (610) covering said bottle portion (600).
  • the figure 6 schematically represents a first device mode for the implementation of steps a) to d) of the object of the invention.
  • FIGS 7a to 9c illustrate another device modality for the implementation of steps a) to d) of the object of the invention.
  • this modality all the steps of the treatment are carried out, without transfer of the plugs, in a wiper reactor (800).
  • the Figures 7a to 8b are cross sections according to the CC plane of the Figure 9c .
  • the figure 7a illustrates step a) pressure impregnation.
  • the figure 7b illustrates step b) vacuum desorption processing.
  • the figure 8a illustrates step c) of spinning.
  • the figure 8b illustrates step d) of drying.
  • FIGS 9a to 9c are longitudinal sections along the axis or central shaft (803, 803 ') and according to the plane AA of the figure 7a , which illustrate different variants of wiper reactors (800).
  • the figure 9a represents a wiper reactor (800, 800a) of spherical shape.
  • the figure 9b represents a wiper reactor (800, 800b) of cylindrical form.
  • the Figure 9c represents a wiper reactor (800, 800c) of bi-frustoconical shape.
  • step a) of said treatment said batch of plugs (900a) can be immersed in a first pressure-resistant container (902) containing said liquid composition (903), and said container (902) under pressure with an air pressure P 1 of between 2 and 6 bars and preferably of 3 to 5 bars, said air pressure P 1 being applied inside said first container (902) on a duration between 1 and 15 minutes and preferably from 3 to 10 minutes.
  • step a) impregnation and after having tested several coating application methods, such as brush removal, spray spraying, dipping, soaking under ultrasound, it appeared to the plaintiff that these methods did not solve the problems posed. These problems were only solved when the treatment included a pressure impregnation of the polymeric CP liquid composition allowing this liquid composition CP to penetrate homogeneously inside the structure of the cork, in the cracks, the craters, slots, and galleries created by insects, or other open crevices opening on the surface of the plug.
  • step a) of impregnation under pressure almost all the anfractuosities is impregnated with said liquid composition CP, even in the case of crevices or cracks not directly open. It therefore seems that the pressure used in step a) of the treatment makes it possible to introduce said liquid composition CP into the entire network of crevices or crevices of the plug.
  • the Applicant has thus observed that at ambient temperature, using the film-forming or polymeric coating with a colored tracer, and for example applying a pressure of 5 bar for 3 minutes or 3 bar for 5 minutes, the penetration goal was totally achieved.
  • the liquid composition CP typically comprising an emulsion of acrylic polymers in aqueous aqueous phase or an aqueous composition based on EVOH, copolymer of ethylene and vinyl alcohol.
  • the batch of caps must be completely immersed in the liquid composition (903), then the lid (904) of said tank will be hermetically sealed.
  • An overpressure of filtered and controlled air (905) is then applied inside the tank (902).
  • the reservoir (902) is temperature controlled to maintain the viscosity of the liquid composition (903) constant.
  • the pressure is then suddenly relaxed inside the tank (902) and the lid (904) is removed.
  • the net (901) is raised above the level of the liquid composition (903) and allowed to drain for a few moments.
  • the amount of CP liquid composition consumed could vary according to various parameters, such as the surface tension of the plugs, the viscosity of the liquid composition CP and therefore its temperature, but also the quality of the plugs.
  • "0" quality corks superior quality called “Super”
  • Super superior quality
  • the treatment according to the invention can also be used with so-called plugged plugs, typically formed from plugs of grade 3 or beyond. In this case, the anfractuosities and cracks of the plug being already clogged, the consumption of liquid composition will be even more reduced.
  • said impregnated batch can be treated under vacuum, inside a vacuum-resistant container (902 '), with a pressure P 2 ranging from 0.1 to 4 mbar. and preferably from 0.5 to 1.5 millibar.
  • Said vacuum may be made inside said container for at least one minute, and preferably in cycles, with the atmospheric pressure being restored between each cycle, the number of cycles ranging from 1 to 10, and preferably ranging from 3 to 7, each cycle comprising a vacuum phase for about one minute.
  • step b) The desorption operation of step b) is produced by the depression of the reservoir containing the batch of plugs to be desorbed. Typically, the tests have shown that a pressure P 2 of 4 mbar can be used per cycle of one minute.
  • the batch of vacuum treated plugs can be, once introduced inside a wringer (910), wrung out in cycles, each cycle comprising a spinning phase lasting from 0.5 to 5 minutes, preferably between 1 and 3 minutes, with a number of cycles of between 1 and 5 and preferably between 2 and 3, a phase of stirring plugs being interposed between each phase spin, lasting between 3 seconds and 1 minute and preferably between 5 seconds and 30 seconds, and during which the plugs change position and place inside the drum of the wringer (910).
