WO2000026103A9 - Synthetic closure for bottle-like containers - Google Patents
Synthetic closure for bottle-like containersInfo
- Publication number
- WO2000026103A9 WO2000026103A9 PCT/US1999/025862 US9925862W WO0026103A9 WO 2000026103 A9 WO2000026103 A9 WO 2000026103A9 US 9925862 W US9925862 W US 9925862W WO 0026103 A9 WO0026103 A9 WO 0026103A9
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- synthetic closure
- ethylene
- copolymer
- styrene
- block copolymer
- Prior art date
Links
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D39/00—Closures arranged within necks or pouring openings or in discharge apertures, e.g. stoppers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D39/00—Closures arranged within necks or pouring openings or in discharge apertures, e.g. stoppers
- B65D39/0005—Closures arranged within necks or pouring openings or in discharge apertures, e.g. stoppers made in one piece
- B65D39/0011—Closures arranged within necks or pouring openings or in discharge apertures, e.g. stoppers made in one piece from natural or synthetic cork, e.g. for wine bottles or the like
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2353/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
Definitions
- the present invention is generally directed to a primary synthetic closure suitable for removable insertion into a bottle or container, and more specifically, to a synthetic closure comprising a thermoplastic elastomer compounded with an ethylene- ⁇ -olefin copolymer and a polypropylene polymer.
- natural cork has been utilized as the primary closure for stopper-type bottle closures.
- 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.
- numerous attempts have been made to develop alternatives to natural cork bottle stoppers, such as the development of synthetic closures.
- recent efforts to develop closures from injection and extrusion plastic processing techniques have encountered numerous pitfalls, particularly in terms of production cost, product performance, and consumer acceptance.
- closures Some of these closures have exhibited a tendency to noticeably taint the product and/or offer low resistance to oxygen permeation into the container.
- some synthetic closures made from known plastic compositions and formulations have generally exhibited poor uniformity in terms of size, shape, weight, and other features important to production, marketing, and performance of synthetic closures.
- the plastic compositions are generally injected into relatively cool molds, leading to the formation of a dense outer skin at the surface of the closure with a porous, foam-like interior.
- the composition of the closure, and the structural relationship between the outer skin and porous core of the closure, are often critical to imparting desired characteristics to the finished closure.
- foamed plastic closures often suffer problems due to wrinkling of the outer skin, which can produce leakage fissures between the closure and the container.
- Other synthetic closures have different sealing problems. For example, some synthetic closures fail to quickly return to normal size after compression, requiring bottles and/or containers to be kept in an upright position for an extended period after insertion of the closure.
- U.S. Patent No. 4,363,849 to Paisley et al. This patent discloses the production of synthetic closures having a natural cork-like appearance, wherein the synthetic material is a polyolefin, such as an ethylene vinyl acetate copolymer (EVA).
- EVA ethylene vinyl acetate copolymer
- special injection molding apparatuses are required in which it is necessary to gradually release the air in the cold molding cavity that is displaced by the injected synthetic resin. This is accomplished by means of controlled minimum venting, or other means in order to maintain the heightened pressure (e.g., about 16,000 psi) within the mold.
- U.S. Patent No. 4,188,457 to Throp discloses -mother plastic composition that is used to form closures for wine bottles.
- thermoplastic composition disclosed by this patent also comprises an EVA copolymer, which material, however, is undesirable because it is not able to quickly expand back to its original formed shape after being compressed by, for example, the jaws of a bottling machine.
- an EVA copolymer synthetic closure does not have adequate elastomeric properties which allows it to sealingly engage an opening of, for example, a wine bottle substantially immediately after being inserted therein by means of a bottling machine. This drawback prohibits the wine bottle from being placed in a horizontal position substantially immediately after corking.
- Still another type of synthetic closure is the kind disclosed in U.S. Patent No. 5,317,047 to Sabate et al.
- This patent discloses, among other things, a composition useful for making synthetic closures, wherein the composition constitutes a mixture of three principal components; namely, (1) powder and particles of natural cork; (2) expandable plastic microspheres of a methyl methacrylate-acrylonitrile copolymer; and (3) a binding agent of a polyurethane or acrylic type.
- a selected amount of such a three-part composition is introduced into a cylindrical shaped mold, heat is then rapidly applied in order to expand the plastic microspheres thereby causing the composition to fill the mold, and finally the expanded composition is allowed to slowly cool in order to properly set the binding agent.
- the resulting synthetic closure made in accordance with U.S. Patent No. 5,317,047 to Sabate et al has many characteristics consistent with that of natural cork; however, it does not posses a protective outer skin like that of many other types of synthetic closures. Because there is no protective outer skin, the resulting synthetic closure suffers from at least two drawbacks.
- the synthetic closure is substantially less durable than a synthetic closure having a protective outer skin (e.g., the pulling action associated with removing the synthetic closure from a bottle using a traditional corkscrew may cause cracking and disintegration that shortens the synthetic closure's useful life).
- the synthetic closure is more amenable to "scoring" when compressed by the jaws of a bottling machine than a synthetic closure encapsulated by a protective outer skin.
- thermoplastic elastomer formulations first invented by Supreme Corq are amenable to both injection and extrusion molding.
- the present invention is directed to an easily removable synthetic closure suitable for removable insertion into a bottle or container.
