Closure

FIELD OF THE INVENTION
This invention relates to closures for containers, particularly wine bottles, and to methods for making same.
BACKGROUND OF THE INVENTION
Wine bottle closures made from natural cork can be a source of chemicals which may produce mouldy taints in the contents of the bottle. These chemicals (such as trichloroanisoles) may originate from the bleaching process used for cork which involves treatment with chlorine or other chloro compounds. Wine which has been exposed to such chemicals is described as being "corked", and it has been estimated that the wine in up to 10% of all bottles of wine sold worldwide may be corked in this manner. Further, cork is becoming an increasingly scarce commodity and is now so expensive that some winemakers have resorted to the use of corks made from agglomerated particles of recycled cork. These so-called "agglo" corks have also been shown to taint wine, probably, in part, as a result of the adhesive used.
Consequently, there is a great need for inexpensive alternatives to cork bottle closures. Two such alternatives are plastic "champagne-style" corks and metal screw-cap "Stelvin" closures. Whilst these types of closures produce an excellent seal, their use has been limited to low grade wines due to their poor aesthetic qualities.
It is now proposed that closures comprising synthetic and/or natural fibres, particularly wool, would be an excellent alternative to cork.
SUMMARY OF THE INVENTION
Accordingly, the present invention provides a closure for a container having an opening, said closure comprising at least one resilient mass of fibres selected from synthetic fibres, natural fibres and mixtures thereof, said at least one resilient mass of fibres having a density in the range of 0.15 to 2.00 g/cm.sup.3 and having one of an interlocked structure, an associated structure and a combination thereof, and wherein the closure is sized and has a density to enable the closure to be sealingly inserted into the opening of said container.
DETAILED DESCRIPTION OF THE INVENTION
The present invention provides a container closure comprising at least one resilient mass of fibres selected from synthetic fibres, natural fibres and mixtures thereof. The at least one resilient mass of fibres has a density in the range of 0.15 to 2.00 g/cm.sup.3 and has one of an interlocked structure, an associated structure or a combination thereof.
By the term "fibres" we refer to materials that may be formed into a yarn, textile, carpet or the like.
Interlocking of fibres may be achieved by, for example, "felting" processes, needle-punching, weaving and/or knitting.
By the use of the term "associated structure" we refer to other structures providing a resilient mass of fibres. Such structures may be prepared by, for example, bonding the fibres, or a portion of the fibres, with an adhesive or polymer(s) having adhesive-like qualities. One particular method envisaged involves melting a polymer(s) present in a fibre-polymer(s) mix such that the polymer(s) bonds to the fibres (i.e. upon cooling). In this way, a network of fibres can be produced with a level of resilience suitable for closures that are intended to be inserted and extracted from an opening in a container. Preferred meltable polymers for use in producing a resilient mass of fibres having an associated structure include polyesters, particularly low melting point polyesters. The meltable polymer may comprise 5.95% by weight, preferably 20-40% by weight, of the resilient mass of fibres. Varying the ratio of the amount of meltable polymer to fibres enables the production of resilient masses of bonded fibres to be produced with a range of densities. A method for bonding wool fibre in this manner is described in Australian patent specification No. 15912/88, the disclosure of which is incorporated herein in its entirety by reference.
The fibres, or a portion of the fibres, may also be present in the form of bonded "felted yarns" or "felted slivers".
Preferred natural fibers include vegetable fibres such as cotton, flax, sisal, linen, cellulose and jute, and animal-derived fibres such as angora, wool, alpaca and mixtures thereof.
Preferred synthetic fibres include cellulose acetate, cellulose triacetate, acrylics, aramids (i.e. aromatic polyamides), rayons, polyolefins (e.g. polypropylene), nylons, polyesters, polyurethanes, terylenes, teflon and mixtures thereof.
Mixtures of the abovementioned synthetic and/or natural fibres may also be suitable. Most preferably, the fibres are sheep wool or fibre mixtures including sheep wool fibres.
Preferably, the resilient mass of fibres has a density in the range of 0.18 to 0.95 g/cm.sup.3, more preferably, in the range of 0.35 to 0.45 g/cm.sup.3.
Closures according to the invention may further comprise one or more coating and/or impregnating additives which may be added, for example, to vary the resilience or density of the fibre mass; to vary the sealing properties of the closure; and/or assist insertion or extraction of the closure. The coating and/or impregnating additives may also be added in order to isolate the fibre mass from the contents of the container.
Accordingly, the fibres comprising the resilient mass and/or the outside of the closure may be coated, wholly or partially (e.g. the ends of the closure only), with a coating material such that the contents of the container do not directly contact fibres. Alternatively, the coating materials could be used to fill part or all of the interfibre spaces (i.e. impregnants) in the closure. Where the contents of the container is a food or beverage, the coating and/or impregnant material would preferably be selected from those which are "food-contact approved". As a further safety measure in food and beverage applications, the mass of fibres would also, preferably, be sterilised.
Suitable coatings include those typically used in packaging materials such as polyethylene dispersions, modified polyethylene dispersions and gels of polymers such as ethylene vinyl copolymer (EVA), solutions and dispersions of poly(vinylidene chloride) and its copolymers (e.g. foamed and non-foam PVC), polyurethanes, natural synthetic rubbers such as ethyl propylene diene rubber (EPDM), acrylic latexes, lacquers and dispersions and various thermoformed films. Paraffins, waxes and silicones may also be suitable coating additives.
The closures may also have more than one coating, each coating being the same or different in composition. It is also to be understood that an impregnant may be used in conjunction with one or more coatings. Including multiple coatings (particularly of wax), may assist in the production of closures having a more uniformly smooth surface (which may enhance the sealing qualities of the closure). Harder coatings such as some PVDC's and hard acrylics may also be machined using a polishing brush or the like to provide a smooth surface. Alternatively, a smooth finish may be achieved by placing the freshly coated fibre mass into a mould and curing the coating additive(s) within the mould.
The coating and/or impregnating additive(s) may comprise 0.01-70% (by weight) of the closure, more preferably 0.1-30% (by weight). Where the additive(s) impregnate the fibres of the fibre mass, it is preferred that they comprise 1-30% (by weight) of the fibre mass.