  • the batch of plugs can be subjected to a centrifugal force of between 20 and 80 Newtons, preferably between 30 and 60 Newtons.
  • this dewatering step c) before the firing of the coating, was necessary to complete or supplement the desorption step b), in order to avoid the excess of polymeric emulsion in the anfractuosities of the plugs, causing lingering bubbles after cooking.
  • these bubbles In addition to the unsightly appearance of these bubbles, they are torn during handling, distribution and installation of plugs thus releasing into the air cork particles may redeposit on different equipment and possibly in the bottled liquid.
  • the spin eliminates the presence of agglomerates of liquid composition CP on the surface of the stopper. All the plugs of a batch having undergone the stages of pressurization and then of evacuation, followed by spinning, respecting the cycles tested by the Applicant, have an absolutely clean outer surface and an example of any visible surface defect. with the naked eye, of any mass of liquid composition CP or polymeric material P.
  • the spin can be practiced in a drum machine with vertical or horizontal axis. Horizontal axis machines will be preferred because of the possible brewing steps between two spin sessions. These stirrings allow the plugs to move to provide different angles of extraction of coating product and thus to homogenize this operation.
  • the Applicant has shown that the choice of a drum machine with a diameter of 450 to 500 mm for a range of rotation speeds of 1200 to 1500 revolutions per minute made it possible to solve the problem posed, provided that cycles were observed. brewing at low speed: about 60 rpm. Preferably, alternating stirring with inversion of the direction of rotation, and spin.
  • the Applicant has shown that the stoppers could be introduced into the drum of the wringer, pre-packed in the net already used during the soaking-impregnation and desorption, said net, typically meshes of the order of 10x10mm having a global volume slightly greater than that of the drum of the wringer, so as not to thwart the effects of centrifugal force during the spin cycles.
  • step d) of the treatment after having extracted the batch of plugs (921) from the wringer (910) in step c) of the treatment, said batch of plugs (921) can be treated in a chamber ( 920), by a flow of hot air at a rate between 3.0 and 20.0 meters per second and preferably between 5.0 and 10.0 meters per second, so as to form said heat treatment, said treatment thermal being intended in particular to remove a solvent from said liquid composition CP, when said liquid composition CP comprises a solvent.
  • the batch of cap can be cooled by a flow of cold air, and possibly the speed of said cold air flow can be increased beyond 15 m / s, so as to expel said batch of caps from said enclosure, and thus to collect the batch of plugs directly into a bag or container adapted for this purpose.
  • Said flow of hot air may be applied at a temperature between 80 and 120 ° C and preferably between 90 and 100 ° C for a period of between 3 and 15 minutes and preferably between 5 and 10 minutes.
  • said flow of hot air may be applied at a temperature of between 40 and 80 ° C. and preferably between 50 and 70 ° C. for a duration of between 1 and 10 minutes and preferably between 2 and 5 minutes.
  • the heating of said flow of hot air can be stopped, said flow of air then passing at ambient temperature, so as to cool at ambient temperature said batch of plug, while a time substantially equivalent to that of said heat treatment.
  • the stoppers should not, preferably , stay in static contact with a wall, so as to obtain plugs having an excellent appearance of traditional stopper and avoid the presence of visible marks on the plugs.
  • the applicant has developed a drying-cooking system as illustrated on the figure 6 . After various tests and a development phase, the solution of the levitation of plugs under forced hot air flow was found to be excellent for obtaining plugs without surface defects.
  • step a) of the treatment it is possible to supply a batch of so-called plugged plugs, and the step b) of evacuation can be eliminated.
  • the invention applies to all types of plugs.
  • types of caps of relatively economic cost which is the case of so-called natural plugs.
  • so-called plugged plugs are also of a substantially similar cost insofar as the additional cost due to clogging treatment is substantially balanced by the lower cost of the starting cork, the latter, of lower quality, having more crevices or cracks, whether in number or depth.
  • the fluids used at the different stages of said treatment must be neutral. and free of germs, bacteria, yeasts and all contaminating sources of pollution for the liquids closed by the corks thus treated.
  • said liquid composition CP (903) may comprise, in addition to said polymeric material P, at least one additive A intended to promote the sliding of the stopper in contact with the glass, so that said treated stopper a "skin" of composition symbolically represented by "L + P + A”.
  • Said first and second polymeric compositions may be different, and for example, only the second impregnation may comprise said additive A.
  • Said liquid composition CP (903), CP 1 or CP 2 may comprise an elastomeric material E chosen from: butyl rubber, nitrile rubber, thermoplastic elastomers such as SIS (styrene isoprene styrene), SBS (styrene butadiene styrene), SEBS (styrene ethylene butylene styrene), MS Polymer (Modified Silicon Polymer) or PDMS (Polydimethylsiloxane).