- the synthetic closure comprises a thermoplastic elastomer and a metaliocene catalyzed ethylene- ⁇ -olefm copolymer.
- the synthetic closure is made from a composition formulated from the ingredients comprising: a thermoplastic elastomer that comprises a styrenic block copolymer; an ethylene- ⁇ -olefin copolymer; a polyproplyene polymer; and a blowing agent; and wherein the closure has a Shore A hardness ranging from 60 to 84.
- the synthetic closure may further comprises an extending oil and/or a processing additive.
- the styrenic block copolymer 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.
- the styrenic block copolymer is a styrene-ethylene/butylene-styrene block copolymer and a styrene-ethylene/propylene- styrene block copolymer, or a mixture thereof. Further preferably, the styrenic block copolymer is a styrene-ethylene/butylene-styrene block copolymer.
- the ethylene- ⁇ -olefin copolymer is an ethylene- butene copolymer, an ethylene-hexene copolymer, an ethylene-octene copolymer, or a mixture thereof.
- the ethylene- ⁇ -olefin copolymer is an ethylene-octene copolymer.
- the polypropylene polymer is a syndiotactic polypropylene polymer and a isotactic polypropylene polymer, or a mixture thereof.
- the polypropylene polymer is a syndiotactic polypropylene polymer.
- the synthetic closure is made from a composition
- a composition comprising: a thermoplastic elastomer that comprises a stryrenic block copolymer, wherein the thermoplastic elastomer ranges from 10% to 95% by weight of the composition; a first polymer that comprises polypropylene, wherein the first polymer ranges from 0% to 25% by weight of the composition; a second polymer that comprises an ethylene- ⁇ -olefin copolymer, wherein the second polymer ranges from 5% to 60%) by weight of the composition; and an extending oil that comprises a polyolefin. wherein the extending oil ranges from 0% to 35% by weight of the composition.
- the present invention is also directed to a synthetic closure adapted to sealingly engage a cylindrical opening of a wine bottle, wherein the synthetic closure comprises a first thermoplastic vulcanizate.
- the first thermoplastic vulcanizate may be a dynamic vulcanized blend that includes an olefin rubber and a polyolefin resin.
- the first thermoplastic vulcanizate may be a dynamic vulcanized blend that includes an ethylene-propylene-diene terpolymer elastomer and a polypropylene and/or a polyethylene.
- the present invention is also directed to a cylindrical shaped synthetic closure adapted for removable insertion into an opening of a wine bottle, wherein the synthetic closure has an inner foamed core structure surrounded by an outer skin layer that is of the same or different material than the inner foamed core structure, and wherein the synthetic closure is further adapted to sealingly engage the opening of the wine bottle, wherein the synthetic closure comprises a polymeric composition that includes a thermoplastic elastomer and a metallocene catalyzed ethylene- ⁇ -olefin copolymer.
- the thermoplastic elastomer is one or more of an ethylene- ⁇ -olefin copolymer thermoplastic elastomer, a thermoplastic polyurethane elastomer, a polyolefin-based thermoplastic elastomer, a thermoplastic polyether ester elastomer, and a styrene block copolymer thermoplastic elastomer.
- the alpha-olefin component of the ethylene- ⁇ -olefin copolymer thermoplastic elastomer ranges from about 2% to 30% by weight of the copolymer, wherein the ethylene- ⁇ - olefin copolymer thermoplastic elastomer is a metallocene catalyzed ethylene- ⁇ -olefin copolymer selected from one or more of an ethylene-butene copolymer, an ethylene- hexene copolymer, and an ethylene-octene copolymer.
- the present invention is further directed to a cylindrical shaped synthetic closure adapted for removable insertion into an opening of a wine bottle, wherein the synthetic closure has an inner foamed core structure surrounded by an outer skin layer that is of the same or different material than the inner foamed core structure, and wherein the synthetic closure is further adapted to sealingly engage the opening of the wine bottle, wherein the synthetic closure comprises a thermoplastic polyurethane elastomer.
- thermoplastic polyurethane elastomer may comprise a plurality of soft flexible segments and a plurality of hard segments, wherein the soft flexible segments comprise one or more long-chain polyols having an average molecular mass ranging from of 60 to 4,000 atomic mass units, and wherein the hard segments comprise one or more polyisocyanates.
- the soft flexible segments may be hydroxyl terminated polyesters or hydroxyl terminated polyethers
- the hard segments may be selected from the group consisting of 4,4'- diphenylmethane diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 3,3'-dimethyl-4,4'-biphenyl diisocyanate, 1,4-benzene diisocyanate, trans- cyclohexane-l,4-diisocyanate, and 1 ,5 -naphthalene diisocyanate.
- the present invention is also directed to methods for manufacturing synthetic closures (as well the synthetic closures made therefrom), methods that include injection, extrusion, and co-extrusion processing techniques.
- the present invention includes a method for manufacturing a synthetic closure adapted for removable insertion and sealable engagement with an opening of a wine bottle, comprising the steps of: compounding a polymeric composition from the ingredients comprising a styrene block copolymer thermoplastic elastomer, an ethylene- ⁇ -olefin copolymer, and a polyproplyene polymer; combining the polymeric composition with a blowing agent under heat to yield a feedstock; injecting the feedstock into a mold having a cylindrical shape; and cooling the mold to form the synthetic closure.