To incorporate or apply coating and/or impregnating additive(s) to the fibre mass, it may be necessary to dry (e.g. by microwave or hot air tumbling) or pre-treat the fibre mass to improve adhesion or incorporation. Where the fibre mass is a wool fibre mass, the pre-treatment(s) may be selected from chlorine treatment, UV treatment and other oxidising treatments such as treatment with sulphuric acid, zinc acetate and hydrogen peroxide.
The coating and/or impregnating additives may be applied or incorporated into the fibre mass by dipping, spraying and/or injecting. Alternatively, individual fibres or bundles of fibres may be coated and then formed into a resilient mass of interlocked and/or otherwise associated fibres.
Preferably, any coating and/or impregnating additives should not greatly affect the resilience of the fibre mass. Thus, the preferred coating and/or impregnating additives are PVC's and polyurethanes, particularly when applied as coatings to the outside of the fibre mass, as these additives are particularly good at preserving the resilience of the fibres in the fiber mass. The PVC's also show low friction qualities which can assist in the insertion and extract on the closure from the opening of a container. These low friction qualities may also be varied by adjusting the amount and/or kind or plasticisers used or extenders (in the case of polyurethane).
Closures according to the invention may also be provided with end caps of coating additive(s), that is caps of about 0.5 to 5.00 mm thick on one or both ends of the closure. Alternatively, and more preferably, closures according to the invention may be provided with end caps composed of an end portion of the fibre mass(es) impregnated with an impregnating additive(s). The impregnated end portion of the fibre mass(es) may be 0.1 to 5.0 mm thick. These caps of coating and impregnating additive(s) may provide structural integrity and avoid any distortion of the closure upon insertion into an opening.
The closures according to the invention may also include more than one mass of fibres. In such embodiments the fibre masses may be bonded together with an adhesive and may have the same or different characteristics. That is, they may, for example, have different densities, different coating and/or impregnating additives to be produced in different manners. One fibre mass may be impermeable to liquids, whilst another may be impermeable to gaseous molecules. Fibre masses may also be bonded to and separated from each other by one or more liquid and/or gas-impermeable membranes. The membranes may also extend to a slightly larger diameter than the fibre mass in order to assist in forming (or entirely form) the seal between the closure and the surface of the container's opening, with the fibre mass providing the necessary compression force.
In addition, due to the resilience of the fibre mass(es), the closures according to the invention may not necessarily resemble a shape which mirrors the opening to be sealed. For instance, a closure for a wine bottle may, preferably, have the shape and dimensions similar to standard cork closures with or without curved ends (concave or convex) but may also be spheroid or ovoid. The closure may also comprise a fibre mass having the standard shape of a cork closure but provided with O-rings formed of rubber or other resilient polymer. The O-rings would thus assist in forming (or entirely form) the seal between the closure and the bottle neck, with the fibre mass providing the necessary compression force. Some of the envisaged shapes and constructions of closures for wine bottles are depicted at FIG. 1.
In order to meet the sealing requirements for the broadest range of containers/contents, and particularly for application in the wine and spirit industry, it is preferred that the closure is substantially impermeable to liquids and gases.
Closures according to the invention may be formed in several manners. One method is by conventional felting of the fibres in sheet form, followed by "punching-out" or cutting out (e.g. using a rotating cutting instrument) of wads of fibres for use as, or in, closures.
Conventional felting and various treatments and pre-treatments for felt are reviewed in Wool Science Review 81 (International Wool Secretariat Development Centre, Valley Drive, Ilkley, Yorks), the disclosure of which is incorporated herein by reference.
Thus, in a further aspect, the invention provides a method for producing a closure of a size and density to enable the closure to be sealingly inserted into an opening of a container, comprising punching-out or cutting out a form from a resilient sheet of synthetic fibres, natural fibres and mixtures thereof having a density in the range of 0.15 to 2.00 g/cm.sup.3 and having one of an interlocked structure, an associated structure and a combination thereof.
The "form" may be suitable for use as a closure, or coating and/or impregnating additives may be added to the form to produce a closure.
Preferably, the resilient sheet of fibres is a sheet of felted fibres, particularly felted wool fibres. The "forms" may be punched out or cut out of sheets of wool felt either through the top or bottom of the sheet or through the ends or sides of the sheet. Punching or cutting the forms from the ends of the sheet should provide forms wherein the fibres predominantly lie in a direction substantially parallel to the longitudinal direction of the form. This orientation of most of the fibres may positively affect the resilient qualities of the form.
Coating and/or impregnating additives as described above, may be added during the production of the felt sheet or following the punching-out or cutting out of the form.
Alternatively, closures according to the invention or suitable forms of a resilient mass of synthetic and/or natural fibres, may be produced by extrusion, for example through a die by means of a single-screw or twin-screw extruder.
Thus, in a yet further aspect, the invention provides a method for producing a closure of a size and density to enable the closure to be sealingly inserted into an opening of a container, comprising extruding through a die a resilient mass of synthetic fibres, natural fibres and mixtures thereof having a density in the range of 0.15 to 2.00 g/cm.sup.3 and having one of an interlocked structure, an associated structure and a combination thereof, and which resilient mass may be subsequently cut into a form.
Again, the "form" may be suitable for use as a closure, or coating and/or impregnating additives may be added to the form to produce a closure.
In such a method, coating and/or impregnating additives may be added during the production of the resilient mass of fibres or following cutting of the resilient mass of fibres. It is also envisaged that the mass of fibres may be extruded into a length having a "daisy flower" or "honeycomb" cross-section which may subsequently be extruded in the presence of impregnating additives (which may be presented in the form of a gas or solution) through a second circular die of smaller cross-section. In this manner, impregnating additives will be incorporated into the mass at the spaces between the fibres.
Closures according to the invention may also be formed by bonding particulate felt sheet in a suitably shaped mould.