  • SIS styrene isoprene styrene
  • SBS styrene butadiene styrene
  • SEBS styrene ethylene butylene styrene
  • MS Polymer Modified Silicon Polymer
  • PDMS Polydimethylsiloxane
  • Said additive A intended to promote the sliding of the plug in contact with the glass may be an anionic emulsion wax, typically based on paraffin wax or carnauba wax or a silicone resin when said first liquid polymer composition CP 1 comprises said composition based on EVOH, in order to cover said EVOH-based polymeric material P with a layer forming both a water barrier and a slip agent, said additive A being able to be an additive A 2 constituting said second liquid polymer composition CP 2 said second polymeric liquid composition then being free of EVOH.
  • Said liquid composition CP (903) may comprise a micronized mineral filler B forming a barrier, in particular to the diffusion of gases, said inorganic filler being chosen from: silica SiO 2 , a silicon oxide SiO x (with x ⁇ 2), titanium oxide TiO 2 , micronized clay, kaolin, barium sulfate.
  • said liquid composition CP (903) can have a dynamic viscosity at 20 ° C of between 5 and 1000 cps (centipoise), and preferably between 10 and 800 cps, of in such a way that said CP liquid composition (903) can penetrate the crevices of the natural cork stoppers and form said skin or said composite skin.
  • said dynamic viscosity is between 5 and 100 cps, and preferably between 10 and 40 cps.
  • said batch of plugs may be contained in a mesh of chemical nature and of mesh size (for example 10 mm ⁇ 10 mm) adapted, capable of passing said liquid composition CP (903) while remaining inert with respect to said liquid composition, and with a mesh size smaller than the smallest dimension of the corks to be treated, so as to have to manipulate a net in which is located said batch of corks, during steps a) to c) of treatment.
  • a mesh of chemical nature and of mesh size for example 10 mm ⁇ 10 mm
  • Another object of the invention is constituted by a cork, typically a batch of corks, obtained by the treatment according to the invention, and characterized in that it has on its entire accessible surface, outer surface and surface internal cavity or crevice said plugs, a cork surface area L, comprising a penetration of said polymeric material P in its mass with an incorporation of said polymer material P cork, so that said treated plug has a composite skin (204); , 301, 304) of composition symbolically represented by "L + P", said composite skin (204, 301, 304) having a thickness E of at least 10 ⁇ m and up to 1 mm, depending on the local hardness or porosity of the natural cork or its constituents.
  • said polymeric material P may be an acrylic resin with a density of between 0.95 and 1.2, and preferably between 0.98 and 1.00, or an aqueous composition based on EVOH, an ethylene copolymer and polyvinyl alcohol.
  • the presence of a "L + P" composite skin is not exclusive of the possibility of having at least locally a part of said polymeric material P deposited on the surface of the cork, in particular within the crevices. of the cap.
  • said surface area of cork L forming said composite skin can comprise, in addition to the incorporation of said polymeric material P cork, the incorporation of said additive A intended to promote the sliding of the cork in contact with the glass, so that said treated plug has a composite skin of composition symbolically represented by "L + P + A” or "L + P / A” according to whether said additive A is incorporated in said polymeric material P or covers said polymeric material P.
  • Said surface area of cork L may comprise, in addition to the incorporation of said polymeric material P to the cork and the incorporation of said additive A, the incorporation of at least one adjuvant chosen from: a micronized mineral filler B forming a barrier, in particular to the diffusion of gases, an elastomeric resin E.
  • Another object of the invention is the use of corks according to the invention, or obtained by the treatment according to the invention, for sealing containers, typically made of glass, containing alcohols, wines or spirits.
  • Cork corks A supply of untreated corks has been supplied to natural cork processors: these plugs, known as natural corks, have not undergone any treatment other than washing with hot water, are called natural. These natural cork stoppers are of standard dimensions 45mmx24mm (height x diameter).
  • the Applicant has therefore selected Vaporcoat TM 2200 E as polymeric liquid composition CP to prepare and test the plugs according to the invention.
  • liquid composition comprising said polymeric material P selected among the materials approved for food contact, a Kuraray EVOH composition, reference AQ-4104, was selected and supplied under reference A22.
  • Silicone and synthetic rubber-based elastomer dispersions particularly a Bluestar silicone dispersion, CAF 72582, have been supplied under reference A50.
  • Tests have also been carried out with a single-vessel device, as shown in FIGS. Figures 7a to 9c which makes it possible to carry out the four stages a) to d) of the treatment in the same reactor.
  • a filtered and controlled air overpressure (905) of 3 bar (1 bar is 10 5 Pa) for 5 minutes.