- the present invention is directed to a method for manufacturing a synthetic closure adapted for removable insertion and sealable engagement with an opening of a wine bottle, comprising the steps of: combining a polymeric composition that comprises a thermoplastic vulcanizate with a blowing agent under heat to yield a feedstock; injecting the feedstock into a mold having a cylindrical shape; and cooling the mold to form the synthetic closure.
- the present invention is directed to a method for manufacturing a synthetic closure adapted for removable insertion and sealable engagement with an opening of a wine bottle, comprising the steps of: combining a polymeric composition that comprises a thermoplastic polyurethane elastomer and/or a polymeric composition that comprises a styrene block copolymer thermoplastic elastomer, an ethylene- ⁇ -olefin copolymer, and a polypropiyene polymer, with a blowing agent under heat to yield a feedstock; injecting the feedstock into a mold having a cylindrical shape; and cooling the mold to form the synthetic closure.
- the present invention is directed to a method for manufacturing a synthetic closure adapted for removable insertion and sealable engagement with an opening of a wine bottle, comprising the steps of: compounding a polymeric composition from the ingredients comprising a styrene block copolymer thermoplastic elastomer, an ethylene- ⁇ -olefin copolymer, and a polypropiyene polymer; combining the polymeric composition with a blowing agent under heat to yield a feedstock; extruding or co-extruding the feedstock through a circular die to form a rod; cooling the rod to yield a cooled rod; and cutting the cooled rod to form the synthetic closure.
- the present invention is also directed to a wine bottle in combination with any one of the synthetic closures disclosed herein.
- Figure 1 depicts a front isometric view of a synthetic closure suitable for removable insertion into a wine bottle, the synthetic closure evidencing a marbled surface texture, an embossed symbol on an end, and printing on its side.
- Figure 2 depicts a front side elevational view of the synthetic closure of
- Figure 3 depicts a top plan view of the synthetic closure of Figure 1.
- Figure 4A is an enlarged cross-sectional partial view (i.e., magnified approximately 15 times) taken substantially along line 2-2 of Figure 2 showing the inner foam structure and outer skin of an exemplary injection molded synthetic closure.
- Figure 4B is an enlarged cross-sectional partial view (i.e., magnified approximately 30 times) taken substantially along line 2-2 of Figure 2 showing the inner foam structure and outer skin of an exemplary injection molded synthetic closure.
- Figure 4C is an enlarged cross-sectional partial view (i.e., magnified approximately 100 times) taken substantially along line 2-2 of Figure 2 showing the inner foam structure and outer skin of an exemplary injection molded synthetic closure.
- Figure 5 A is an enlarged cross-sectional partial view (i.e., magnified approximately 15 times) showing the inner foam structure and outer skin of an exemplary first extrusion molded synthetic closure.
- Figure 5B is an enlarged cross-sectional partial view (i.e., magnified approximately 30 times) showing the inner foam structure and outer skin of the exemplary first extrusion molded synthetic closure of Figure 5 A.
- Figure 5C is an enlarged cross-sectional partial view (i.e., magnified approximately 100 times) showing the inner foam structure and outer skin of the exemplary first extrusion molded synthetic closure of Figure 5 A.
- Figure 6A is an enlarged cross-sectional partial view (i.e., magnified approximately 15 times) showing the inner foam structure and outer skin of an exemplary second extrusion molded synthetic closure.
- Figure 6B is an enlarged cross-sectional partial view (i.e., magnified approximately 30 times) showing the inner foam structure and outer skin of the exemplary second extrusion molded synthetic closure of Figure 6A.
- Figure 6C is an enlarged cross-sectional partial view (i.e., magnified approximately 100 times) showing the inner foam structure and outer skin of the exemplary second extrusion molded synthetic closure of Figure 6A.
- Figure 7A is a perspective top view of a first representative synthetic cork having a hard plastic top coupled to a elastomeric shaft in accordance with the present invention.
- Figure 7B is a cross-sectional view taken substantially along line 7B-7B of Figure 7A showing the hard plastic top having an extension that extends downwardly into the elastomeric shaft.
- Figure 7C is a cross-sectional view taken substantially along line 7C-7C of Figure 7B showing a portion of the hard plastic top encircling the shaft, and a portion of the shaft encircling the extension of the hard plastic top.
- Figure 8A is a perspective top view of a second representative synthetic cork having a hard plastic top coupled to a elastomeric shaft in accordance with the present invention.
- Figure 8B is a cross-sectional view taken substantially along line 8B-8B of Figure 8 A showing the hard plastic top having an extension that extends downwardly into the elastomeric shaft.
- Figure 8C is a cross-sectional view taken substantially along line 8C-8C of Figure 8B showing a portion of the hard plastic top encircling the shaft, and a portion of the shaft encircling the extension of the hard plastic top.
- Figure 9A is a perspective top view of a third representative synthetic cork having a hard plastic top coupled to a elastomeric shaft in accordance with the present invention.
- Figure 9B is a cross-sectional view taken substantially along line 9B-9B of Figure 9A showing the hard plastic top having an extension that extends downwardly into the elastomeric shaft.
- Figure 9C is a cross-sectional view taken substantially along line 9C-9C of Figure 9B showing a portion of the hard plastic top encircling the shaft, and a portion of the shaft encircling the extension of the hard plastic top.
