WO2001014219A1

WO2001014219A1 - Secondary synthetic closure for sealing corked bottles or containers

Info

Publication number: WO2001014219A1
Application number: PCT/US2000/040668
Authority: WO
Inventors: Grant Good; Andy Salvador; Jerome M. Zech, Jr.
Original assignee: Supreme Corq Inc
Current assignee: Supreme Corq Inc
Priority date: 1999-08-20
Filing date: 2000-08-16
Publication date: 2001-03-01
Anticipated expiration: 2002-02-20
Also published as: AU7882100A

Abstract

The present invention is directed to secondary synthetic closures for use with bottles or containers having a primary closure associated therewith. In one embodiment, the secondary synthetic (26) closure is adapted to sealingly engage a bottle or container (10) (such as a wine bottle) having a removable primary closure (22) recessively inserted therein, wherein the bottle or container (10) has a cylindrical neck portion (14) and a cylindrical opening (16) therethrough, wherein the primary closure (22) sealingly engages the cylindrical neck portion (14), and wherein the secondary synthetic closure (26) has a disk shape. In another embodiment, the secondary synthetic closure (28) is adapted to sealingly engage a bottle or container (10) having a removable primary closure (22) inserted therein, wherein the bottle or container (10) has a cylindrical neck portion (14) and a cylindrical opening (16) therethrough, wherein the primary closure (22) sealingly engages the cylindrical neck portion (14), and wherein the secondary synthetic closure (28) is in the form of a capsule adapted to encapsulate at least a portion of the cylindrical neck portion (14) and the cylindrical opening (16) therethrough. The secondary synthetic closures of the present invention comprise a thermoplastic elastomer. The present invention is also directed to methods of secondarily sealing corked and/or synthetically closed bottles and containers with the novel secondary closures.

Description

SECONDARY SYNTHETIC CLOSURE FOR SEALING CORKED BOTTLES OR CONTAINERS

TECHNICAL FIELD

The present invention is generally directed to a secondary synthetic closure for sealing corked and synthetically closed bottles or containers, and more specifically, to a secondary synthetic closure comprising a thermoplastic elastomer.

BACKGROUND OF THE INVENTION

Historically, natural cork has been utilized as the primary closure for stopper-type bottle closures. There are, however, several disadvantages associated with the use of natural cork. For example, natural cork may have variable properties with respect to, among other things, color, drying, shrinkage or expansion, crumbling, sticking to containers and seal formation. These features are generally undesirable in terms of production and consumer costs as well as product performance.

As a result of the disadvantages associated with natural cork, numerous attempts have been made to develop alternatives to natural cork bottle stoppers, such as the development of synthetic closures. To date, one of the most successful synthetic closures, which overcomes many of the disadvantages associated with natural cork, are the synthetic closures manufactured by Supreme Corq (Kent, Washington U.S.A.). Specifically, U.S. Patent Nos. 5,480,915, 5,496,862, 5,692,629, 5,710,184, and 5,855,287 all to Burns and owned by Supreme Corq (and are all expressly incorporated herein by reference), disclose various synthetic closures for removable insertion into bottles and containers. These synthetic closures are made from formulations that comprise a "thermoplastic elastomer" material. Such synthetic closures have proved to be a significant improvement over both natural corks and other prior art closure assemblies.

A drawback common to both synthetic and natural cork closures, however, has been providing a suitable secondary seal. Secondary seals have recently been deemed desirable by, for example, many wineries because such seals provide a protective integument which makes product tampering more difficult. Secondary seals also allow for the display of a decorative graphic designs, embossed and/or debossed markings, any one of which may be desirable for purposes of product marketing.

One current method of secondary sealing involves the use of a metal foil wrapped over the bottle opening and around the bottle neck. This method, however, is not desirable for many beverage manufactures, such as some wineries, because of the perceived health risks associated with lead that may be contained in the foil, and because of the additional consumer inconvenience associated with removing the metal foil before "uncorking" the bottle or container. Another current method of secondary sealing involves forming a wax seal directly onto the bottle having a primary closure inserted therein by dipping the opening and neck of the bottle into a vat of melted wax. This method, however, has the disadvantages of requiring the bottle to be inverted during the sealing process, and of leaving an aesthetically unpleasing wax residue around the neck of the bottle. Moreover, such a wax residue may crumble in an undesirable way upon removal of the primary closure.

Still another current method of secondary sealing involves the use of a secondary closure coupled directly on top of a recessively inserted primary bottle closure, wherein the primary bottle closure is a natural cork closure. Exemplary in this regard are the wax secondary closures disclosed in U.S. Patent Nos. 5,553,726, 5,449,080, 5,447,246, and 5,261,547 all to Finke and owned by WineCap Company (Sonoma, California, U.S.A.). More specifically, these patents disclose various wax and conventional thermoplastic discs that are to be applied on top of recessed corks that have previously been inserted into a bottle or container. Significant disadvantages associated with such wax and thermoplastic discs include: (1) undesirable product contamination by wax and/or wax-like particles caused by crumbling and/or breakage of the secondary closure during removal from, for example, a wine bottle; and (2) adhesion difficulties associated with their incompatibility with "thermoplastic elastomer" type primary closures. Accordingly, there is still a need in the art for novel and improved secondary closures for sealing corked and/or synthetically closed bottles and containers. The present invention fulfills these needs and provides for further related advantages.

