EP2533957A2 - Traitement de bouchons en liege naturel et bouchons obtenus par ledit traitement - Google Patents
Traitement de bouchons en liege naturel et bouchons obtenus par ledit traitementInfo
- Publication number
- EP2533957A2 EP2533957A2 EP11708530A EP11708530A EP2533957A2 EP 2533957 A2 EP2533957 A2 EP 2533957A2 EP 11708530 A EP11708530 A EP 11708530A EP 11708530 A EP11708530 A EP 11708530A EP 2533957 A2 EP2533957 A2 EP 2533957A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- batch
- plugs
- treatment
- cork
- liquid composition
- 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.)
- Granted
Links
Classifications
-
- 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.
- the international application WO2007 / 115612 discloses a stopper formed from cork granules coated with a polyurethane resin.
- the international application WO2007 / 107209 describes 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.
- the international application W096 / 28378 discloses a cork plug encapsulated in a layer, preferably PVC or polyurethane, formed for example by molding and heat treatment.
- international application WO91 / 04836 discloses a cork stopper treatment comprising a washing step using 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 international application WO03 / 031276 discloses a cork stopper treatment comprising the deposition of a synthetic resin powder on the cap, and the fusion of this resin by infrared heating.
- the aim of the invention is to obtain plugs that comprise an effective barrier against the migration of said harmful molecules.
- the plugs have moisture contents that vary from one plug to another as well as over time, and this, according to many parameters, especially with ambient relative humidity or depending on whether the plug is or not in permanent contact with the bottled liquid.
- the moisture content inside the cork is fundamental to maintaining its physical characteristics throughout its life, until the first opening of the bottle. Variations of 3 to> 10% moisture were measured on different lots of commercial corks, before introduction into the neck of the bottles, while the standard provides for 4 to 8% moisture cork.
- the mechanical characteristics of compression and elastic recovery of the plugs depend for the most part on the moisture contained in the plug.
- the invention therefore aims to produce natural cork stoppers having an internal humidity within a restricted range and a predetermined value. d) In a significant percentage of cases, with commercial cork stoppers, problems are encountered with the opening of the bottle and with the extraction of the cork, in particular when the bottle is uncorked, a loss of physical integrity or mechanical strength of the plug, which leads to both a difficult plug extraction - it must be done repeatedly to extract the entire neck cap - and often to contamination liquid conditioned by debris of this plug, resulting in a degradation of the quality and the drinkable quantity of the bottled liquid.
- the object of the invention is to obtain natural cork stoppers which retain their physical integrity, in particular during their extraction from the neck, often many years after the liquid has been packaged.
- the invention aims at obtaining natural cork stoppers which have an opening force situated in a restricted range and of predetermined value.
- the invention aims to obtain plugs which have an oxygen permeability in a relatively narrow range, as already mentioned, and predetermined to be adapted to the type of liquid or wine conditioning. h) Although corking wine bottles is a constantly evolving field, the fact remains that the majority of wine bottles produced in the world are closed by a natural cork, the natural cork keeps despite its disadvantages, an excellent brand image linked to an idea of tradition. The invention aims to obtain plugs that retain the appearance of traditional natural cork stoppers.
- the Applicant has found that the plugs of the prior art do not allow not to obtain a liquid and gaseous seal, particularly with pressures inside the container ranging from 10 bar to 15 bar, ie from 1 MPa to 1.5 MPa, for a temperature range typically ranging from 0 ° C. to 50 ° C, and this for a period of up to several years, even several decades.
- the plugs and treatments according to the invention aim to solve these problems.
- 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. DESCRIPTION OF THE INVENTION
- the treatment of natural cork stoppers successively comprises the following steps a, c and d:
- a complementary step b) of vacuum treatment can be incorporated, the treatment of natural cork stoppers then comprising successively the following steps a) to d):
- each plug having a "composite skin" of cork L impregnated with polymeric material P, represented symbolically by "L + P".
- 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.
- This skin corresponds to all the accessible surfaces of the stopper and which comprise corky tissue, these accessible surfaces being:
- the so-called outer surface of the stopper comprising the cylindrical surface of the stopper and the two circular faces at the ends of the stopper
- the so-called internal surface comprising all the surfaces of the cavities, cracks and any type of open crevices, that is to say opening onto said external surface.
- 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.
- the stoppers according to the invention placed in contact with a hydroalcoholic medium do not alter its taste or the smell.