- Figure 10 is a triangular diagram showing the composition of a polymeric material in accordance with an embodiment of the present invention, wherein the polymeric material includes a thermoplastic elastomer, an ethylene- ⁇ -olefin copolymer, a polyproylene polymer, and wherein the relative amounts on a weight percent basis of the thermoplastic elastomer, the ethylene- ⁇ -olefin copolymer, and the polyproylene polymer vary with one another as set forth.
- the present invention is generally directed to a primary synthetic closure suitable for insertion into and subsequent removal from a bottle or container, and more specifically, to a synthetic closure comprising a thermoplastic elastomer optionally compounded with a metallocene catalyzed ethylene- ⁇ -olefin copolymer and/or a polypropylene polymer (as well as various processing additives).
- the thermoplastic elastomer comprises a styrenic block copolymer compounded with an ethylene-octene copolymer and a high crystallinity polypropylene.
- the thermoplastic elastomer comprises a thermoplastic elastomer vulcanizate.
- thermoplastic elastomers of the present invention are optionally compounded with one or more other polymers to yield a composition suitable for forming a primary synthetic closure adapted for sealable engagement and removable insertion into a bottle or container.
- thermoplastic elastomers of the present invention are blended together with natural cork particles to yield a composition suitable for forming a primary synthetic closure adapted for sealable engagement and removable insertion into a bottle or container.
- the various thermoplastic elastomers blends disclosed herein are amenable to, among other things, injection, extrusion, and co-extrusion processing techniques.
- synthetic closures are in many ways more resilient (e.g., less amenable to scoring) than existing synthetic closures.
- the synthetic closures of the present invention are, in general, relatively less expensive to produce than many of the existing types of synthetic closures.
- thermoplastic elastomers such as, for example, thermoplastic elastomers, metallocene catalyzed ethylene- ⁇ -olefin copolymers, polypropylene polymers, and natural cork particles -
- ingredients such as, for example, thermoplastic elastomers, metallocene catalyzed ethylene- ⁇ -olefin copolymers, polypropylene polymers, and natural cork particles -
- this Detailed Description of the Invention has been further sub-divided into eight subsections; namely: (1) Overview of Polymer Nomenclature and Theory; (2) Suitable Thermoplastic Elastomers; (3) Suitable Ethylene- ⁇ -olefin Copolymers; (4) Suitable Polypropylene Polymers; (5) Suitable Additives; (6) Exemplary Compounding Techniques; (7) Exemplary Synthetic Closure Manufacturing Processes; and (8) Alternative T-Shaped Closure Embodiments.
- a polymer is a macromolecule (i.e.. a long chain molecular chain) synthetically derived from the polymerization of monomer units or which exists naturally as a macromolecule (but which is still derived from the polymerization of monomer units).
- the links of the molecular chain are the monomer units.
- polypropylene is a polymer derived from the monomer propylene (CH 2 CHCH 3 ). More specifically, polypropylene is a "homopolymer" - that is, a polymer consisting of a single repeating unit, namely, the monomer propylene (CH 2 CHCH 3 ).
- a "copolymer” is a polymer containing two (or more) different monomer units.
- a copolymer may generally be synthesized in several ways. For example, a copolymer may be prepared by the copolymerization of two (or more) different monomers. Such a process yields a copolymer where the two (or more) different monomers are randomly distributed throughout the polymer chain. These copolymers are known as "random copolymers.” Alternatively, copolymers may be prepared by the covalent coupling or joining of two homopolymers.
- a block copolymer containing homopolymer A and homopolymer B may be schematically represented by the following formula: (A) x (B) y where (A) x is a homopolymer consisting of x monomers of A, (B) y is homopolymer consisting of y monomers of B, and wherein the two homopolymers are joined by a suitable covalent bond or linking spacer group.
- block copolymers may also have three or more block components (e.g., a "tri -block copolymer” schematically represented by the formula (A) x (B) y (A) x or simply A-B-A, as well as a "multiblock copolymer” schematically represented by the formula (A-B) n ).
- exemplary thermoplastic elastomer materials i.e.,
- TPEs 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 polyolefins, thermoplastic elastomers based on polyamides, and styrene based thermoplastic elastomers.
- TPUs thermoplastic polyurethane elastomers
- TPOs polyolefin-based thermoplastic elastomers
- TPVs dynamically vulcanized elastomer-thermoplastic blends
- thermoplastic polyether ester elastomers thermoplastic elastomers based on hal
- thermoplastic 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.
- thermoplastic elastomers of the present invention possess unique thermal and mechanical properties 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).
- T g glass transition temperature
- T m melting temperature
- soft segments soft segments that have a low T g ( «room temperature).
- the hard and soft segments are generally chosen such that the free energy of mixing is positive.
- 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.
- 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.
- 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, and solution casting processing equipment.
- 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, any of the thermoplastic elastomer materials (as well as various combinations thereof) classified-above may be used to produce the primary synthetic closures of the present invention.
- the several different classifications of the above-identified thermoplastic elastomer materials are more fully identified and described below.
- thermoplastic elastomer materials 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 polyolefins, thermoplastic elastomers based on polyamides, and styrene based thermoplastic elastomers.