Further, as mentioned above, closures according to the invention may comprise at least one resilient mass of fibres having an associated structure produced by melting polymer(s) in a fibre-polymer(s) mix. Meltable fibre-polymer(s) mixtures may be formed, for example, by extrusion into a cylindrical shape prior to heating. During or following heating, the cylindrical form may be compressed, if desired, to a suitable density. The cooled cylindrical form may then be cut into suitable closure shapes.
Thus, in a still further aspect, the present invention provides a method for producing a closure of a size and density to enable the closure to be sealingly inserted into an opening of a container, the method comprising preparing a mixture of meltable polymer(s) and fibres selected from synthetic fibres, natural fibres and mixtures thereof, forming the mixture into a substantially cylindrical form, heating said substantially cylindrical form so as to melt the meltable polymer(s), and allowing said substantially cylindrical form to cool.
Closures according to the invention may be readily adapted to be suitable for sealing openings in many different kinds of container. However, the closures are primarily intended for use in the wine and spirit industry, and particularly for sealing wine barrels and wine bottles. The closures are hereinafter described in respect to their use in sealing wine bottles.
It is believed that wool closures would have considerable appeal to winemakers and drinkers alike for several reasons. That is:
Wool is relatively inexpensive and widely available.
Wool is a natural product with a pleasant appearance.
When interlocked (e.g. felted) or provided with an associated structure, it has been found that wool fibres within a closure retain sufficient resilience to prevent compression set of the closure upon insertion into the neck of a bottle. This enables wool closure to provide a satisfactory seal.
Wood closures according to the invention may be inserted into the neck of a bottle using standard corking machines. They may also be extracted using an ordinary cork screw.
When wool fibres are used, it is preferable that they are from scoured, unspun wool. Wool fibres that have been subjected to further cleaning processes (e.g., carding and combing) are likely to require lesser volumes of any desired additives, however the use of such fibres may result in the loss of some of the rustic appeal of the closure. Alternatively, clean vegetable matter such as wood chips and/or splinters (especially oak chips and/or splinters of 0.5 to 4 mm in length) may be added to clean wool to provide a rustic "freckled" appearance. Further, clean wool may be readily dyed with food-approved colourants to restore a rustic appearance to the closure. Food-approved colourants may also be used to give the closures a colour resembling that of cork closures.
In preliminary taint testing trails of felted wool, using neutral dry white wine, olfactory taints caused by the wool were sometimes detected. This tainting can be avoided by isolating the wool fibres through the use of a coating and/or impregnating additive(s) as described above. However, as a further precaution, it is preferred that the wool fibres be subjected (either before, during or after formation into a resilient mass) to a taint removing or altering process. Such processes include treatments such as those described above for improving adhesion or incorporation of coating and/or impregnating additives; particularly, treatment with sulphuric acid (up to 10 wt %), zinc acetate (11.5 wt %) and hydrogen peroxide. Other suitable processes for taint removal or alteration may include treatment with acetic acid (10 wt %), ammonia solutions (2.5 wt %), sodium bicarbonate (25 wt %), ammonium persulphate, persulfuric acid, and processes involving evacuation and steam.
It has been found that in order to achieve good sealing qualities, wool closures for use with wine bottles should preferably comprise at least one resilient mass of felted wool coated with one or more relatively soft coating additives. Coatings of a soft polyurethane such as the food-contact approved polyurethane 6012A (UniRoyal Chemical Co.) are particularly suitable, especially when used with an undercoat of ethylene vinyl acetate (EVA) copolymer. Soft locating materials do, however, tend to increase the insertion and extraction forces required and, thus, use of an outer coating of a lubricant material such as a paraffin, wax or silicone is preferred. One particularly suitable lubricant coating additive is the silicone product Gensil (Rhone-Poulenc).
Accordingly, wool closures for use with wine bottles preferably comprise at least one resilient mass of felted wool fibres, said mass coated in;
a first, inner, layer of a coating additive selected from ethylene vinyl acetate copolymer natural latex, poly vinyl alcohol (PVA), poly vinyl hydroxyl (PVOH), styrene-butadiene and acrylics.
a second, intermediate, layer of an impregnating agent selected from polyurethane natural latex and silicones, and
a third, outer, layer of a lubricant material.
Optionally, the wool closure may include a cap on the end of the closure that is intended to face the wine, composed of an end portion of the fibre mass(es) impregnated with an impregnating additive(s). Preferably, the impregnating additive(s) is the same impregnating additive(s) as that used in the said intermediate layer.
Such end caps may be prepared by placing the wool fibre mass to be capped into an evacuation mould (either before or after coating by, for example, brushing or dipping), immersing the mould holding the wool fibre mass into a reservoir of a suitable impregnating additive(s) and drawing the additive(s) into the end portion(s) of the wool fibre mass by application of a vacuum. Subsequently, the mould holding the wool fibre mass is removed from the reservoir and vacuum line, and the impregnating additive(s) allowed to cure (e.g. by heating in an oven) before the capped fibre mass is removed from the mould. The process (for producing caps at both ends of a substantially cylindrical fibre mass) is shown schematically at FIG. 3. The process effectively produces a cap(s) of a fibre-impregnating additive(s) composite. Formation of the composite cap(s) can be controlled by mould design, evacuation conditions, temperature and viscosity of the polymer in the reservoir. The evacuation mould may also be adapted to form composite edges on all faces of the wool fibre mass.
Wool closures for use with wine bottles also preferably comprise a single resilient mass of wool fibres included, preferably having a shape and dimension similar to a standard cork closure, that is, of substantially cylindrical shape of 24 to 55 m length and 17 to 28 mm (more preferably, 21 to 23 mm) diameter. The use of a single substantially cylindrical mass with a diameter of 21 to 23 mm requires only very thin coats of additives to be applied (e.g. 0.05 to 1.00 mm), otherwise the insertion and extraction forces shall be unacceptable.
The invention shall now be further described with reference to the following non-limiting examples and accompanying drawings.