SUMMARY OF THE INVENTION In brief, the present invention is directed to secondary synthetic closures for use with bottles or containers having a primary closure associated therewith. In one embodiment, the secondary synthetic closure is adapted to sealingly engage a bottle or container (such as a wine bottle) having a removable primary closure recessively inserted therein, wherein the bottle or container has a cylindrical neck portion and a cylindrical opening therethrough, wherein the primary closure sealingly engages the cylindrical neck portion, and wherein the secondary synthetic closure has a disk shape. In another embodiment, the secondary synthetic closure is adapted to sealingly engage a bottle or container having a removable primary closure inserted therein, wherein the bottle or container has a cylindrical neck portion and a cylindrical opening therethrough, wherein the primary closure sealingly engages the cylindrical neck portion, and wherein the secondary synthetic closure is in the form of a capsule adapted to encapsulate at least a portion of the cylindrical neck portion and the cylindrical opening therethrough.

An essential characteristic of the present invention is that the secondary synthetic closure must comprise a thermoplastic elastomer. In this regard, the thermoplastic elastomer of the present invention may comprise a thermoplastic polyurethane elastomer, a polyolefin-based thermoplastic elastomers, a thermoplastic elastomer based on dynamically vulcanized elastomer-thermoplastic blends, a thermoplastic polyether ester elastomer, a thermoplastic elastomer based on halogen- containing polyolefins, a thermoplastic elastomer based on polyamides, a styrenic thermoplastic elastomer, or various mixtures thereof.

In one embodiment, the thermoplastic elastomer material of the secondary synthetic closure is a styrene block copolymer. The styrene block copolymer may be selected from the group consisting of one or more of a styrene- ethylene/butylene-styrene block copolymer, a styrene-ethylene/propylene-styrene block copolymer, a styrene-butadiene-styrene block copolymer, and a styrene-isoprene- styrene block copolymer. Alternatively, the thermoplastic elastomer material is a thermoplastic elastomer vulcanizate and/or a metallocene catalyzed ethylene-α-olefin copolymer, such as an ethylene-octene-olefm copolymer. The thermoplastic elastomer material of the present invention may have a Shore A hardness ranging from 60 to 90.

The present invention is also directed to methods for secondarily sealing corked and/or synthetically closed bottles and containers with the secondary closures disclosed herein. In one embodiment, the inventive method involves (1) providing a wine bottle having a removable primary closure recessively inserted therein, wherein the wine bottle has a cylindrical neck portion and a cylindrical opening therethrough, wherein the primary closure sealingly engages the cylindrical neck portion; and then (2) coupling to the recessively inserted primary closure a secondary synthetic closure having a disk shape, wherein the secondary synthetic closure is adapted to sealingly engage the cylindrical neck portion, and wherein the secondary synthetic closure comprises a thermoplastic elastomer material. In another embodiment, the inventive method involves (1) providing a wine bottle having a removable primary closure inserted therein, wherein the wine bottle has a cylindrical neck portion and a cylindrical opening therethrough, wherein the primary closure sealingly engages the cylindrical neck portion; and then (2) encapsulating at least a portion of the cylindrical neck portion and the cylindrical opening therethrough with a secondary synthetic closure, wherein the secondary synthetic closure is in the form of a capsule, and wherein the secondary synthetic closure comprises a thermoplastic elastomer material.

The present invention is also directed to a wine bottle that has been sealed with a secondary synthetic closure as disclosed herein.

These and other aspects of the present invention will be apparent upon reference to the following detailed description and attached Figures. BRIEF DESCRIPTION OF THE DRAWINGS

Figure 1 depicts a wine bottle having a removable primary closure recessively inserted therein, and a secondary closure sealingly engaged to the bottle in accordance with a first embodiment of the present invention. Figure 2A depicts a top plan view of a secondary closure in accordance with the present invention.

Figure 2B depicts a side elevation view of the secondary closure of Figure 2A.

Figure 2C depicts a top perspective view of the secondary closure of Figure 2A.

Figure 3 depicts a wine bottle having a removable primary closure inserted therein, and a secondary closure sealingly engaged to the bottle in accordance with a second embodiment of the present invention.

DETAILED DESCRIPTION OF THE INVENTION As noted above, the present invention is generally directed to a secondary synthetic closure for sealing corked and synthetically closed bottles or containers, and more specifically, to a secondary synthetic closure comprising a thermoplastic elastomer. The present invention is also directed to methods of secondarily sealing corked and/or synthetically closed bottles and containers with the secondary closures disclosed herein. In one embodiment, the secondary synthetic closure comprises a "thermoplastic elastomer," wherein the thermoplastic elastomer comprises a styrene block copolymer. In alternative embodiments, the secondary synthetic closures comprise other thermoplastic elastomer materials such as, for example, thermoplastic polyurethane elastomers (i.e., TPUs), polyolefin-based thermoplastic elastomers (i.e., TPOs), thermoplastic elastomers based on dynamically vulcanized elastomer-thermoplastic blends (i.e., TPVs), thermoplastic polyether ester elastomers, thermoplastic elastomers based on halogen-containing polyolefms, and thermoplastic elastomers based on polyamides. The physical characteristics associated with each of these thermoplastic elastomers (and the various embodiments associated therewith) are more fully described below. In addition, and although many specific details of certain embodiments of the present invention are set forth in the following detailed description and accompanying Figures, those skilled in the art will recognize that the present invention may have additional embodiments, or that the invention may be practiced without several of the details described herein.