- TPUs thermoplastic polyurethane elastomers
- TPOs polyolefin-based thermoplastic elastomers
- TPVs dynamically vulcanized elastomer-thermoplastic blends
- thermoplastic polyether ester elastomers thermoplastic elastomers based on
- thermoplastic polyurethane elastomers i.e., TPUs
- TPUs thermoplastic polyurethane elastomers
- the soft flexible segments generally comprise either hydroxyl terminated polyesters or hydroxyl terminated polyethers
- the hard segments generally comprise 4,4'-diphenylmethane diisocyanate.
- the hard segments may, however, comprise hexamethylene diisocyanate, 4,4'- dicyclohexylmethane diisocyanate.
- 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.
- Exemplary of the commercially available TPU thermoplastic elastomers include those available from DuPont (E. I. Du Pont de Nemours and Company, United States) under the tradename HYLENE, as well as those available from Morton (Morton International Specialty Chemicals) under the tradename IROGRAN.
- the polyolefin-based thermoplastic elastomers (i.e., TPOs) of the present invention generally include random block copolymers (e.g., ethylene ⁇ -olefin copolymers), 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).
- random block copolymers e.g., ethylene ⁇ -olefin copolymers
- block copolymers e.g., hydrogenated butadiene-is
- thermoplastic elastomers generally depend on crystallization of polymer chains to produce an elastomeric structure.
- 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.
- TPO stereoblock copolymers changes in intrachain tacticity (i.e., alternating stereoregularities) provide for the alternating crystalline and amorphous sequences.
- TPO thermoplastic elastomers embrace more than one thermoplastic elastomer classification as set forth above.
- thermoplastic elastomers based on halogen-containing polyolefins 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.
- PVC poly( vinyl chloride)
- MBR melt-processable rubber
- NBR acrylonitrile-butadiene elastomer
- CPO copolyester
- TPUs thermoplastic polyurethane elastomers
- 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”
- dynamic vulcanization This proprietary processing technology has provided several novel thermoplastic elastomer materials (referred to herein as “thermoplastic vulcanizates”) that have many properties as good or even, in some aspects, better than those of traditional styrenic block copolymers.
- Exemplary in this regard are the proprietary products prepared by the dynamic vulcanization of blends of olefin rubber with polyolefin resin such as those sold by Shell and Advanced Elastomer Systems (Shell Chemical Company, United States; Advanced Elastomer Systems, L.P., United States) under the tradename SANTOPRENE.
- thermoplastic vulcanizates now generally referred to as TPVs, include various blends of ethylene-propylene-diene terpolymer (EPDM) elastomer with polypropylene and/or polyethylene, as well as blends of polyolefins with diene rubbers such as butyl rubber, natural rubber, acrylonitrile-butadiene copolymer (NBR), and styrene-butadiene copolymer (SBR).
- EPDM ethylene-propylene-diene terpolymer
- NBR acrylonitrile-butadiene copolymer
- SBR styrene-butadiene copolymer
- 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. Exemplary of the thermoplastic polyether ester elastomers are the polyether-ester block copolymers sold by DuPont (DuPont Engineering Polymers) under the tradename HYTREL.
- 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.
- 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.
- 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( ⁇ -methylstyrene), copolymers of ⁇ - methylstyrene, and poly(p-tert-butyl-styrene), although these types of polystyrene segments are generally less preferred.
- the polydiene segments may include, for example, polyisoprene, polybutadiene, ethylene-propylene copolymers, and ethylene-butylene copolymers.
- Exemplary of the styrenic thermoplastic elastomers are those sold by Shell (Shell Chemical Company, United States) under the tradename KRATON.
- the thermoplastic elastomer may comprise one or more styrenic block copolymers.
- 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).
- SEBS styrene-ethylene/butylene-styrene block copolymer
- SEPS styrene- ethylene/propylene-styrene block copolymer
- SBS styrene-butad
- the thermoplastic elastomer of the present invention comprises a styrene-ethylene butylene-styrene block copolymer (e.g., Tuftec, Asahi Chemicals, Japan).
- a styrene-ethylene butylene-styrene block copolymer e.g., Tuftec, Asahi Chemicals, Japan.
- SBS and SIS are A-B- A type block copolymers having unsaturated elastomeric central segments
- 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.
- thermoplastic elastomers may be compounded with one or more of an ethylene- ⁇ -olefin copolymer and/or a polypropylene polymer to yield a composition suitable for forming a primary synthetic closure adapted for sealable engagement and removable insertion into a bottle or container.
- the one or more ethylene- ⁇ -olefin copolymers of the present invention generally comprise metallocene catalyzed ethylene- ⁇ -olefin copolymers, and more preferably, metallocene catalyzed ethylene- ⁇ -olefin copolymers selected from one or more of an ethylene-butene copolymer, an ethylene-hexene copolymer, and an ethylene-octene copolymer (any one of which may also be classified as a thermoplastic elastomer).
- the alpha-olefin component of the ethylene- ⁇ -olefin copolymer ranges from 2% to 30% by weight of the copolymer.
- the metallocene catalyzed ethylene- ⁇ -olefin copolymers have densities (gm/cc) generally ranging from 0.86 to 0.95, melt indexes (ASTM 1238) generally ranging from 0.2 to 30, and melting points (°C, by DSC) generally ranging from 50-120.
- the metallocene catalyzed ethylene- ⁇ -olefin copolymer comprises an ethylene-octene copolymer (e.g., Engage, Dupont Dow Elastomers, United States).