BRIEF DESCRIPTION OF THE FIGURES
FIG. 1 diagrammatically shows the longitudinal cross-sectional shape and construction of closures according to the invention intended for sealing wine bottles: (A) square, (B) rectangular, (C) rectangular with concave ends, (D) square with concave ends, (E) rectangular with convex ends, (F) two square fibre mass construction including a liquid and gas-impermeable membrane, (G) rectangular with O-ring, (H) three fibre mass construction with thermoformed skin, (I) "barrel", (J) rectangular with "arrow head" flange, (K) rectangular with flaps, (L) rectangular with peripheral O-rings, and (M) rectangular with bevel and (N) rectangular with composite end cap of and end portion of fibres impregnated with an impregnating additive.
FIG. 2A provides a diagrammatic elevation representation of the test cells used for testing oxygen permeability. The test cell was made from brass, the various ports being 1/8" Swagelock fittings. (1) and (2) are gas flushing ports, (3) is the sampling port, (5) is a tube into which a sample closure (4) is placed, and (6) is a perforated support tube.
FIG. 2B provides a diagrammatic plan view of the test cells for testing oxygen permeability.
FIG. 3 provides a schematic plan of a process for forming composite end caps on substantially cylindrical masses of fibres. An evacuation mould (1) holding a fibre mass (12) in a manner such that the end portions of the fibre mass are exposed (L.sub.1 is typically 1-4 mm) is placed in a reservoir (14) of a suitable impregnating additive(s) and a vacuum briefly applied through vacuum line (13). The mould holding the impregnated fibre mass is subsequently removed from the reservoir. The impregnating additive(s) is/are cured in an oven (15) before removing the capped fibre mass from the mould.

EXAMPLE 1
Preparation of Closures
MATERIALS AND METHODS
Preparation of Wads (fibre masses)
Cylindrical wad forms were cut from wool felt sheet of density 0.35 g/cm.sup.3 (manufactured by P&F Filtration Ltd, Australia), 0.40 g/cm.sup.3 and 0.45 g/cm.sup.3 (manufactured by Bury Cooper and Whitehead Ltd, U.K.). Cutting was performed by rotating cutting instrument or by forcing a steel punch of chosen internal diameter in a mechanical press through the felt. The speed of cutting was slow enough to allow the wad to remain uncompressed. Excessive speed cutting speed tended to cause concave sides on the wad. The wads had diameters of 17 mm, 18 mm, 21.5 mm, 22 mm, 22.5 mm, 25 mm or 28 mm and were 27 mm, 28 mm, 38 mm or 43 mm in length when cut out of the felt. When creasing of certain coated wads of 28 mm diameter was observed to prevent an adequate seal to the bottle neck; the wads of smaller diameter were used.
Impregnation of Wads (1)
The wads were weighed and placed in the appropriate impregnating liquid either in a beaker held in a desiccator, or in a Quickfit standard taper (Female, B24) ground glass fitting. The wad in the beaker was impregnated by exhaustion of air from the desiccator using the vacuum generating by a water tap aspirator. The wad sank into the impregnating medium when the air was removed. The desiccator was removed from the vacuum source, opened and the wad removed and weighed before drying. When the impregnating liquid was sucked through the wad the vacuum source was removed and the wad was weighed before and after drying. In some cases, the wad was inverted and the impregnating liquid passed through again. Wads from both treatments were typically dried in a microwave oven at 202 watts for 4 minutes.
Impregnation of Wads (2)
The closures of examples 51-57 were provided with composite end caps of fibres and impregnating polyurethane 6012A. Such end caps were produced according to the process depicted in FIG. 3. In particular, wads of 21.5 mm and 22.0 mm diameter and thickness (length) of 38 mm and 43 mm were placed in a mould (11) with a horizontal bore of internal diameter of 21.0 mm, 21.5 mm or 22.0 mm. The wads when placed in the mould have exposed overhang end portions of L.sub.1 of about 1-4 mm. The mould holding the wad was placed in a reservoir of polyurethane 6012A at >50.degree. C. (preferably, 80-100.degree. C.) and a vacuum applied for about 1-4 seconds through vacuum lines (13). Curing was subsequently achieved in an oven before removing the capped wad from the mould.
Coatings
(1) Wax and silicone coatings.
Wax or silicone coatings were applied by dipping the wads into the coating agent with the aid of tweezers. Wax coating weights were controlled by control of the temperature of the wax with lower coating weights being obtained at higher temperatures.
(2) PVC Plastisol Coatings.
Two PVC plastisols were used initially. The first, W.R. Grace AD07-2126.3 does not foam when heated to 180.degree. C. for 5 minutes. The second, Daraseal 700 (Sicpa), foams under these conditions. The coating was achieved by first pouring plastisol, (5 g for 28 mm was length, 7 g for 48 mm wad length) into a cylindrical aluminium mould, 48 mm deep with an internal diameter of 20 mm. A wad of 18 mm (non-foaming plastisol) or 17 mm (foaming plastisol) diameter was then lowered carefully into the mould to within 4 mm of the bottom. The wad was held by means of a screw hook inserted into the top of the wad and the wad was slowly turned to assist in the distribution of the plastisol. The mould and its contents was then heated in a fast-recovery oven at (180.degree. C. for non-foaming and 200.degree. C. for foaming) for 5 minutes, followed by cooling before removal of the coated wad. The base of the mould was unscrewed and the wad removed. When the non-foaming PVC was used the coated wad had a PVC layer approximately 1 mm thick around the diameter and 2 mm thick at the bottom. When the foamable plastisol was used the foam layer was approximately 1.5 mm thick at the sides and 3-4 mm thick at the bottom.
The non-foaming plastisol is essentially transparent and light pink in colour so that the felt can be seen inside the coating. The foam layer is white and opaque.
(3) Latex Coatings.
A curtain rod hook was inserted into the end of the wad, which was then dipped into latex (from various suppliers: Morton, Michelman, B.A.S.F., Dragon Chemicals and Dussek Campbell) leaving the top uncoated. The wad was removed and placed immediately into a fast recovery oven at 105.degree. C. for five minutes, then re-immersed in the latex and placed in a fast recovery oven at 95.degree. C. for five minutes.
(4) Thermoformed Skin Coatings.