In addition, and in contrast to known thermoplastic secondary closures (i.e., wax discs), a critical limitation of the secondary closures of the present invention is that they comprise a composition having a thermoplastic elastomer material (thereby providing for several related advantages as disclosed herein). As used herein, the term "thermoplastic elastomer" refers to those block and/or graft copolymers that are characterized as having, at room temperature, a major proportion of a soft segment and a minor proportion of a hard segment, as well as fine dispersions, that form a two-phase morphology in the solid state. As such, thermoplastic elastomers are readily distinguishable from conventional thermoplastic materials. Exemplary thermoplastic elastomer materials of the present invention include, but are not limited to, any one or combination of the following: thermoplastic polyurethane elastomers (i.e., TPUs), polyolefin-based thermoplastic elastomers (i.e., TPOs), thermoplastic elastomers based on dynamically vulcanized elastomer- thermoplastic blends (i.e., TPVs), thermoplastic polyether ester elastomers, thermoplastic elastomers based on halogen-containing polyolefms, thermoplastic elastomers based on polyamides, and styrene based thermoplastic elastomers. As is appreciated by those skilled in the art, each of these materials may be characterized (unlike conventional single-phase thermoplastic materials) as having one or more copolymers that comprise a major proportion of a soft segment and a minor proportion of a hard segment so as to result in a composition having a two-phase morphology. Because of this unique chemical structure, such segmented thermoplastic elastomers provide for several of the advantages associated with the present invention.

Stated somewhat differently and without necessarily prescribing to any scientific theory, it is believed that the thermoplastic elastomers of the present invention possess unique thermal and mechanical properties (in contradistinction to known wax secondary closures) because they consists of hard segments that have a high glass transition temperature (i.e., T_g) or melting temperature (T_m) alternating with soft segments that have a low T_g («room temperature). In addition to these constraints, the hard and soft segments are generally chosen such that the free energy of mixing is positive. As such, the mutual incompatibility of the segments induces microphase separation in the solid state. The hard segments tend to aggregate to form glassy or semicrystalline hard domains interspersed in a continuous soft segment matrix (hence, a two-phase morphology). The boundaries between these two phases are not well defined because there exists some degree of forced compatibility due to the relatively short average chain lengths and molecular weight distributions (i.e., generally below 4,000 atomic mass units) associated with each of the two types of segments.

In addition to the foregoing and as further appreciated by those skilled in the art, the soft segments contribute to the flexibility and extensibility of the thermoplastic elastomer, whereas the glassy or semicrystalline domains of the hard segments serve as physical crosslinks that impedes chain slippage and viscous flow. Because the crosslinks associated with the hard segments are physical in nature (in contradistinction to the chemical bonds found in vulcanized rubber), they are thermally reversible. As such, heating above the softening or melting point of the hard segment causes the hard domains to disassociate and become fluid. Without the hard segment tie points, the thermoplastic elastomer is able to flow, and therefore can be melt processed in conventional thermoplastic processing equipment, such as, for example, conventional injection molding, extrusion molding, blow molding, solution casting and calendering processing equipment.

As noted above, the thermoplastic elastomers of the present invention may comprise thermoplastic polyurethane elastomers (i.e., TPUs), polyolefin-based thermoplastic elastomers (i.e., TPOs), thermoplastic elastomers based on dynamically vulcanized elastomer-thermoplastic blends (i.e., TPVs), thermoplastic polyether ester elastomers, thermoplastic elastomers based on halogen-containing polyolefms, thermoplastic elastomers based on polyamides, and styrene based thermoplastic elastomers. Moreover, the polymer chains associated with the soft and hard segments associated with each of these thermoplastic elastomers may be synthesized with any number of monomer units - so as to range from short to long - wherein the soft and hard segment chain lengths define, in large part, the physical properties of the thermoplastic elastomer. The lengths of the soft and hard segments notwithstanding, each of the these theremoplastic elastomers may be used to produce the secondary closures of the present invention and are therefore more fully described below.

The thermoplastic polyurethane elastomers (i.e., TPUs) of the present invention are generally made from long-chain polyols with an average molecular weight of 60 to 4,000, chain extenders with a molecular weight of 61 to 400, and polyisocyanates. Within the genus of TPUs, the soft flexible segments generally comprise either hydroxyl terminated polyesters or hydroxyl terminated polyethers, whereas the hard segments generally comprise 4,4'-diphenylmethane diisocyanate. The hard segments may, however, comprise hexamethylene diisocyanate, 4,4'- dicyclohexylmethane diisocyanate, 3,3'-dimethyl-4,4'-biphenyl diisocyanate, 1,4- benzene diisocyanate, tr_. ^,-cyclohexane-l,4-diisocyanate, and 1,5 -naphthalene diisocyanate. As is appreciated by those skilled in the art, the characteristics of the hard segment and to a large extent the physical properties of the TPU are generally determined by the choice of the polyisocyanate and its associated chain extender. In the context of the present invention, the most important chain extenders for the above - identified TPUs are linear diols such as, for example, ethylene glycol, 1 ,4-butanediol, 1 ,6-hexanediol, and hydroquinone bis(2-hydroxyethyl) ether.