- metallocene polymerization technology now allows for the manufacturing of relatively high molecular weight copolymers of very specific tacticities (e.g., isotactic and syndiotactic polymers), as well as the polymerization of almost any monomer - beyond the traditional C 3 to C 8 olefins - in an exact manner.
- a metallocene as is appreciated by those skilled in the art, is a positively charged metal ion sandwiched between two negatively charged cyclopentadienyl anions.
- ethylene- ⁇ -olefin copolymers derived from metallocene based catalyst technology, include polyolefin "plastomers” or POPs (the name given to Exxon's EXACT product line, which is manufactured with proprietary EXXPOL catalyst technology, Exxon Chemical, United States) and polyolefin "elastomers” or POEs (the name given to Dupont Dow Elastomer's ENGAGE product line, which is manufactured with its proprietary INSITE catalyst technology, Dupont Dow Elastomers LLC, United States).
- polyolefin "plastomers” or POPs the name given to Exxon's EXACT product line, which is manufactured with proprietary EXXPOL catalyst technology, Exxon Chemical, United States
- polyolefin "elastomers” or POEs the name given to Dupont Dow Elastomer's ENGAGE product line, which is manufactured with its proprietary INSITE catalyst technology, Dupont Dow Elastomers LLC, United States).
- POPs polyolefin plastomers
- POEs elastomers
- any one of the above-identified ethylene- ⁇ -olefin copolymers, or combinations thereof, may be used in the various compositions of the present invention.
- thermoplastic elastomers and/or ethylene- ⁇ -olefin copolymers may be compounded with a polypropylene
- polypropylene is a polyolefin which is generally formed by low-pressure polymerization of propylene using an organometallic mixed catalyst (e.g., Ziegler-Natta catalyst); however, polypropylene may be formed by use of a metallocene catalyst.
- organometallic mixed catalyst e.g., Ziegler-Natta catalyst
- Polypropylene is known to exist in three distinct structures: atactic polypropylene, syndiotactic polypropylene, and isotactic polypropylene. All three structures (and various combinations thereof) are suitable for the various compositions associated with the present invention.
- atactic polypropylene the methyl groups of each propylene monomer are randomly disposed on either side of the stretched carbon chain - that is, the stereochemistry at the chiral centers is random.
- Such random atactic polypropylene is generally produced by free-radical polymerization at high pressures. Because atactic polypropylene has an irregular stereochemistry, it is considered noncrystalline, has a low softening point, and generally has poor mechanical properties.
- syndiotactic polypropylene the methyl groups of each propylene monomer alternate regularly from one side of the stretched carbon chain to the other; whereas with isotactic polypropylene, the methyl groups of each propylene monomer are all on the same side of the stretched carbon chain.
- syndiotactic and isotactic polypropylene have regular stereochemistries (i.e., the stereochemistry at the chiral centers is ordered), and both are generally made using Ziegler-Natta catalysts.
- syndiotactic and isotactic polypropylene are generally much more crystalline than atactic polypropylene. That is, the regular arrangement of methyl groups along the stretched carbon chain allows them to fit together better in a crystal lattice structure. Without necessarily prescribing to any particularly scientific theory, it is believed that the higher crystallinity associated with syndiotactic and isotactic polypropylene allows for higher crystallinity in the formed synthetic closures of the present invention.
- syndiotactic and isotactic polypropylene decreases the pathways (e.g., interstitial gaps and irregularities) from which gases such as, for example, O 2 , CO, and SO 2 may migrate through.
- gases such as, for example, O 2 , CO, and SO 2 may migrate through.
- syndiotactic and isotactic polypropylene are generally preferred.
- thermoplastic elastomer and/or metallocene catalyzed ethylene- ⁇ -olefin copolymer are compounded with a polymer that comprises polypropylene, wherein the polypropylene is selected from one or more of a syndiotactic polypropylene and an atactic polypropylene.
- the polypropylene comprises a syndiotactic polypropolyene. (e.g., Profax 6323, Montell Polyolefins, The Netherlands). 5. Suitable Additives
- thermoplastic elastomer blends may be compounded (albeit optionally) 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).
- processing additives any number of various processing additives may be added to enhance one or more physical characteristics and properties of the synthetic closures disclosed herein. Exemplary of such processing additives are those identified in Gachter R., M ⁇ ller H., The Plastics Additives Handbook, 4 th ed., Hanser Publishers, Kunststoff, Germany (1996) (incorporated herein by reference in its entirety).
- thermoplastic elastomer blends of the present invention are compounded with an extending oil that comprises a polyolefin oil.
- extending oil includes carbonaceous materials added to the composition to reduce costs, or improve physical properties.
- the thermoplastic elastomer materials of the present invention are compounded with a processing additive.
- processing additive includes any additive that aids in the processing or workability of the materials and/or compositions to be formed into primary synthetic closures.
- 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 primary closures.
- 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.
- thermoplastic elastomer and/or metallocene catalyzed ethylene- ⁇ -olefin copolymer and/or polypropylene are also compounded with a polymer that comprises an ethylene-propylene copolymer (used to impart a higher degree of toughness).
- a "filler" such as calcium carbonate and/or natural cork particles may also be compounded together with the one or more other ingredients to yield a suitable composition for making a synthetic closure.
- the above-identified ingredients may be compounded together as in the following exemplary manner.