Wads of 22 mm diameter and thickness of 28 mm were covered with a commercial laminating adhesive (Lamal, Coates Bros, Sydney) and tightly packed to approximately half their thickness by thermoforming a skin of Surlyn (Du Pont plastics) ionomer film around them on a commercial blister packing machine. The film did not form a crease-free skin beyond half the thickness of the film. A wad was tested for its effectiveness in preventing liquid loss from a bottle of wine simulant after insertion into the bottle with the skin-covered end towards the wine simulant. The use of tubular forms of thermoformed skin should avoid creasing problems. The ends of a closure enclosed in a tubular thermoformed skin may be dipped in sealing plastic.
(5) Polyurethane Coatings.
Wads of 21.5 mm and 22.5 mm diameter and thickness (length) of 38 mm and 43 mm were dried in an evacuation oven at about 110.degree. C. (-1 atm) for 1 hour then coated by dipping or brushing with polyurethane 6012A (UniRoyal Chemical Co.). The freshly coated wads were then placed in a mould having an internal bore diameter of 21.0 or 21.5 mm and then the polyurethane was cured. In some cases, an EVA undercoat was first applied before coating with polyurethane.
Two-part closures with a membrane in between
Wads were cut in halves to give two wads of thickness approximately 14 mm each. These were combined to give a single wad by means of a circular piece of double-sided adhesive tape based on a film of polypropylene. This type of wad was found to break easily due to inadequate cohesion. Wads impregnated with an acrylic emulsion were used and found to have adequate cohesion to allow insertion into the bottles but the seal against the glass at the top joint was not found to be satisfactory for wine applications.
Three-part closures
Three wads of 22 mm diameter were taken and two were skin packed with Surlyn in one case and Primacor (ethylene acrylic acid copolymer) in the other. These two wads were then cut in halves by means of a Stanley Knife and the unsealed end was discarded in each case. Half of the third wad was impregnated with Michelman Prime 4990R emulsion of ethylene acrylic acid copolymer to give some additional adhesion to the bottle neck. The latter half-wad was placed between the other two wads with the double-sided tape as adhesive. The wad inserted into the wine simulant using a hand corking machine and the Surlyn-skinned end wad towards the outside of the bottle.
EXAMPLE 2-36
Wool Felt-Latex Closures
All closure examples 1-35 were made using wads of 0.35 g/cm.sup.3 woo felt. The felt wads used in the closures of Examples 2-22 were 28 mm in diameter, and 27 mm in length. The felt wads used in the closures of Examples 23-28 were also 27 mm in length but varied in diameter as indicated in Table 1.
TABLE 1__________________________________________________________________________Ex- Dry Closuream- Flet Pull Out Forceple FDA diameter Solution % (kg)No Latex Name Type Compliance (mm) Solid % Coating 1 day 2 days Film__________________________________________________________________________ Properties2 Glascol C36 acrylic unconfirmed 28 2.5 11 59 32 hard, brittle3 Glascol C36 acrylic unconfirmed 28 5 15 40 others 43 hard, brittle push through 384 Glascol C36 acrylic unconfirmed 28 10 29 55 61 hard, brittle 35 865 Q-thane urethane unconfirmed 28 2.5 15 26 36 hard, flexible, 25 32 after 4 days 23 water immersion at room temperature softening and heavy whitening observed6 Michhelman X300 acrylic 176,170 26 2.5 13 21 29 soft, waxy 176,180 17 207 Michelman X300 acrylic 176,170 28 5 14 23 31 soft, waxy 176,180 38 328 Michelman X300 acrylic 176,176 28 10 31 33 26 soft, waxy 176,180 29 38 30 369 Michelman X300 acrylic 176,170 28 15 32 30 -- soft, waxy 176,180 37 2910 Michelman 50A acrylic 176,176 25 2.5 16 37 27 Medium hard- 37 33 ness, ductile 41 31 cohesion. After 4 days water immersion at room temperature slight softening and heavy whitening observed11 Michelman 66725 Polyethylene not approved 28 5 17 16 15 soft, waxy 15 22 15 2012 Michelman 48040 microwax not approved 28 5 15 13 14 medium hard- 13 17 ness, waxy 1413 BASF 193D polyvinylidene unconfirmed 28 5 18 28 32 hard, brittle 30 23 23 2214 Michelman 01546 microwax unconfirmed 28 5 11 10 14 very soft, waxy 18 13 1015 Michelman 763 acrylic 176,180 28 5 14 34 33 Medium hard- 175,350 35 37 ness, firm 175,3207 30 45 cohesion. After 4 days water immersion at room tem- perature slight soften- ing and whitening observed16 BASF 360D acrylic unconfirmed 28 5 14 40 46 Soft and 57 41 ductile. After 58 56 4 days water 55 immersion at room temperature softening and whitening observed17 Michelman 240 polymeric unconfirmed 28 5 14 13 15 Medium hard- acrylic 15 ness, waxy 1218 Michelman 124 microwax unconfirmed 28 5 15 10 14 soft, waxy19 Michelman 93135 high not approved 28 5 15 19 21 medium hard- density 17 22 ness, flaky polyethylene20 Michelman 40-H H.S. polymeric 176,170 28 2.5 11 17 soft, low film acid 176,180 17 strength 14 After 4 days water immer- sion at room temperature slight softening and heavy whitening observed21 Michelman P20 precoat 20 unconfirmed 26 2.5 9 18 19 Soft medium 26 16 coherence. After 4 days water immersion at room tem- perature softening and heavy whitening observed22 Michelman 103D1 polyethylene 176,170 28 5 14 14 -- soft, waxy (anionic emulsifier)23 Michelman 103D1 polyethylene 176,170 25.4 5 14 8 -- soft, waxy (anionic 6 emulsifier)24 Michelman 103D1 polyethylene 176,170 22.2 5 14 pushed in soft, waxy (anionic emulsifier)25 Michelman 42745 wax 175,105 26 5 11 16 -- firm, waxy (nonionic 175,300 21 emulsifier) 175,320 20 176,170 176,18026 Michelman 42745 wax 175,105 25.4 5 11 11 -- firm, waxy (nonionic 175,300 9 emulsifier) 175,320 6 176,170 176,18027 Michelman 42745 wax 175,105 22.2 5 11 pushed in firm, waxy nonionic 175,300 emulsifier) 175,320 176,170 176,18028 Michelman Prime ethylene 177,3100c 22.2 5 18 7 -- hard, strong 4990R acrylic 176,170b 10 acid 176,180 10 175,105 175,300b 175,320b29 Michelman Prime ethylene 177,3100c 25.4 5 16 35 -- Hard, firm. 4990R acrylic 176,170b 33 After 4 days acid 176,180 25 water immer- 175,105 24 sion at room 175,300b 16 temperature 175,320b 25 slight softening observed30 Serfene 121 polyvinylidene unconfirmed Hard, brittle. chloride After 4 days water immer- sion at room temperature slight whitening observed31 Michelman 368 wax unconfirmed medium hard- ness, waxy32 Michelman 160 carnuaba approved medium hard- wax ness, waxy33 Michelman 162 carnuaba approved medium hard- wax ness, waxy34 BASF S504 acrylic unconfirmed medium-soft, ductile cohesion. After 4 days water immer- sion at room temperature softening and whitening observed35 Michelman 40A acrylic unconfirmed medium hardness, ductile cohesion36 BASF BASOPLAST acrylic unconfirmed hard, brittle 400DS (low wetout)__________________________________________________________________________ *average value based on weight changes and accounting for 10% moisture loss on drying
Table 1 provides the characteristics for closure Examples 2-36 and results for extraction tests on these examples. Data from duplicate examples are provided in some instances. By way of comparison, standard cork closures typically required an extraction force of 35-40 kg.