The polyolefin-based thermoplastic elastomers (i.e., TPOs) of the present invention generally include random block copolymers (e.g., ethylene α-olefin copolymers based on a metallocene polymerization catalysis process), block copolymers (e.g., hydrogenated butadiene-isoprene-butadiene block copolymers), stereoblock polymers (e.g., stereoblock polypropylene), graft copolymers (e.g., polyisobutylene-g-polystyrene and EPDM-g-pivalolactone), and blends (e.g., blends of ethylene-propylene random copolymer with isotactic polypropylene and dynamically vulcanized blends of EPDM with a crystalline polyolefin). As is appreciated by those skilled in the art, all of these thermoplastic elastomers generally depend on crystallization of polymer chains to produce an elastomeric structure. For example, in the TPO random block copolymers (which are structurally similar to TPU random block copolymers) ethylene sequences long enough to crystallize at use temperature act as physical crosslinks for the amorphous elastic chain segments. In the TPO stereoblock copolymers, changes in intrachain tacticity (i.e., alternating stereoregularities) provide for the alternating crystalline and amorphous sequences.

The thermoplastic elastomers based on halogen-containing polyolefms of the present invention include those thermoplastic elastomers having halogen atoms attached to the polymer backbone, as well as some blends of poly(vinyl chloride) (PVC) with crosslinked or elastomeric polymers. Exemplary in this regard is melt-processable rubber (MBR), as well as blends of PVC with acrylonitrile-butadiene elastomer (NBR), copolyester (CPO), and thermoplastic polyurethane elastomer (TPU).

The thermoplastic elastomers based on dynamically vulcanized elastomer-thermoplastic blends of the present invention are generally made through the relatively new processing technology referred to as "dynamic vulcanization" This proprietary processing technology has provided for novel thermoplastic elastomer materials that have many properties as good or even, in some aspects, better than those of styrenic block copolymers. Exemplary in this regard are the proprietary products prepared by the dynamic vulcanization of blends of olefin rubber with polyolefin resin (SANTOPRENE thermoplastic elastomers, Advanced Elastomer Systems, L.P., United States). Other thermoplastic vulcanizates, now referred to as TPVs, include blends of ethylene-propylene-diene terpolymer (EPDM) elastomer with polypropylene and/or polyethylene, as well as blends of polyolefms with diene rubbers such as butyl rubber, natural rubber, acrylonitrile-butadiene copolymer (NBR), and styrene-butadiene copolymer (SBR).

The thermoplastic polyether ester elastomers of the present invention are generally multiblock copolyether esters with alternating, random-length sequences of either long-chain or short-chain oxyalkylene glycols connected by ester linkages. These materials are related structurally to the polyurethane and the polyamide thermoplastic elastomers in that they also contain repeating high-melting blocks that are capable of crystallization (hard segments) and amorphous blocks having a relatively low glass transition temperature (soft segments). Typically, the hard segments are composed of short-chain cyclic ester units such as teramethylene terephthalate, whereas the soft segments are generally derived from aliphatic polyether glycols. The thermoplastic elastomers based on polyamides of the present invention are generally characterized as having a polyamide hard segment and an aliphatic polyester, aliphatic polyether, and/or aliphatic polycarbonate soft segment. The polyamide-based thermoplastic elastomers, like the TPVs, are relative newcomers to the family of thermoplastic elastomers. Lastly, the styrenic thermoplastic elastomers of the present invention are generally characterized as polystyrene-polydiene block copolymers, where both ends of each polydiene chain are terminated by polystyrene segments. With this type of thermoplastic elastomer, the rigid polystyrene domains act as multifunctional junction points to give a crosslinked elastomer network similar in some aspects to that of conventional vulcanized rubber. The polystyrene segments may include substituted polystyrene such as, for example, poly(α-methylstyrene), copolymers of α- methylstyrene, and poly(/?-t-r/-butyl-styrene), although these types of polystyrene segments are generally less preferred. In addition, the polydiene segments may include, for example, polyisoprene, polybutadiene, ethylene-propylene copolymers, and ethylene-butylene copolymers.

As noted above, in one embodiment of the present invention the thermoplastic elastomers used for manufacturing the secondary synthetic closures disclosed herein comprise one or more styrenic block copolymers. Preferably, such styrenic block copolymers include one or more of a styrene-ethylene/butylene-styrene block copolymer (SEBS), a styrene-ethylene/propylene-styrene block copolymer (SEPS), a styrene-butadiene-styrene block copolymer (SBS), and a styrene-isoprene- styrene block copolymer (SIS) (e.g., KRATON thermoplastic elastomer compounds, Shell Chemical Company, United States). In one embodiment, the thermoplastic elastomer of the present invention comprises a styrene-ethylene/butylene-styrene block copolymer (e.g., Tuftec, Asahi Chemicals, Japan). As is appreciated by those skilled in the art, SBS and SIS are A-B-A type block copolymers having unsaturated elastomeric central segments, whereas SEBS and SEPS are A-B-A type block copolymers having saturated elastomeric central segments. Accordingly, because of their structure, SBS and SIS are more sensitive to oxidation than SEBS and SEPS and are therefore less preferred.

In order to optimize the processability and to enhance the permeability characteristics of gases such as O₂, C0₂ and SO₂ (through, for example, increased polymer crystallinity), the thermoplastic elastomer materials of the present invention are generally compounded to a large extent with other polymers, and may also be compounded with various oils, plasticizers, fillers and extenders, as well as other specialty additives (collectively referred to as processing additives). Indeed, and as appreciated by those skilled in the polymer compounding art, any number of various processing additives may be added to enhance one or more physical characteristics and properties of the secondary closures disclosed herein. Exemplary of such processing additives are those identified in Gachter R., Muller H., The Plastics Additives Handbook, 4^th ed., Hanser Publishers, Munich, Germany (1996) (incorporated herein by reference in its entirety).