- desired weight percentages of styrene-ethylene/butylene-styrene block copolymer, polypropylene and ethylene- ⁇ -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).
- the resulting pellets are ready for manufacturing the various synthetic closures of the present invention. 7.
- Exemplary Synthetic Closure Manufacturing Processes 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).
- the compounded ingredients (e.g., pellets) of the present invention may be formed into primary synthetic closures by any number of suitable processing techniques.
- the synthetic closures of the present invention may be formed by injection molding, extrusion, and casting.
- a thermoplastic elastomer compounded with other polymers in accordance with the present invention is used as a feedstock for an injection molding process.
- a thermoplastic elastomer compounded with other polymers in accordance with the present invention is used as a feedstock for an extrusion molding process (e.g., the extrusion molding process described in U.S. Patent No. 5,904.965 to Noel et al., which is incorporated herein be reference in its entirety).
- the feedstock is combined with a suitable blowing agent (e.g., using automatic metering and mixing devices mounted directly on an injection molding machine), heated to a suitable temperature, and injected into a mold.
- a suitable blowing agent e.g., using automatic metering and mixing devices mounted directly on an injection molding machine
- the mold has a desired shape, such as, for example the shape of a wine cork.
- the shape is that of a cylinder having a height of about 36.5 millimeters or about 44.5 millimeters, and a diameter of about 21.5 millimeters (i.e., dimensions corresponding to that of two types of conventional wine closures), wherein the cylinder has a radius at an edge (e.g., a rounded edge).
- the cylinder may, however, have either a chamfer or a bevel at an edge.
- the compounded ingredients are mixed with a suitable blowing agent prior to the synthetic closure formation process (e.g., injection molding or extrusion molding).
- a suitable blowing agent e.g., injection molding or extrusion molding
- chemical blowing or foaming agents are additives which are able to evolve gas, such as N 2 or CO 2 , through chemical reactions that produce foam structures in a polymeric matrix.
- the blowing agent is an azodicarbonamide (or modified azocarbonamide) or a sodium bicarbonate, or mixture thereof (e.g., Spectratech FM1150H, Quantum Chemical Corp., United States).
- the blowing agent generally comprises greater than 1 % by weight of the total feedstock, and typically comprises a range that includes at least 1.3%, 1.5% or 2.0% by weight of the total feedstock, and less than 9.0%, 5.0%, 4.0% or 3.0% by weight of the total feedstock.
- the blowing agent comprises from about 1.3% to about 3.0%, typically from about 1.5% to about 2.5%, and preferably about 2.0% by weight of the total feedstock.
- the feedstock and suitable blowing agent are allowed to form a mixture, which is generally injected into a cylindrical mold over a period of from about 0.02 to about 6 seconds, typically from about 0.03 to about 2 seconds, and preferably from about 0.04 to 1 second.
- the molding pressure is generally from about 200 psi to about 900 psi, typically from about 300 psi to about 800 psi, and preferably from about 400 psi to about 700 psi.
- the molding temperature is generally from about 300°F to about 550°F, typically from about 325°F to about 425°F, and preferably from about 350°F to about 375°F, and further preferably about 350°F.
- the mixture is generally maintained in the mold from about 20 seconds to about 90 seconds, typically from about 30 seconds to about 80 seconds, and preferably from about 35 to about 60 seconds.
- the injection molding process is preferably performed as quickly as practicable and with no special venting.
- the mold is opened and the formed closure removed.
- the mixture is injected into the mold at a rate and temperature such that the softened or molten mixture randomly coils about the mold, much like a string being lowered into a bottle, to produce a visible random curling pattern along the surface of the formed closure, as generally depicted in Figures 1 and 2.
- the mixture is injected at a rate and temperature such the random curling pattern is minimized or even avoided (e.g., Figure 3).
- the air in the mold cavity at the beginning of a molding cycle is preferably removed by employing a vacuum assist coordinated with the injection of the mixture.
- the vacuum assist may be applied for about the last second of the injection period, or it may be first applied after the end of the injection period. Applying the vacuum assist too early in the injection period may result in overly large cell spaces within the formed closure, yielding an overly spongy product. Failure to employ a vacuum assist may result in increased molding cycle times. As is appreciated by those skilled in the art, molding times, pressures, venting, cooling, vacuum assisting, product removal, and other factors relevant to injection molding will be based, to a large extent, upon the precise combination of materials included in the overall composition, as well as the type, size and shape of the mold.
- blowing agent used may be determined by one skilled in the art taking to account the exact composition of polymers and other ingredients used, as well as the injection or extrusion molding conditions.
- the use of too much blowing agent will generally result in a synthetic closure that has excessively large cells (i.e., bubbles) in its interior, thus causing the closure to be overly spongy and potentially inconsistent during production.
- the use of too little blowing agent will generally result in a synthetic closure that does not have enough cells or inadequately sized cells.
- Such a closure may be too hard for routine removal and reinsertion using, for example, a corkscrew, among other problems.
- the average cell size of the foamed embodiments of the present invention ranges from about 0.02 millimeters to about 0.50 millimeters, and the average cell density ranges from about 8,000 cells/cm 3 to about 25,000 cells/cm 3 .
- the number and size of the cells should in one preferred embodiment correspond to that of Figures 4A-C, whereas in the case of a co-extrusion molding process (wherein an inner formed core has integrally bonded thereover an outer skin layer), the number and size of the cells should in other preferred embodiments correspond to that of Figures 5A-C and/or Figures 6A-C.