- FIG. 1a is a view of a bottle neck (101) closed off by a stopper (100) and covered with an overcap (102), this view forming, on the half-right portion of the figure, a half side view, and on the half-left part of the figure, an axial half-section in the axial direction (104) of the cap and the neck.
- Figures 1b and 1c are cross-sectional sections of the plug, perpendicular to its axial direction, which illustrate said composite skin (204) forming an outer composite skin (301).
- Figure 1b is a photograph - macrography - of this sectional portion, a black dye tracer having been incorporated in the liquid composition.
- Figure 1c is the schematic representation of Figure 1b.
- FIGS 2a to 2d are sections 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.
- Figure 2a is a photograph showing a left half-cut (300b) of a plug.
- Figure 2b is a schematic representation of a right half-section (300a) of the plug of Figure 2a.
- Figure 2c is an enlarged photograph of the framed portion A of Figure 2a.
- Figure 2d is a schematic representation of Figure 2c.
- Figure 3 is a diagram relating to plugging and plugging forces, the extraction having been performed 26 days after capping and storage at room temperature at 15 ° C.
- Tests E1 to E7 correspond to plugs obtained with the treatment according to the invention.
- Curve B average extraction value
- Curve D maximum capping value
- Curve E mean value in capping
- Curve F minimum capping value.
- Figure 4 is a diagram of the moisture content of corks after 9 months of residence in the neck of an empty bottle and stored at 15 ° C.
- FIG. 5 schematically represents, in axial section, the device used for measuring 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).
- FIG. 6 schematically represents a first device modality 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).
- FIG. 7a illustrates the step a) of impregnation under pressure.
- Fig. 7b illustrates step b) vacuum desorption processing.
- Figure 8a illustrates the step c) of spinning.
- Figure 8b illustrates step d) of drying.
- Figures 9a to 9c are longitudinal sections along the axis or central shaft (803,
- FIG. 9a represents a wiper reactor (800, 800a) of spherical shape.
- Figure 9b shows a wiper reactor (800, 800b) of cylindrical shape.
- FIG. 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 of between 2 and 6 bar and preferably of 3 to 5 bar, said air pressure P ⁇ being applied inside said first container (902) over a period of time 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 it seems that, during step a) of impregnation under pressure, almost all the anfractuosities are impregnated with said liquid composition CP, even in the case 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.
- a batch of raw corks (900) previously packaged in a suitable net (901) whose mesh size does not exceed the smallest size of the corks to be treated is introduced into a pressure-resistant reactor or tank (902) inside which the CP liquid composition (903), typically comprising an aqueous aqueous acrylic polymer emulsion or an aqueous EVOH-based composition, has previously been introduced.
- the CP liquid composition (903) typically comprising an aqueous aqueous acrylic polymer emulsion or an aqueous EVOH-based composition
- 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 so as 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.
- 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 Applicant has observed that several alternating cycles of evacuation and relaxation, significantly increased the desorption level. Thus, series of 3 to 5 alternating cycles of evacuation for 1 min and relaxations gave excellent results. The conditions of this desorption are such that this desorption affects only the liquid composition CP "free" which is in the crevices, and not the liquid composition that has penetrated into the cork to form said composite skin "L + P".
- 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.
- 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.
- 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 plugs could be introduced into the drum of the wringer, pre-packed in the net already used during the dipping-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 caps should not, preferably, remain in static contact with a wall, so as to obtain plugs having an excellent appearance of traditional plug and avoid the presence of visible marks on the plugs.
- the Applicant has developed a drying-baking system as illustrated in FIG. 6. After various tests and a development phase, the solution of the levitation of the plugs under hot air flow was found to be excellent for obtaining plugs without surface defects.
- the polymeric emulsion in aqueous phase forming said liquid composition requires a phase of evaporation of the solvent.
- the solvent in question is water, which is the preferred case, the water must be evaporated, before coagulation and polymerization of the coating, otherwise bubble formation would be observed.
- the following Time / Temperature cycle will be preferred:
- the plug batch can be cooled by a flow of cold air velocity, and possibly the speed of said cold air flow can then be increased beyond 15 m / s, so as to expel said batch of plugs from said enclosure, and thus to collect the batch of plugs directly into a bag or container adapted for this purpose.
- 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 desorption step b) plugs can thus be suppressed, having no reason to be.