In one preferred embodiment, the thermoplastic elastomer material of the present invention comprises a mixture of a styrene-ethylene/butylene-styrene (SEBS) block copolymer, a metallocene catalyzed ethylene-α-olefin copolymer, and a high crystallinity polypropylene (i.e._t a syndiotactic polypropylene). Without necessarily prescribing to any particularly scientific theory, it is believed that the higher crystallinity associated with syndiotactic polypropylene allows for higher crystallinity in the formed secondary synthetic closures of the present invention. The higher degree of crystal lattice structure within the secondary synthetic closures decreases, but does not totally eliminate, the pathways (e.g., interstitial gaps and irregularities) from which gases such as O₂, CO₂ and SO₂ may migrate through. Moreover, it is believed that having appropriate pathways for some gas permeation through the primary and secondary closure assembly (e.g., gas permeation consistent with that of high grade natural cork and thermoplastic elastomer type primary closures) is needed for the proper aging of certain premium beverages such as wine.

Although the above-identified mixture is generally preferred, the mixture may include a TPV (e.g., SANTOPRENE thermoplastic elastomer vulcanizate compounds, Advanced Elastomer Systems, L.P., United States) as opposed to a SEBS. In addition, the ethylene-α-olefin copolymer may be an ethylene-butene copolymer, an ethylene-hexene copolymer, an ethylene-octene copolymer, or a mixture thereof. An ethylene-octene copolymer (e.g., ENGAGE metallocene catalyzed ethylene-α-olefin copolymer, Dupont Dow Elastomers, United States), however, is preferred. In another embodiment, the thermoplastic elastomer materials of the present invention are compounded with an extending oil that comprises a polyolefm oil. As used within the context of the present invention, the term "extending oil" includes carbonaceous materials added to the composition to reduce costs, or improve physical properties. In still another embodiment, the thermoplastic elastomer materials of the present invention are compounded with a processing additive. As used within the context of the present invention, the term "processing additive" includes any additive that aids in the processing or workability of the materials and/or compositions to be formed into secondary synthetic closures. For example, one or more other materials may be compounded with the overall composition so as to improve the composition's processability and/or performance characteristics of the secondary closures. Thus, the term processing additives encompasses various oxygen scavengers that may added to the overall composition (e.g., Daraform 25515-C-l, Darex Container Products, United States), as well as biological growth inhibitors useful in killing and/or preventing the proliferation of molds and bacteria. Other materials may also be compounded with the overall composition, such as coloring and flavoring agents, to thereby enhance the aesthetic and olfactory appeal of the secondary synthetic closures.

As is appreciated by those skilled in the art. the above-identified ingredients (which are associated with one preferred embodiment of the present invention) may be compounded together as in the following exemplary manner. First, desired weight percentages of styrene-ethylene butylene-styrene block copolymer, polypropylene and ethylene-α-olefin copolymer, as well as desired amounts of processing additive or other specialty chemicals (e.g., antioxidants, colorants, and stabilizers) may be added together in an appropriately sized first mixer (e.g., 350 lb. Capacity Henschel Mixer w/cooler). This dry blend may then be mixed and allowed to reach a temperature of 80°F prior to feeding to an appropriately sized second continuous mixer (e.g., via a Colortronic MH 60 dosing feeder to a 4 inch Farrel Continuous Mixer). The blades of the second continuous mixer may then be rotated (e.g., at 175 rpm) so as to cause the dry blend to flux into a homogeneous melt at an elevated temperature (e.g., 340°F). The molten composition may then be transferred via a transfer line jacketed with nitrogen to a single screw pelletizing extruder (e.g., a single screw pelletizing extruder having a length to diameter ratio of 8 to 1). The molten composition may then be extruded through the die of the extruder (e.g., a multi-hole die), cooled in a water bath, and strand cut through a cutter (e.g., through a Cumberland cutter at a rate of 120-130 lbs. per hour).

As is further appreciated by those skilled in the art, the compounded ingredients of the present invention may be formed into secondary synthetic closures by any number of suitable processing techniques. For example, the secondary synthetic closures of the present invention may be formed by injection molding, extrusion, and casting. In one exemplary embodiment, a thermoplastic elastomer material made in the manner as set forth above is used as a feedstock for an injection molding process. The feedstock is combined with a suitable blowing agent (e.g., using automatic metering and mixing devices mounted directly on the injection molding machine or extruder), heated to a suitable temperature, and injected into a disk shaped mold (e.g., a disk shaped mold having a diameter equal to that of a standard wine closure and a height ranging from 2 to 3 millimeters). The precise amount of blowing agent used may be determined by one skilled in the art by taking into account the exact composition of polymers and other ingredients used, as well as the molding or extrusion conditions. Moreover, the injection molding process readily allows for an emblem or other decorative design to be embossed to the secondary synthetic closure. In another exemplary embodiment, the thermoplastic elastomer material is used in a cast molding process (i.e., no blowing agent), wherein the thermoplastic elastomer material, in a liquid state, is poured into a disk shaped mold having appropriate dimensions (e.g., disk shaped mold having height ranging from 1 to 5 millimeters and diameter ranging from 15 to 20 millimeters, or disk shaped mold having diameter about equal to that of standard wine bottle and height of about 2 millimeters). The cast molding process also readily allows for an emblem or other decorative design to be embossed to the secondary synthetic closure.