  • the compressed air was turned off and the inside of the vessel was allowed to return to atmospheric pressure.
  • the net (901) was raised above the bath formed by the liquid composition (903), so that fillet and batch of plugs (900) drip for two minutes. minutes, so as to recover the excess of said liquid composition CP.
  • autoclave container was self-regulated in temperature around 38 ° C so as to maintain the viscosity of the liquid composition CP constant.
  • the inside of the tank was evacuated with a pressure controlled by a vacuum meter (905 ') of 1 millibar for 1 minute. Then the vacuum was turned off and this second tank (902 ') was put back to atmospheric pressure. This cycle was repeated 5 times.
  • the lid (904 ') was removed and said batch of plugs (900') was removed from said second tank (902 ').
  • the desorbed CP liquid composition (906) was recovered at the bottom of the tank (902 '). This small amount (906) of said CP liquid composition was extracted, either by gravity or with a pump, to then be filtered and recycled in the first step a) pressure impregnation.
  • the batch of plugs (900 ') was then subjected to alternating cycles of spinning and stirring, the net being of a volume slightly greater than that of the drum of the wringer.
  • the polymer exudates which have been pumped back by the pump (912) were recovered to a recovery tank, to be filtered and recycled to the impregnation circuit.
  • the batch of corks was extracted from the wringer directly with the aid of the net (901).
  • the plugs were dumped from the net directly into a highly ventilated vertical duct furnace (920).
  • the plugs were held by a calibrated wire mesh (924) above the low temperature heating system (923).
  • the heating was increased to its set point and a vertical hot air stream ("A" circuit), from bottom to top, was circulated with a flow rate or flow rate that was high enough to maintain the plugs (921). levitation or suspension in the air.
  • a second calibrated grid (925) in the upper part of the duct retained any plugs lighter than the average of the batch, and under the upward pressure, would have risked escaping from the duct (920).
  • the heating (923) was raised to its nominal level after a first solvent evaporation step.
  • the plugs have been maintained in a levitation or flotation state in order to avoid the sticking effects between them, but also to avoid any excessive contact against the wall of the vertical duct (920).
  • the walls of the vertical duct (920) have been surface-treated with PTFE deposition or any other material promoting sliding and limiting the risk of material accumulation of the coating object of the invention.
  • the air velocity has been lowered, for example to around 3 m / s, in order to force all the plugs to go down to the lower grid (924) and thus to allowing the flap (926) to move to obstruct the vertical duct (920) without being obstructed by possible levitation plugs and thus open the horizontal duct (927).
  • the batch of said plugs is expelled to the outside of the vertical oven, via a movable flap (926) closing off the main vertical duct , to direct them towards the exit through the horizontal duct thus released, with a speed of expulsion for example of 10 m / s.
  • the plugs (928) are collected in an intermediate packing net (929), or in their final packaging.
  • the final packaging is advantageously made out of dust so as not to introduce external dust into the plugs conditioned for their end use.
  • compositions CP (903) were prepared by mixing a composition or polymeric material P in the form of an aqueous dispersion, and a slip agent A, also in the form of an aqueous dispersion.
  • test E1 was also performed by supplementing it with a subsequent application of a slip agent, which may correspond to the products A30, A31 or possibly A50.
  • plugs with two impregnations were produced, a first with a liquid composition CP 1 comprising 80% by weight of A 21 and 20% with a barrier mineral filler, and a second with a liquid composition CP 2 comprising 80% by weight. weight of A21 and 20% of A31.
  • plugs with two impregnations were produced, a first with a liquid composition CP 1 comprising 80% by weight of A21 and 20% of a barrier inorganic filler, and a second with a liquid composition CP 2 comprising 60% by weight. weight of A21, 20% of A31 and 20% of a dispersion of an elastomer.
  • each of these impregnations can be carried out according to the method PR1 and / or PR2, with all the possible combinations: PR1-PR1, PR2-PR2, PR1-PR2, PR2-PR1; "PR2-PR1" meaning that the first impregnation is carried out according to the method PR2 which does not comprise step b) vacuum treatment, while the second impregnation is carried out according to the method PR1 which itself comprises one.
  • plugs were made with impregnation with a liquid composition CP comprising the Kuraray EVOH composition A22, reference AQ-4104, using each of the PR1 or PR2 method, said impregnation being followed by an application of at least one layer, and preferably two layers, of a Bluestar Silicone Fluid Dispersion A50, reference CAF 72582, said application being followed by drying under a pulsed air flow, the Applicant having observed that it was thus possible to advantageously obtain a silicone resin-based outer layer forming both a moisture barrier to protect the underlying moisture-sensitive EVOH layer, and a slip agent for cap.