The extraction results where the bottle was not filled with liquid provides an indication of the compression forces with time and the interaction of the closure with glass.
The film properties were determined by drying the latex on a petri dish and evaluating dried film by a simple finger nail scratch test.
EXAMPLE 37-44
Effect of Closure Diameter (uncompressed) on Closure Length in Bottle
The effects of varying the diameter of the closure on the length of the closure when inserted into the neck of the bottle was investigated.
Table 2 provides the results for wool felt-based closures under compression in the bottle neck. All wads used in the closure had an initial fibre density of 0.35 g/cm.sup.3 and a length of 28 mm.
TABLE 2______________________________________ Pre- Post- Original Compression Compression diam. Length LengthExample (mm) (mm) (mm)______________________________________37 Untreated wad 28 28-29 3438 Untreated wad 25.4 27-28 3039 Untreated wad 22 27 3040 Untreated wad 21 31 0.45 nominal density 30 mm original length41 Impregnated with 22 29-30 30 5% Micryl 76342 Impregnated with 25.4 29-30 34 5% Micryl 76343 Impregnated with 28 Too hard to 5% Micryl 763 insert into bottle44 Impregnated with 25.4 30 31 5% Michelman 4990R______________________________________
EXAMPLE 45
Oxygen Permeability Tests performed on various closure
Wool felt-based closures of various construction were tested for oxygen permeability as follows:
Six test cells were constructed from brass as shown in FIG. 2. The top, bottom and cork tube were soldered together, and the joins sealed using Loctite 290 sealant. The gas flushing ports (1) and (2) were sealed using solid 1/8" brass rod. The gas sampling port (3) was sealed using a silicone rubber septum.
The closure sample (4) was loaded into the top tube (5) using a cork inserter. Both gas flushing port caps were removed and nitrogen passed through the cell for ten minutes. During flushing the exit port (2) was blocked for short periods to allow gas build up to occur and cause turbulence within the cell. The exit port (2) was sealed first, followed by the entry port (1). The gas composition was analysed initially and at 24 hour intervals, using syringe extraction and gas chromatography. From these results the oxygen permeation was calculated.
The results of the tests are provided at Table 3.
TABLE 3__________________________________________________________________________Oxygen Ingress (ml/day)Blank cell Day 1 Day 2 Day 3 Day 6 Day 7 Day 8 Day 9__________________________________________________________________________ 0.00 0.00 0.00 0.07 0.07 0.09 0.14__________________________________________________________________________ Oxygen Ingress (ml/day)26 mm diameter wad (low Day Day Daydensity) 1 2 3 Day 6__________________________________________________________________________UntreatedSingle coated (40H @ 2.3%) 110Single coated (P20 @ 2.5% 220Single coated (x300 @ 2.5% 220Silicone coated cork 0.7 0.7 0.7 0.7Paraffin coated cork 1.1 1.1 1.1 1.1__________________________________________________________________________ Oxygen Ingress (ml/day)18 mm diameter wad Day 1 Day 2 Day 3 Day 6 Day 8 Day__________________________________________________________________________Foamed PVC composite, 0.22 0.11 0.22 0.11 0.10 0.10wax coating (particulated 3.70 4.20 5.20 3.50 3.40 3.200.35 g/cm.sup.3 wool felt)PVC plasticiser low density, 0.22 0.11 0.13 0.09 0.08 0.09wax coating 2.00 2.20 2.90 2.10 2.10 2.10Silicone coated cork 0.11 0.22 0.22 0.22 0.19 0.17Paraffin coated cork 0.00 0.11 0.11 0.06 0.07 0.07Silicone coated cork 0.7 0.7 0.7 0.7Paraffin coated cork 1.1 1.1 1.1 1.1__________________________________________________________________________ Oxygen Ingress (ml/day)18 mm diameter wad Day 1 Day 2 Day 5 Day 6 Day 7__________________________________________________________________________PVC plasticiser, low density 2.48 1.74 1.92 0.48 0.41no wax 3.30 2.39 2.42 0.36 0.03PVG foam, low density wax 0.37 0.26 0.48 0.22 0.22coating 0.22 0.06 0.02 0.03 0.06PVG plasticiser, high 0.11 0.05 0.03 0.00density wad 0.06 0.05 0.03 0.00__________________________________________________________________________ Oxygen Ingress (ml/day)18 mm diameter wad Day Day Day(0.35 g/cm.sup.3) 1 2 5 Day 6__________________________________________________________________________Double coated (360D @ 0.15 0.06 0.15 0.1550% solids) low density 2.53 2.42 4.51 0.72Thermoformed, low density 14.7 9.02 1.20 0.49 1__________________________________________________________________________ Low density = 0.35 g/cm.sup.3
EXAMPLE 46
Extraction strength tests on various closures
Tests were carried out to determine the force required to remove various closures from the bottle.