The secondary synthetic closures of the present invention may also be formed by directly pouring a selected amount of liquefied theremoplastic elastomer material into the opening of a bottle having a removable primary closure recessively inserted therein so as to define a disk shaped space (i.e., the top surface of the recessed primary closure and the plane transverse across the annular surface associated with the bottle opening defines a space in the shape of a disk). In this alternative method, the selected amount of liquefied theremoplastic elastomer material fills the defined disk shape above the recessively inserted primary closure. As used herein, the term "disk shape" is understood to encompasses cylinders and frustums of cones having respective diameters greater than their respective heights.

In addition to the foregoing description, the secondary synthetic closures of the present invention may also be illustrated in the context of a wine bottle having a removable primary closure recessively inserted therein as shown in Figure 1 (not to scale). More specifically, and as shown in Figure 1, a translucent wine bottle 10 comprises a body 12 integrally connected to a cylindrical neck portion 14. The neck portion 14 has a cylindrical opening 16 therethrough. In conjunction, the cylindrical neck portion 14 and cylindrical opening 16 define an axis 18, as well as an annular surface 20.

As is further shown in Figure 1 , wine bottle 10 has a removable primary closure 22 recessively inserted therein. The primary closure 22 is "recessively inserted" because it sealingly engages neck portion 14 and resides below a plane 24 defined by the annular surface 20. In this configuration, the top surface (not shown) of the primary closure 22 and plane 24 transverse across the annular surface 20 defines a disk shape. A secondary closure 26 in accordance with the present invention fills the defined disk shape. In addition, the secondary closure 26 is coupled to primary closure 22 recessively inserted into neck portion 14, and sealingly engages the cylindrical neck portion 14 of wine bottle 10. The secondary closure 26 may be coupled to primary closure 22 by means of an interposing adhesive (not shown).

Further illustrations of a secondary closure in accordance with the present invention are shown in Figures 2A-C. More specifically, Figure 2 A illustrates a top plan view of a secondary synthetic closure 26, whereas Figure 2B illustrates a corresponding side elevation view and Figure 2C illustrates a corresponding perspective view of the secondary synthetic closure of Figure 2A. As shown, an emblem depicting wine grapes has been embossed onto exemplary secondary synthetic closure 26.

In yet another embodiment, the secondary closure of the present invention takes the shape and form of a capsule. More specifically, the secondary closures may be in the form of a capsule adapted to encapsulate the neck portion of, for example, a wine bottle. As used herein, the term "capsule" refers to an integument designed to cover the neck portion and opening of a bottle. This embodiment of the present invention may also be illustrated in the context of a wine bottle having a primary closure inserted therein (but not necessarily recessively inserted therein). More specifically, and as shown in Figure 3, wine bottle 10 has removable primary closure 22 (not shown) inserted therein; however, the primary closure has been inserted so as to be flush with annular surface 20 (not shown). As shown, a secondary synthetic closure 28 in accordance with another embodiment of the present invention encapsulates a portion of the cylindrical neck portion and the cylindrical opening therethrough. As is appreciated by those skilled in the art, a capsule may be manufactured be by various plastic processing techniques.

For example, the capsule embodiment of the present invention may be formed by calendering. As is appreciated by those skilled in the art, calendering generally involves extruding a mass of melted plastic material (e.g., thermoplastic elastomer) between successive pairs of corotating, parallel rolls to form a film or sheet. A suitable calendar for forming the capsule embodiment generally has four heavy, large steel rolls assembled in the inverted "L" configuration. Moreover, and in the context of the capsule embodiment, the calendar is preferably set to form a sheet having a thickness ranging from 0.05 to 0.75 millimeters, and more preferably from about 0.30 to 0.50 millimeters. After the calendering process, the formed sheet may then be cut into appropriate shapes (e.g., rectangular strips having affixed circles) which shapes may then be wrapped around and over the neck portion of a bottle. The seams may then be closed by, for example, cold seal, smooth seal, and slit seal techniques.

Because the secondary synthetic closures of the present invention are made from a "thermoplastic elastomer" material, they provide for several advantages over known secondary closures. For example, wax secondary closures have experienced adhesion difficulties, especially in the context of coupling to synthetic primary closures (and in particular those synthetic closures made with a thermoplastic elastomer). Without necessarily prescribing to any scientific theory, it is believed that such adhesion difficulties are due, in large part, to surface dissimilarities associated with the opposing surfaces of a wax secondary closure and a synthetic primary closure. Such surface dissimilarities inhibits mutual attractive forces between the opposing surface molecules, and impedes adhesive coupling therebetween. It is believed that the secondary synthetic closures of the present invention reduce this problem, especially when the underlying primary closure comprises a thermoplastic elastomer.

As another example, metal foil secondary synthetic closures have perceived health risks and added consumer inconvenience associated with the foil removal; the secondary synthetic closures of the present invention alleviate this problem because (1) there are no perceived health problems associated with thermoplastic elastomers, and (2) the secondary closure may be readily pierced by, for example, a cork screw during the uncorking process, without any unwanted crumbling or breakage.

Finally, the thermoplastic elastomer secondary closures of the present invention eliminate the crumbling problems associated with known wax secondary closures. Stated somewhat differently, known wax secondary closures are generally susceptible to crumbling upon removal of the closure assembly from, for example, a wine bottle, and have therefore resulted in undesirable product contamination by wax and/or wax-like particles. This problem is eliminated because the thermoplastic elastomer secondary closures of the present invention do not crumble or disintegrate upon insertion of a cork screw. As stated above, a cork screw may readily penetrate a thermoplastic elastomer secondary closure and insert into a natural cork or synthetic thermoplastic elastomer primary closure, and will do so without any breakage or cracking of the secondary closure.