- the fluids used at the different stages of said treatment whether in particular the compressed air in step a) of the treatment, or of the hot air in step d) of the 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 liquid composition CP (903) can form an emulsion or a dispersion in aqueous phase of at least one polymeric material P chosen from polymeric materials:
- said polymeric material P preferably being an acrylic polymer emulsion in an aqueous medium or an aqueous EVOH-based composition, a copolymer of ethylene and vinyl alcohol.
- said treatment may comprise:
- a complementary treatment comprising, for example, a said second succession of at least steps a), c) and d), from a said second polymeric liquid composition CP 2 , at least the said second liquid polymer composition CP 2 comprising said additive A intended to promote the sliding of said plugs, so as to form a said second impregnation, so that said treated plug has a composite "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), CPi or CP 2 can comprise an elastomeric material E chosen from: butyl rubber, nitrile rubber, thermoplastic elastomers such as SIS (styrene isoprene styrene), SBS (styrene butadiene styrene), SEBS (Ethylene styrene butylene styrene), MS Polymer (Modified Silicon Polymer) or PDMS (Polydimethylsiloxane).
- E elastomeric material chosen from: butyl rubber, nitrile rubber, thermoplastic elastomers such as SIS (styrene isoprene styrene), SBS (styrene butadiene styrene), SEBS (Ethylene styrene butylene styrene), MS Polymer (Modified Silicon Polymer) or PDMS (Polydimethylsilox
- 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 ! comprises said aqueous 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), TiO 2 titanium oxide, 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.
- 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).
- Liquid compositions comprising a film-forming or polymeric material
- a liquid composition comprising said polymeric material P selected among the materials approved for food contact has been selected and supplied:
- A21 VaporCoat TM 2200 e from Michelman Inc.
- the Applicant has therefore selected the 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.
- A30 ML160PFHS.E by Michelman Inc. (Carnauba Wax Emulsion)
- A31 ML723HSA-E from Michelman Inc. (Paraffin emulsion).
- a drying device comprising:
- a vertical drying column forming a cylindrical tube (920), adapted to be supplied with air (hot or cold) at its lower part, and comprising:
- a perforated lower grid (924) forming a support for the batch of plugs to be dried
- a turbine (922) for propelling air into a lower lateral duct
- an air heating means such as electric heating resistors (923).
- B5- Centralized control means of these equipments, with recording of the parameters. These means have not been shown in FIG. B6 - A plug retention net capable of holding 100 caps per test. All equipment has been supplied commercially, with the exception of the B4 drying device which has been designed and constructed in the context of the invention. Tests have also been carried out with a single-vessel device, as shown in FIGS. 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 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 into 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).
- a drying cycle comprises the following steps A to F:
- a second cycle comprising an elevation of the heating temperature, with an air temperature of 80 ° C. ⁇ 10 ° C. (In some embodiments, this temperature can range up to 90 ° C. ⁇ 10 ° C. - Expulsion of corks and packaging
- 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-i comprising 80% by weight of A21 and 20% of a barrier inorganic filler, and a second with a liquid composition CP 2 comprising 80% by weight. by weight of A21 and 20% of A3.
- plugs with two impregnations were produced, a first one with a liquid composition CP 2 comprising 80% by weight of A 21 and 20% of a mineral barrier 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.
- FIGS. 2a to 2d the sections of these plugs, as illustrated in FIGS. 2a to 2d, have shown, by using a colored contrast agent, on the one hand, an excellent penetration of the film-forming liquid composition into the crevices of the cork. and, on the other hand, the formation of a "L + P" composite skin on the surface of the cork plug suberous tissue, as shown in Figures 1b and 1c.
- 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. After storage for 26 days at 15 ° C, 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 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.
- 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.
- a corked bottle is supplied with a natural cork stopper and the bottle body is cut so as to remove its lower part.
- the cut should be as clean and as flat as possible so that the top of the bottle (601) with its stopper (600) can be placed on a flat plate (611), typically made of stainless steel, in an area where it is perforated for pass two ducts (613) and (614).
- the connection between the bottom end of the bottle and the stainless steel plate (601) is made perfectly tight by depositing a bead (612) thick (typically 20 to 30 mm) of epoxy resin.
- a purity controlled gas typically pure argon or pure nitrogen.
- This gas is evacuated via the conduit (614) which is connected to a means making it possible to measure the quantity of foreign atoms (for example oxygen atoms) which have been introduced inside the bottle (Oxtran type machines ).