The procedure was as per ISO 9729:1991(E), with the exception that a commercially available corkscrew was used rather than machining the standard corkscrew. The storage conditions varied from one day to eight days with and without wine simulant (12% v/v ethanol in a saturated potassium bitartrate solution). The Results are shown at Tables 4 and 5.
TABLE 4__________________________________________________________________________Pull out tests (24 hours exposure to wine simulantSample Force(N) Comments__________________________________________________________________________Untreated no result Wad wet, push through no result Wad wet, push through no result Wed wet, push throughThermoformed with SURLYN 107.1 Wad was above neck of bottle 19.6 Wed turned iu bottle, thus corkscrew did not penetrate through the wed 19.8 Wad was wet, above bottle neck and tt turned in the bottle, plastic on wed tornSingle wax coated @ 110.degree. C. 39.2 Wad wet, wax splitting 9.8 Wad wet, wax splitting no result Push throughTwo piece wad no result Wad separated after being pushed through no result no resultDouble coated (350D @ 50% 245 Wad above bottle neck 380D changed to white coloursolids were in contact with alcohol 284.2 Wad above bottle neck, 360D changed to white colour were in contact with alcohol 58.8 Wad above bottle neck 350D changed to white colour were in contact wlth alcohol19 mm low density (0.35 g/cm.sup.3 nominal)PVC plasticizer in 21 mm no result Push throughcylinder no result Push through19 mm high density (0.45 g/cm.sup.3 nominal)PVC foam in 21 mm cylinder 44 157 Bottom of wad damaged, slight absorption of blue dye on wadPVC plastisol in 21 mm cylinder 370 Bottom of wad split, some blue dye absorbed18 mm low density (0.35 g/cm.sup.3 nominal)Foam PVC wax coated 20 Wax lifted from wad, no wax left in bottle neck, wad turned in bottlePVC plasticiser wax coated 98 Wax on wad lifting, wax left in bottle neck 58.8 Wax on wad lifting, wax left in bottle neckPVC plasticiser in 21 mm 98.8 Wad stained on the side with blue dye bottomcylinder 197.5 puckered Bottom puckered18 mm high density (0.45 g/cm.sup.3)PVC plastisol 171.5 WAd picked up some wax, possibly form corking 107.8 machine 58.8 Push through. Wad had picked up wax possibly from corker Wad turned in bottle, wax remained on wad however wax was liftingSingle wax coated @ 160.degree. C. No result Push through No resultDouble wax coated @ 160.degree. C. No result Push through. Wad had dropped in bottle neck No result Push through, very little wax remained on wad17 mm high density (0.45/cm.sup.3)PPVC plasticizer wax coated 95 Wax remained on wad, no wax on bottle, wad 10 mm above bottle neck 39.2 Wax remained on wadNatural corkParaffin coated 297.9 188.2 282.2Silicon coated 172.3 235.2 164.6__________________________________________________________________________
TABLE 5______________________________________Pullout tests(controls of corks and untreated wads with no simulant) ForceSample (N) Comments______________________________________Pullout performed after 24 hours0.35 nominal density 270 240 2300.45 nominal density Zero Pushed in. The harder wad requires greater effort to engage thread of corkscrew.Cork Parrafin coated 150 150 160Cork Silicon coated 130 220 30 28Pullout performed after 7 daysCork Paraffin coated 290 270 280 170 210 230Cork Silicone coated 100 120 125 130 130 120______________________________________
EXAMPLE 47
Liquid Leakage Storage Tests
Liquid leakage with various wool felt-based closure constructions were assessed by weighing the sealed bottle containing the wine simulant at 24 hour intervals. The results are provided at Table 6.
TABLE 6______________________________________STORAGE TEST Water loss [g] 1 days 2 days 3 days 4 days 5 days 6 days______________________________________Low Density(0.35 g/cm.sup.3)22 mm wadUntreated 9.5 0.9 2.0 1.4 0.3 2.2 7.9 0.6 1.9 1.5 3.3 2.0 8.7 0.7 1.9 1.7 3.6 2.0Thermoformed +0.1 0.0 0.0 0.0 0.0 0.0with SUFLYN 4.9 0.3 1.2 0.5 1.3 1.7 3.6 0.7 1.3 1.5 3.8 2.2Single wax 3.5 0.0 2.2 0.4 1.1 1.5coated @ 5.4 0.9 1.8 1.6 3.7 2.1110.degree. C. 5.1 0.7 1.7 1.8 4.2 2.4Two piece wad 6.3 0.7 1.8 1.7 4.1 2.0 6.2 0.6 1.6 1.4 3.1 1.9 7.7 0.7 1.8 1.6 3.6 2.3Double coated +0.3 +0.1 0.0 0.1 0.0 0.0(360D @ +0.3 0.0 +0.1 0.0 0.1 0.050% solids) 4.4 0.3 0.5 0.8 2.4 0.2High density18 mm wadcoated withPVC plasticiserNo wax coating 0.0 0.0 +0.1 0.0 0.0 0.0 0.0 0.0 0.0Single wax 0.0 0.0 0.0coated @ 0.0 0.0 0.0160.degree. C.Double wax 0.0 1.0 1.6coated @ 0.3 0.1 0.5160.degree. C.______________________________________ Note: high density wads are 0.45 g/ml
EXAMPLE 48
Evaluation of Properties of Wood Felt-PVC Plastisol Closures Against ISO Standards for Cork
EXPERIMENTAL
Six of the Wool felt-PVC plastisol closures described in Example 1 (approximately 33.times.20 mm) were inserted into 750 ml bottles which had previously been filled with 10% aqueous ethanol solution, sufficient to allow an ullage distance of 15 mm from the level of the solution and the underside of the closure. The force required to remove the cork from the bottles (extractive force) was determined after a period of eight days, using a Mecmesin AGF1000 digital force gauge.