In order to better illustrate the preferred compositions associated with some of the embodiments of the present invention, several examples are presented. It is to be understood, however, that the following examples are provided for purposes of illustration, not restriction.

Example 1

A composition suitable for making the secondary synthetic closures of the present invention may be formulated by combining three major polymeric components together with an extending oil and minor amounts of processing additives.

Specifically, the composition may be formulated by combining the following ingredients in the following weight percentages:

(1) 16.0% by weight of a high crystallinity polypropylene (Profax 6323, Montell Polyolefms, The Netherlands);

(2) 25.8% by weight of a styrene-ethylene/butylene-styrene block copolymer (Tuftec JT56F, Asahi Chemicals., Japan);

(3) 18.5% by weight of a metallocene catalyzed ethylene-octene copolymer having a Shore A hardness 94, density 0.902, octene content 13.5% by weight, and melting point of 100°C. (Engage 8402, Dupont Dow Elastomers, United States);

(4) 18.5% by weight of a metallocene catalyzed ethylene-octene copolymer having a Shore A hardness 96, density 0.913, octene content 9.0% by weight, and melting point of 107°C. (Engage 8403, Dupont Dow Elastomers, United States); (5) 20.6% by weight of a polyolefm extending oil (Hydrobrite 380 PO); and

(6) 0.6% by weight of processing additives (~ 0.56% Kemamide E, Witco Polymer Chemical Group, United States, and ~ 0.04% Irganox 1010, Ciba Specialty Chemicals, Switzerland).

Such a formulated composition was found to have Shore A hardness 74.

Example 2 A composition suitable for making the secondary synthetic closures of the present invention may be formulated by combining three major polymeric components together with an extending oil and minor amounts of processing additives.

Specifically, the composition may be formulated by combining the following ingredients in the following weight percentages: (1) 11.0% by weight of a high crystallinity polypropylene (Profax 814,

Montell Polyolefms, The Netherlands);

(2) 30.8% by weight of a styrene-ethylene/butylene-styrene block copolymer (Tuftec JT56F, Asahi Chemicals., Japan);

(3) 16.5% by weight of a metallocene catalyzed ethylene-octene copolymer having a Shore A hardness 94, density 0.902, octene content 13.5% by weight, and melting point of 100°C. (Engage 8402, Dupont Dow Elastomers, United States);

(4) 16.5% by weight of a metallocene catalyzed ethylene-octene copolymer having a Shore A hardness 96, density 0.913, octene content 9.0% by weight, and melting point of 107°C. (Engage 8403, Dupont Dow Elastomers, United States);

(5) 24.6% by weight of a polyolefm extending oil (Hydrobrite 380 PO); and (6) 0.6% by weight of processing additives (~ 0.56% Kemamide E, Witco Polymer Chemical Group, United States, and ~ 0.04% Irganox 1010, Ciba Specialty Chemicals, Switzerland).

The formulated composition was found to have Shore A hardness 74.

Example 3

A composition suitable for making the secondary synthetic closures of the present invention may be formulated by combining two major polymeric components together with an extending oil and minor amounts of processing additives.

(1) 40.8% by weight of a styrene-ethylene/butylene-styrene block copolymer (Tuftec JT56F, Asahi Chemicals., Japan);

(2) 12.5% by weight of a metallocene catalyzed ethylene-octene copolymer having a Shore A hardness 94, density 0.902, octene content 13.5% by weight, and melting point of 100°C. (Engage 8402, Dupont Dow Elastomers, United States); (3) 12.5% by weight of a metallocene catalyzed ethylene-octene copolymer having a Shore A hardness 96, density 0.913, octene content 9.0% by weight, and melting point of 107°C. (Engage 8403, Dupont Dow Elastomers, United States);

(4) 32.6% by weight of a polyolefm extending oil (Hydrobrite 380 PO); and

(5) 0.6% by weight of processing additives (~ 0.56% Kemamide E, Witco Polymer Chemical Group, United States, and ~ 0.04% Irganox 1010, Ciba Specialty Chemicals, Switzerland).

The formulated composition was found to have Shore A hardness 60. Example 4

(1) 25.0% by weight of a high crystallinity polypropylene (Profax 6323, Montell Polyolefms, The Netherlands); (2) 30.0% by weight of a styrene-ethylene/butylene-styrene block copolymer (Septon 8004, Kuraray Co. Ltd., Japan);

(3) 19.4% by weight of a metallocene catalyzed ethylene-octene copolymer having a Shore A hardness 72, density 0.87, octene content 24.0% by weight, and melting point of 60°C. (Engage 8400, Dupont Dow Elastomers, United States)

(4) 24.0% by weight of a polyolefm extending oil (Hydrobrite 380 PO); and

(5) 1.6% by weight of processing additives (~ 1.5% Kemamide E, Witco Polymer Chemical Group, United States, and ~ 0.1% Irganox 1010, Ciba Specialty Chemicals, Switzerland).

The formulated composition was found to have Shore A hardness 84.

While the products and methods of the present invention have been described in the context of the embodiments illustrated and described herein, the invention may be embodied in other specific ways or in other specific forms without departing from its spirit or essential characteristics. Therefore, the described embodiments are to be considered in all respects only as illustrative and not restrictive. The scope of the present invention is, therefore, indicated by the appended claims rather than by the foregoing description, and all changes that come within the meaning and range of equivalency of the claims are to embraced within their scope.