  • Bottles have been closed with the plugs of the previous tests, using the usual method: using an instrumented commercial device to measure the vertical force, the plug is compressed radially and then introduced by mechanical push vertical in the neck of a bottle.
  • the caps were extracted with a device to measure the extraction effort.
  • test E0 The commercially treated natural cork bottles 45 x 24mm treated with silicones (test E0) have extraction values ranging from 20 to 30 daN with a standard deviation of 3.90, which is already remarkable because it is not rare to find on the market extraction values on natural cork fluctuating between 10 and 50 daN and even from 30 daN to more than 60 daN in the case of plugged corks.
  • the extraction values range from 23 to 30 daN with a relatively low standard deviation of 2.19.
  • the Applicant has checked the internal hygrometry of the plugs obtained in the tests according to the invention, as well as the hygrometry at the start. All the caps of the tests have moisture content values, measured at 20 ° C, between 4 and 5%, values substantially identical to those of the initial plugs.
  • the plugs of the control test E0 also have a humidity level in the same range of values.
  • the commercial natural cork stoppers treated with silicones (E0), had an average humidity measured at the beginning of 4.4%, and a mean humidity, measured after 9 months, of 5.5%.
  • tests E1 to E7 had an average humidity initially measured after impregnation of 5.2%, and after 9 months, this average humidity was still 5.2%.
  • test plugs E0 to E7 were immersed for 24 hours in a container containing water from the network. At the end of this period, and after a drying time of 24 hours in the open air, a new series of measurements was carried out and the following results appeared:
  • test E0 Commercial natural cork stoppers treated with silicones
  • test E0 had a moisture content initially measured ranging from 4.6 to 5.8% moisture. After immersion and drying, after 48 hours, the measured average humidity increased from 6.6% to 9.6% moisture.
  • the plugs of the tests E1 to E7 which are the subject of the invention had a humidity measured initially ranging from 4.7 to 5.4% of moisture. After immersion and drying, after 48 hours the measured average humidity ranged from 5.0 to 5.2% moisture.
  • corks treated according to his invention do not evolve over time, even in the presence of a liquid.
  • the Applicant has concluded that the corks treated according to his invention can equip coated or uncoated bottles, which is not the case for standard commercial bottles, they must not under any circumstances remain upright, since said plugs must keep in constant contact with the liquid, otherwise the cork loses its moisture, becomes hardened and loses its elasticity, resulting in a loss of watertightness due to lack of contact force or springback, inside the cervix. the bottle.
  • the applicant has carried out comparative tests of oxygen permeability of corks on bottles, in marketing conditions, which means with liquid inside said bottles.
  • One batch of bottles was capped with standard commercial 45 x 24mm silicone-treated plugs (E0 test) and another batch of the same size, with corks treated with the material and the conditions of the pack. invention (tests E1 to E7).
  • haloanisole contents released in the hydroalcoholic solution were determined by SPME (Solid Phase Micro Extraction) and SBSE (Stir Bar Sorptive Extraction):
  • the invention makes it possible to economically produce a large variety of corks with properties and performances adapted to the particular requirements of each type of wine to be bottled, in particular by adding to said liquid composition of all kinds of additives, such as TiO 2 , SiO 2 , SiOx, talc, clays, kaolin, barium sulfate.
  • additives such as TiO 2 , SiO 2 , SiOx, talc, clays, kaolin, barium sulfate.

Claims (15)

  1. Behandlung von Verschlüssen aus natürlichem Kork (900), umfassend aufeinander folgend die folgenden Schritte a, c und d:
    a) Bereitete einer Charge einer Vielzahl von so genannten natürlichem Verschlüssen (900a), und Imprägnieren der Charge in einer flüssigen Zusammensetzung CP (903), umfassend mindestens einen polymeren Stoff P, unter einem Druck P1, der höher als der atmosphärisch Druck PA ist, um eine so genannte imprägnierte Charge zu erhalten,
    c) dann Schleudern der imprägnierten Charge, um eine so genannte geschleuderte Charge zu erhalten,
    d) schließlich Unterziehen der geschleuderten Charge einer thermischen Behandlung, um eine Charge von so genannten behandelten Verschlüssen (928) zu erhalten, wobei jeder Verschluss (928) eine "Verbundhaut" (204, 301, 304) aus Kork L aufweiset, die mit polymerem Stoff P imprägniert ist, symbolisch dargestellt durch "L + P".