The method used was identical with that specified in ISO 9727, Section 7.6.1, International Organisation for Standardisation (ISO 9729: Cylindrical stoppers of natural cork--physical tests--reference methods, Geneva: ISO; 1991) except that bottles with Stein type bore were used in place of those with the CETIE type bore profile, as the latter were not available. The corking machine used was of a three jaw design rather than the four jaw design specified.
Absorption
Six of the wool felt-PVC plastisol closures were numbered and weighed, inserted into bottles filled with 10% ethanol solution and stored in a horizontal position for eight days. After this time they were removed, placed on a Whatman No. 4 filter paper for one minute, and then reweighed (the same six closures were used in this test and in the extraction strength test described above).
The method followed is based on ISO 9727, Section 7.8, Stein bore rather than CETIE bore bottles were used, and a three jaw corking machine was used.
Absorption was calculated as follows: ##EQU1##
Where m.sub.f =final weight of closure, g
m.sub.i =initial weight of closure, g
Wine Travel
The Varanda apparatus was used to test the resistance of the closures to wine travel. Closures were inserted into three of each of 18 mm and 19 mm internal diameter acrylic "bottle necks" using a corking machine, which were inverted then filled with dye solution after two hours and attached to the apparatus and tested according to the instructions supplied. The closures were trimmed of excess plastic before insertion. For comparative purposes, natural wine corks (44.times.24 mm) were also tested. All closures were then examined for wine travel after 10 minutes exposed to pressures of 0.5 bar, 1.0 bar, 1.5 bar, 2.0 bar and 2.5 bar.
RESULTS
Extraction force
Results of extraction force are summarised in Table 7. Extraction force should lie between 200 N and 300 N; the results for five of the six closures tested lie within this range, while the result for one closure was low. It must be noted that these standards relate to corks inserted into bottles with the CETIE type bore, while bottles with a Stein type bore were used in the tests. The slightly greater diameter of the CETIE bore may be expected to result in slightly lower values for extraction force.
Absorption
Results of the absorption tests are also summarised in Table 7. The CTCOR specifications for absorption following the test method described have also been obtained; the absorption for natural corks should be less than 3%, and for agglomerate corks, less than 40%. The results obtained were well below both these specifications.
Wine Travel
Virtually no travel of the dye solution was observed in any of the six closures tested, ever at the maximum test pressure of 2.5 bar. Two of the closures were cut in half lengthwise after testing, and this revealed that the dye had not penetrated the coating. In comparison, considerable travel was observed in the natural wine corks at a pressure of 0.5 bar. It is acknowledged, however, that the behaviour of these corks may not be typical of all corks.
TABLE 7______________________________________Results of measurements of extraction forceand absorption of wool felt - PVC plastisol closures Extraction Force AbsorptionClosure (N) (% w/w)______________________________________1 244 0.162 281 0.153 166 1.024 218 0.125 299 0.166 259 0.16mean 244.5 0.295______________________________________
The results indicate that the wool felt-PVC plastisol closures performed well in terms of extraction force, absorption and wine travel. Some closures had slightly low extraction force, compared with available standards. This may be able to be improved upon by increasing the diameter of the closures.
EXAMPLE 49-57
Wool Felt-Polyurethane Closures
All closure examples 49-57 were made using wads of 0.4 g/cm.sup.3 wool felt. The felt wads used in the closures were 21.5, 22.0 or 22.5 mm in diameter and 38 or 40 mm in length. The wads were coated and/or capped with the polyurethane 6012A (UniRoyal Chemical Co.), and in some cases undercoated with EVA. Extraction forces and wine travel test results are shown in Table 8.
TABLE 8______________________________________Exam-ple Closure Characteristics Extraction Travel @No. L.sub.M D.sub.M D.sub.MD L.sub.CAP Coating Force(N) 2 bar______________________________________49 43 21.5 21.0 0 PU 289 8750 43 22.0 21.5 0 PU 464 4051 43 21.5 21.0 2.5 PU 342 7552 38 21.5 21.0 2.5 PU 294 053 43 22.0 21.5 2.5 PU 399 054 43 22.5 22.0 2.5 PU 553 055 43 22.0 21.5 1.0 EVA/FU 264 2456 43 22.0 21.5 2.5 EVA/PU 315 057 43 22.0 21.5 4.0 EVA/PU 392 0______________________________________ PU = polyurethane 6012A EVA = ethyl vinyl acetate (undercoat) L.sub.M = mass length (mm) D.sub.M = mass diameter (mm) D.sub.MD = mould diameter (mm) L.sub.CAP = length of composite end cap (mm)
It will be appreciated by persons skilled in the art that numerous variations and/or modifications may be made to the invention as shown in the specific embodiments without departing from the spirit or scope of the invention as broadly described. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive.

Number	Date	Country	Kind
PN 4852	Mar 1994	AUX
PN 7741	Aug 1994	AUX

Number	Name	Date
926895	Quillot	Jul 1909
1463570	Bragdon	Jul 1923
1466113	Bragdon	Aug 1923
1763129	Broadhurst	Jun 1930
3772136	Workman	Nov 1973
3874541	Lagneaux et al.	Apr 1975
4081884	Johst et al.	Apr 1978
4091136	O'Brien et al.	May 1978
4176095	Aziz et al.	Nov 1979
4182458	Meckler	Jan 1980
4349122	Klar et al.	Sep 1982
5052578	Goodwin	Oct 1991
5229439	Gueret	Jul 1993

Number	Date	Country
3245378	Jul 1979	AUX
1591288	Nov 1988	AUX
291802	Jul 1971	ATX
331392	Apr 1903	FRX
1508722	Nov 1967	FRX
1518450	Feb 1968	FRX
168705	Jan 1905	DEX
178740	Dec 1905	DEX
6909984	Jan 1970	NLX
211675	Feb 1923	GBX
458227	May 1936	GBX
557937	Jun 1942	GBX
2093054	Aug 1982	GBX

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Entry
Wool Science Review 61, International Wood Secretariat, Development Centre, pp. 3-58 "A Winery Evaluates Synthetic Cork," Tom Mackey, Wines and Vines, Jul. 1992.
ISO 9729, 1991.
ISO 3863.
ISO 9727, 1991.