- the assembly is placed under a chamber (610), and the latter is filled with oxygen. To properly assess the tightness of the closure, it is necessary to wait several tens of days, before starting to measure the amount of oxygen that has infiltrated the inside of 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).
- the analyzes were made with a dry gas (argon) and at room temperature.
- Test E0 cork lot cork natural commercial: 0.00030 to 0.1277 cm 3 / 24H / Bottle.
- Test E1 to E7 cork lot natural cork treated according to the invention: 0.00005 to 0.0050 cm 3 / 24H / Bottle.
- control plugs have a very large dispersion of the results (from 3.10 -4 to 0.12 cm 3 2 / day, which is considerable compared with the range 5.10 -5 ⁇ 5.10 -3 cm 3 0 2 / day, for plugs according to the invention, which corresponds to a relatively low dispersion of values. - and secondly that the values of permeability have dropped sharply and that they have been divided by at least 10.
- haloanisole contents released in the hydroalcoholic solution were determined by SPME (Solid Phase Micro Extraction) and SBSE (Stir Bar Sorptive Extraction):
- the Applicant has also carried out tests of sensory and taste analysis of water, in which plugs had been immersed beforehand for at least 24 hours, each in a glass of water deemed organoleptically neutral. It appeared that after a significant number of tests representative: - at least 80% of commercial natural cork stoppers (test E0), have produced odors and tastes of corks making water hard to drink.
- test E1 to E7 did not induce any detectable organoleptic deviation olfactory or tasting water.
- 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 Ti0 2 , Si0 2 , SiOx, talc, clays, kaolin, barium sulfate.
- additives such as Ti0 2 , Si0 2 , SiOx, talc, clays, kaolin, barium sulfate.
- Natural cork stoppers 900a Natural cork stoppers 900a
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Forests & Forestry (AREA)
- Closures For Containers (AREA)
- Chemical And Physical Treatments For Wood And The Like (AREA)
- Medicines Containing Plant Substances (AREA)
Abstract
Description
Claims
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)
Publication Number | Publication Date |
---|---|
EP2533957A2 true EP2533957A2 (fr) | 2012-12-19 |
EP2533957B1 EP2533957B1 (fr) | 2013-05-01 |
Family
ID=42790567
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP11708530.8A Not-in-force EP2533957B1 (fr) | 2010-02-08 | 2011-02-07 | Traitement de bouchons en liege naturel et bouchons obtenus par ledit traitement |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP2533957B1 (fr) |
ES (1) | ES2421614T3 (fr) |
FR (1) | FR2956058B1 (fr) |
PT (1) | PT2533957E (fr) |
WO (1) | WO2011095713A2 (fr) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2017021866A1 (fr) | 2015-08-04 | 2017-02-09 | Reliable Cork Solutions, Unip. Lda | Dispositif de colmatage de bouchons en liège |
Family Cites Families (14)
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 (fr) * | 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 |
EP0773090B1 (fr) * | 1995-11-07 | 2003-09-03 | Portocork Internacional, S.A. | Méthode pour la fabrication de bouchons en liège pour bouteilles |
AU1595497A (en) | 1996-02-19 | 1997-09-02 | 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 |
-
2010
- 2010-02-08 FR FR1000497A patent/FR2956058B1/fr not_active Expired - Fee Related
-
2011
- 2011-02-07 EP EP11708530.8A patent/EP2533957B1/fr not_active Not-in-force
- 2011-02-07 PT PT11708530T patent/PT2533957E/pt unknown
- 2011-02-07 ES ES11708530T patent/ES2421614T3/es active Active
- 2011-02-07 WO PCT/FR2011/000073 patent/WO2011095713A2/fr active Application Filing
Non-Patent Citations (1)
Title |
---|
See references of WO2011095713A2 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2017021866A1 (fr) | 2015-08-04 | 2017-02-09 | Reliable Cork Solutions, Unip. Lda | Dispositif de colmatage de bouchons en liège |
Also Published As
Publication number | Publication date |
---|---|
PT2533957E (pt) | 2013-08-02 |
WO2011095713A3 (fr) | 2011-09-29 |
ES2421614T3 (es) | 2013-09-04 |
WO2011095713A2 (fr) | 2011-08-11 |
FR2956058A1 (fr) | 2011-08-12 |
FR2956058B1 (fr) | 2012-02-03 |
EP2533957B1 (fr) | 2013-05-01 |
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