  2. Behandlung von Verschlüssen aus natürlichem Kork (900) nach Anspruch 1, umfassend außerdem einen Schritt b) der Behandlung unter Vakuum, der zwischen die Schritte a) und c) eingeschoben ist, um aufeinander folgend über die folgenden Schritte a) bis d) zu verzügen:
    a) Bereitstellen einer Charge einer Vielzahl von so genannten natürlichen Verschlüssen (900a), Imprägnieren der Charge in einer flüssigen Zusammensetzung CP (903), umfassend mindestens einen polymeren Stoff P, unter einem Druck P1, der höher als der atmosphärisch Druck PA ist, um eine so genannte imprägnierte Charge zu erhalten,
    b) dann Behandeln der imprägnierte Charge und Vakuum unter einen Druck P2 < PA, um eine unter Vakuum behandelte Charge zu erhalten,
    c) dann Schleudern der unter Vakuum behandelten Charge, um eine so genannte geschleuderte Charge zu erhalten,
    d) schließlich Unterziehen der geschleuderten Charge einer thermischen Behandlung.
  3. Behandlung nach einem der Ansprüche 1 bis 2, wobei in Schritt a) die Charge aus Verschlüssen (900) in einen ersten druckresistenten Behälter (902), der die flüssige Zusammensetzung (903) enthält, eingetaucht wird, und der Behälter (902) bei einem Luftdruck P1 zwischen 2 und 6 bar und vorzugsweise zwischen 3 und 5 bar unter Druck gesetzt wird, wobei der Luftdruck P1 auf das Innere des ersten Behälters (902) während einer Dauer wischen 1 und 15 Minuten und vorzugsweise zwischen 3 und 10 Minuten angewendet wird.
  4. Behandlung nach einem der Ansprüche 2 bis 3, wobei in Schritt b) des Behandelns die imprägnierte Charge unter Vakuum im Inneren eines Behälters behandelt wird, der ausgelegt ist um unter Vakuum zu halten (902'), mit einem Druck P2, der von 0,1 bis 4 mbar reicht und vorzugsweise von 0,5 bis 1,5 Millibar reicht.
  5. Behandlung nach einem der Ansprüche 1 bis 4, wobei in Schritt c) der Behandlung nach der erneuten Aussetzung an die freie Luft, die Charge aus Verschlüssen, behandelt unter Vakuum, nachdem sie in das Innere einer Schleuder (910) eingeführt wurde, in Zyklen geschleudert wird, wobei jeder Zyklus eine Schleuderphase mit einer Dauer von 0,5 bis 5 Minuten, vorzugsweise zwischen 1 und 3 Minuten umfasst, mit einer Anzahl von Zyklen zwischen 1 und 5 und vorzugweise zwischen 2 und 3, und wobei eine Phase des Rührens der Verschlüsse wischen jede Schleuderphase mit einer Dauer zwischen 3 Sekunden und 1 Minute und vorzugsweise zwischen 5 Sekunden und 30 Sekunden eingeschoben wird, und in deren Verlauf die Verschlüsse im Inneren der Schleudertrommel (910) ihre Position und ihren Standort ändern.
  6. Behandlung nach einem der Ansprüche 1 bis 5, wobei in Schritt d) der Behandlung nachdem die Charge von Verschlüssen (921) in Schritt c) der Behandlung aus der Schleuder (910) entnommen wurden, die Charge von Verschlüssen (921) in einem Schutzbehälter (920) durch eine heißen Luftstrom mit einer Geschwindigkeit zwischen 3, 0 und 20,0 Metern pro Sekunde und vorzugsweise wischen 5,0 und 10,0 Metern pro Sekunde beharzdalt wird, um die thermische Behandlung zu bilden, wobei die thermische Behandlung insbesondere dazu ausgelegt ist, um ein Lösemittel der flüssigen Zusammensetzung CP zu entfernen, wenn die flüssige Zusammensetzung CP ein Lösemittel enthält.
  7. Behandlung nach einem der Ansprüche 1, 2, 3, 4 und 6, wobei in Schritt a) der Behandlung eine Charge von so genannten abgedichteten Verschlüssen (900b) bereitgestellt wird, und der Schritt b) der Aussetzens an ein Vakuum weggelassen wird.
  8. Behandlung nach einem der Ansprüche 1 bis 7, wobei die flüssige Zusammensetzung CP (903) außer dem polymeren Stoff P mindestens einen Zusatzstoff A umfasst, der dazu ausgelegt ist, um das Gleiten des Verschlusses beim Kontakt mit dem Glas zu erleichtern, so dass der behandelte Verschluss eine "Haut" mit der Zusammensetzung aufweiset, die symbolisch durch "L+P+A" dargestellt ist.
  9. Behandlung nach einem der Ansprüche 1 bis 8, wobei die flüssige Zusammensetzung CP (903) eine Emulsion oder eine Dispersion in wässeriger Phase mit mindestens einem polymeren Stoff CP bildet, der unter den polymeren Materialien ist, die:
    a) für den Kontakt mit Lebensmittel zugelassen sind,
    b) ausgelegt sind, um eine Barriere gegen die so genannten schädliche Moleküle zu bilden,
    wobei der polymere Stoff P vorzugsweise eine Emulsion von Acrylpolymeren in wässrigem Milieu oder eine wässrige Zusammensetzung auf der Basis von EVOH, EthylenVinylalkohol-Copolymer, ist.