Claims

1. A secondary synthetic closure adapted to sealingly engage a bottle or container having a removable primary closure recessively inserted therein, wherein the bottle or container has a cylindrical neck portion and a cylindrical opening therethrough, wherein the primary closure sealingly engages the cylindrical neck portion, and wherein the secondary synthetic closure has a disk shape and comprises a thermoplastic elastomer.

2. A secondary synthetic closure adapted to sealingly engage a bottle or container having a removable primary closure inserted therein, wherein the bottle or container has a cylindrical neck portion and a cylindrical opening therethrough, wherein the primary closure sealingly engages the cylindrical neck portion, and wherein the secondary synthetic closure is in the form of a capsule adapted to encapsulate at least a portion of the cylindrical neck portion and the cylindrical opening therethrough and comprises a thermoplastic elastomer.

3. The secondary synthetic closure of claim 1 or 2 wherein the bottle is a wine bottle.

4. The secondary synthetic closure of claim 1 or 2 wherein the thermoplastic elastomer is a thermoplastic polyurethane elastomer, a polyolefin-based thermoplastic elastomers, a thermoplastic elastomer based on dynamically vulcanized elastomer-thermoplastic blends, a thermoplastic polyether ester elastomer, a thermoplastic elastomer based on halogen-containing polyolefms, a thermoplastic elastomer based on polyamides, a styrenic thermoplastic elastomer, or a mixture thereof.

5. The secondary synthetic closure of claim 4 wherein thermoplastic elastomer is a styrenic thermoplastic elastomer.

6. The secondary synthetic closure of claim 5 wherein the styrenic thermoplastic elastomer is a styrene-ethylene/butylene-styrene block copolymer, a styrene- ethylene/propylene-styrene block copolymer, a styrene-butadiene-styrene block copolymer, a styrene-isoprene-styrene block copolymer, or a mixture thereof.

7. The secondary synthetic closure of claim 5 wherein the styrene block copolymer is a styrene-ethylene/butylene-styrene block copolymer and a styrene- ethylene/propylene-styrene block copolymer, or a mixture thereof.

8. The secondary synthetic closure of claim 5 wherein the styrene block copolymer is a styrene-ethylene/butylene-styrene block copolymer.

9. The secondary synthetic closure of claim 1 or 2, further comprising an extending oil.

10. The secondary synthetic closure of claim 1 or 2, further comprising a processing additive.

11. The secondary synthetic closure of claim 1 or 2 wherein the thermoplastic elastomer is a metallocene catalyzed ethylene-α-olefm copolymer.

12. The secondary synthetic closure of claim 11 wherein the thermoplastic elastomer is a metallocene catalyzed ethylene-octene-olefin copolymer.

13. The secondary synthetic closure of claim 1 or 2 wherein the thermoplastic elastomer further comprises a polypropylene polymer.

14. The secondary synthetic closure of claim 13 wherein the polypropylene polymer is a syndiotactic polypropylene polymer, an isotactic polypropylene polymer, or a mixture thereof.

15. The secondary synthetic closure of claim 13 wherein the polypropylene polymer is a syndiotactic polypropylene polymer.

16. The secondary synthetic closure of claim 1 or 2, wherein the thermoplastic elastomer material has a Shore A hardness ranging from 60 to 90.

17. The secondary synthetic closure of claim 1 or 2, wherein the thermoplastic elastomer comprises: a thermoplastic elastomer that comprises a styrenic block copolymer; an ethylene-α-olefin copolymer; and a polyproplyene polymer.

18. The secondary synthetic closure of claim 17, wherein the styrenic block copolymer is a styrene-ethylene/butylene-styrene block copolymer.

19. The secondary synthetic closure of claim 17, wherein the ethylene-α- olefin copolymer is an ethylene-octene-olefin copolymer.

20. The secondary synthetic closure of claim 17, wherein the polyproplyene polymer is a syndiotactic polyproplyene polymer.

21. The secondary synthetic closure of claim 17, wherein the styrenic block copolymer is a styrene-ethylene/butylene-styrene block copolymer, wherein the ethylene-α-olefin copolymer is an ethylene-octene-olefin copolymer, and wherein the polyproplyene polymer is a syndiotactic polyproplyene polymer.

22. The secondary synthetic closure of claim 1 or 2, further comprising an oxygen scavenger.

23. The secondary synthetic closure of claim 1 or 2, further comprising a biological growth inhibitor.

24. A method for sealing a corked or synthetically closed wine bottle, comprising the steps of: providing a wine bottle having a removable primary closure recessively inserted therein, wherein the wine bottle has a cylindrical neck portion and a cylindrical opening therethrough, wherein the primary closure sealingly engages the cylindrical neck portion; and coupling to the recessively inserted primary closure a secondary synthetic closure having a disk shape, wherein the secondary synthetic closure is adapted to sealingly engage the cylindrical neck portion, and wherein the secondary synthetic closure comprises a thermoplastic elastomer material.

25. A method for sealing a corked or synthetically closed wine bottle, comprising the steps of: providing a wine bottle having a removable primary closure inserted therein, wherein the wine bottle has a cylindrical neck portion and a cylindrical opening therethrough, wherein the primary closure sealingly engages the cylindrical neck portion; and encapsulating at least a portion of the cylindrical neck portion and the cylindrical opening therethrough with a secondary synthetic closure, wherein the secondary synthetic closure is in the form of a capsule.

26. A wine bottle sealed with the secondary synthetic closure of claim 1 or