  10. Behandlung nach einem der Ansprüche 1 bis 9, umfassend
    a) eine so genannte erste Aufeinanderfolge mindestens der Schritte a), c) und d) aus einer so genannten ersten polymeren flüssigen Zusammensetzung CP1 gebildet typischerweise aus der flüssigen Zusammensetzung CP, die den polymeren Stoff P umfasst, um eine so genannte erste Imprägnierung zu bilden,
    b) und eine komplementäre Behandlung, umfassend z.B. eine so genannte zweite Aufeinanderfolge von mindestens den Schritten a), c) und d), aufs einer so genannten zweiten polymeren flüssigen Zusammensetzung CP2wobei mindestens die zweite polymere flüssige Zusammensetzung CP2 den Zusatzstoff A umfasst, der ausgelegt ist, um das Gleiten der Verschlüsse zu erleichtert, um eine so genannte zweite Imprägnierung zu bilden, so dass der behandelte Verschluss eine Verbund-"Haut" mit einer Zusammensetzung aufweist, die symbolisch durch "L + P / A" dargestellt ist.
  11. Behandlung nach einem der Ansprüche 1 bis 10, wobei die flüssige Zusammensetzung CP (903), CP, oder CP2 ein elastomeres Material E umfasst, ausgewählt aus: dem Butylkautschuk, dem Nitrilkautschuk, den thermoplastischen Zusammensetzungen wie z.B. SIS (Styrenisoprenstyren), SBS (Styrenbutadienstyren), SEBS (Styrenethylenbutylenstyren), MS Polymer (modifiziertes Silikonpolymer) oder PDMS (Polydimethylsiloxan).
  12. Behandlung nach einem der Ansprüche 8 bis 11, wobei der Zusatzstoff A, der ausgelegt ist, um das Gleiten des Verschlusses beim Kontakt mit dem Glas zu erleichtern, ein Wachs in anionischer Emulsion ist, typischerweise auf der Basis von Paraffinwachs oder Carnaubawachs, oder ein Silikonwachs, wenn die erste polymere flüssige Zusammensetzung CP die wässrige Zusammensetzung auf der Basis von EVOH umfasst, um den polymeren Stoff P auf der Grundlage von EVOH mit einer Schicht zu bedecken, die gleichseitig eine Barriere gegen das Wasser und ein Gleitmittel bildet, wobei der Zusatzstoff A ein Zusatzstoff A2 sein kann, der die zweite polymere flüssige Zusammensetzung CP2 bildet, wobei dann die zweite polymere flüssige Zusammensetzung frei von EVOH ist.
  13. Behandlung nach einem der Ansprüche 1 bis 12, wobei die flüssige Zusammensetzung CP (903) einer mikronisierte mineralische Ladung B umfasst, die eine Barriere bildet, insbesondere gegen die Gasdiffusion, wobei die minoralische Ladung ausgewählt ist aus: dem Silicium SiO, einem Siliciumoxid SiOx (mit x< 2), dem Titanoxid TiO2, dem mikronisierten Ton, dem Kaolin, dem Bariumsulfat.
  14. Verschluss aus Kork, erhalten durch die Behandlung nach einem der Ansprüche 1 bis 13, dadurch gekennzeichnet, dass er auf seiner gesamten zugängliche Fläche, der externen und der internen Fläche, Hohlräume oder Aushöhlungen der Verschlüsse umfasst, einen Oberflächenbereich des Korks L, umfassend eine Einbringung des polymeren Stoffs P in seine Masse mit einem Einschluss des polymeren Stoffs P in den Kork, so dass der behandelte Verschluss eine Verbundhaut (204, 301, 304) mit einer Zusammensetzung umfasst, die symbolisch durch "L+P" dargestellt ist, wobei die Vorbundhaut (204, 301, 304) eine Dicke E aufweist, die mindestens 10 µm beträgt und bis zu 1 mm reichen kann, je nach der lokalen Härte oder Porosität des natürlichen Korks oder seiner Bestandteile, und optional dadurch gekenntzeichnet, dass der Oberflächenbereich des Korks L, der die Verbundhaut (204, 301 304) bildet, außerdem den Einschluss des polymeren Materials P in den Kork und den Einschluss des Zusatzstoffes A, den Einschluss von mindestens einem Hilfsmittel umfasst, ausgewählt aus: einer mikronisierten mineralischen Ladung B, die eine Barriere bildet, insbesondere gegen die Gasdiffusion, ein elastomeres Harz E.
  15. Verschluss aus Kork nach Anspruch 14, wobei der Oberflächenbereich des Korks L, der die Verbundhaut (204, 301 304) bildet, außer dem Einschluss des polymeren Stoffs P in den Kork den Einschluss des Zusatzstoffes A umfasst, der dazu ausgelegt ist, um das Gleiten des Verschlusses beim Kontakt mit dem Glas zu erleichtern, so dass der behandelte Korken eine Verbundhaut mit einer Zusammensetzung aufweist, die symbolisch durch "L + P + A" dargestellt ist, oder durch "L+P / A", je nachdem, ob der Zusatzstoff A in den polymeren Stoff P eingeschlossen ist oder den polymeren Stoff P beschichtet, und optional dadurch gekennzeichet, dass der Oberflächenbereich des Korks L, der die Verbundhaut (204, 301 304) bildet, außer dem Einschluss des polymeren Stoffs P in den Kork und den Einschluss des Zusatzstoffes A, den Einschluss von mindestens einem Hilfsmittel umfasst, ausgewählt aus: einer mikronisierten mineralischen Ladung B, die eine Barriere bildet, insbesondere gegen die Gasdiffusion, ein elastomeres Harz E.
EP11708530.8A 2010-02-08 2011-02-07 Bearbeitung von verschlussstopfen aus natürlichem kork und durch diese bearbeitung gewonnene verschlussstopfen Not-in-force EP2533957B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR1000497A FR2956058B1 (fr) 2010-02-08 2010-02-08 Traitement de bouchons en liege naturel et bouchons obtenus par ledit traitement
PCT/FR2011/000073 WO2011095713A2 (fr) 2010-02-08 2011-02-07 Traitement de bouchons en liege naturel et bouchons obtenus par ledit traitement

Publications (2)

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EP2533957A2 EP2533957A2 (de) 2012-12-19
EP2533957B1 true EP2533957B1 (de) 2013-05-01

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EP11708530.8A Not-in-force EP2533957B1 (de) 2010-02-08 2011-02-07 Bearbeitung von verschlussstopfen aus natürlichem kork und durch diese bearbeitung gewonnene verschlussstopfen

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EP (1) EP2533957B1 (de)
ES (1) ES2421614T3 (de)
FR (1) FR2956058B1 (de)
PT (1) PT2533957E (de)
WO (1) WO2011095713A2 (de)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
PT108751B (pt) 2015-08-04 2021-01-14 Reliable Cork Solutions, Unipessoal Lda. Dispositivo de rectificação e melhoramento de rolhas de cortiça

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2904524A (en) * 1957-01-02 1959-09-15 Armstrong Cork Co Cork composition containing epoxy resin
FR1574820A (de) * 1968-04-24 1969-07-18
US4042543A (en) * 1976-02-13 1977-08-16 Strickman Robert L Material for stoppers
FR2635292B1 (fr) 1988-08-12 1990-11-16 Henkel France Procede de traitement de bouchons en liege
AUPN177495A0 (en) 1995-03-16 1995-04-13 Dewar, Diane Improved closure
GB9519972D0 (en) 1995-09-28 1995-11-29 Ag Patents Ltd Improved container stoppers
ATE248690T1 (de) * 1995-11-07 2003-09-15 Portocork Internacional S A Verfahren zur herstellung von flaschenkorken
WO1997030098A1 (en) 1996-02-19 1997-08-21 Imperial Chemical Industries Plc Process for binding cork
DE10147626A1 (de) * 2001-09-27 2003-04-24 Wacker Chemie Gmbh Verfahren zur Imprägnierung von Flaschenkorken
WO2003031276A1 (fr) 2001-10-05 2003-04-17 Polymer Systems Co., Ltd. Procede de formation d'une pellicule sur un bouchon de liege
US20040166345A1 (en) 2003-02-26 2004-08-26 Wicht Charles A. Processes and articles useful for preventing cork taint in beverages
DE102006019818A1 (de) * 2005-05-02 2006-11-09 Basf Ag Verwendung wässriger Wachsdispersionen zur Imprägnierung von Lignocellulose-Materialien
DE102006013102A1 (de) 2006-03-20 2007-09-27 Henkel Kgaa Diffusionsreduzierende Korkbeschichtung
DE102006016054A1 (de) 2006-04-04 2007-10-11 Henkel Kgaa PU Korkbeschichtung

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WO2011095713A3 (fr) 2011-09-29
ES2421614T3 (es) 2013-09-04
WO2011095713A2 (fr) 2011-08-11
FR2956058B1 (fr) 2012-02-03
EP2533957A2 (de) 2012-12-19
FR2956058A1 (fr) 2011-08-12
PT2533957E (pt) 2013-08-02

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