- many of the synthetic closures of the present invention are manufactured such that they have structural features that allows them, when sealingly engaged within the cylindrical opening of a wine bottle, to be removed with a normal corkscrew using a force of approximately approximately 15 to 35 kn, and preferably from about 22 to 28 kn, and more preferably from about 24 to 26 kn.
- the synthetic closures of the present invention include bi-compositional closures that have an elastomeric shaft coupled to a hard plastic top (e.g., a T-shaped closure).
- the elastomeric shaft is made from one of the compounded thermoplastic elastomer compositions disclosed herein.
- the hard plastic top may be made from any suitable hard plastic, many varieties of which are well known in the art, such as an acrylonitrile-butadiene- styrene (ABS) (e.g., Dow #478, Dow Chemicals, United States) and/or high impact polystyrene (HPS) (e.g., Dow AIM 4800, Dow Chemicals, United States).
- ABS acrylonitrile-butadiene- styrene
- HPS high impact polystyrene
- Such bi- compositional synthetic closures may be used, for example, as a bottle closure or stopper for liquor, wine, spirits and specialty foods, among other things.
- the bi-compositional or "T-top" synthetic closures of the present invention may be produced by using a variety of known molding and joining methods.
- the shaft portion of the synthetic cork may be formed by conventional processing techniques such as injection molding, extrusion, vacuum forming, and solution casting.
- the synthetic cork is made using co-injection molding equipment that injection molds two different types of materials at or about the same time.
- FIG. 7A depicts a top perspective view of three representative synthetic corks each having a hard plastic top coupled to a thermoplastic elastomer shaft in accordance with the present invention.
- Figure 7A depicts a synthetic cork having a bulbous shaped hard plastic top
- Figure 8A depicts a synthetic cork having a cylindrical shaped hard plastic top with a plurality of longitudinal grooves on the outer circumference
- Figure 9A depicts a synthetic cork having a cylindrical shaped plastic hard top with a plurality of longitudinal ridges on the outer circumference.
- the bulbous shape, the plurality of longitudinal grooves, and the plurality of longitudinal ridges allow one to more easily grip the synthetic cork, thereby facilitating removal and insertion of the synthetic cork into a suitable container or bottle.
- FIG. 7B, 8B, and 9B therein is shown a cross- sectional view taken substantially along line IB- IB, line 2B-2B, and line 3B-3B of Figures 7A, 8A, and 9A, respectively.
- each of these figures depicts a hard plastic top having an extension, wherein the extension extends downwardly into the thermoplastic elastomer shaft.
- the extension portion of the hard plastic top allows the production of a more cost-effective product.
- FIG. 7C, 8C, and 9C therein is shown a cross- sectional view taken substantially along line 1C-1C, line 2C-2C, and line 3C-3C of Figures 7B, 8B, and 9B, respectively.
- each of these figures depicts a preferred shape of the extension and exemplary configurations of the interface between the hard plastic top and the thermoplastic elastomer shaft.
- the plurality of longitudinal cogs of the extension portion of the hard plastic top strengthens the coupling between thermoplastic shaft and hard plastic top.
- the bi-compositional synthetic corks of the present invention are typically used as a bottle closure or stopper for liquor, wine, spirits and specialty foods.
- thermoplastic elastomer shaft is a strong material that provides superior properties for such uses, while the hard plastic top makes the closure easy to grasp, remove and reinsert.
- the co-injection molding process is also preferred both because of its cost-effectiveness, and because it permanently attaches the thermoplastic elastomer shaft to the hard plastic top, thereby allowing for multiple openings and resealings of containers with reduced incidence of separation or breakage of the shaft from the top (although other manufacturing processes can also provide such benefits).
- the bi-compositional synthetic corks of the present invention may be produced such that both the hard plastic top and the thermoplastic elastomer shaft are of the same color, or of different colors as desired.
- a composition was formulated by combining three major polymeric components together with an extending oil and minor amounts of processing additives.
- composition was formulated by combining the following ingredients in the following weight percentages: (1) 16.0% by weight of a high crystallinity polypropylene (Profax 6323.
- the formulated composition (i.e., compound no. 18S having approximately 20% PP, 33% TPE, and 47% ethylene- ⁇ -olefin copolymer) was found to have Shore A hardness 74.
- the formulated composition was combined with a blowing agent (Hydroceral CT 1 131, B.I. Chemicals, Unites States) and injection molded at a temperature of about 350°F.
- the resulting synthetic closures were found to have excellent dimensional stability (i.e., no "necking" or shrinkage), resilience, and internal cell structure.
- the synthetic closures were found to have a hard external skin.
- Example 2 A composition was formulated by combining three major polymeric components together with an extending oil and minor amounts of processing additives. Specifically, the composition was formulated by combining the following ingredients in the following weight percentages:
- the formulated composition i.e., compound no. 20S having approximately 15% PP, 41% TPE, and 44% ethylene- ⁇ -olefin copolymer
- Shore A hardness 74 The formulated composition was then combined with a blowing agent (Hydroceral CT 1131, B.I. Chemicals, Unites States) and injection molded at a temperature of about 350°F.
- the resulting synthetic closures were found to have excellent dimensional stability (i.e., no "necking" or shrinkage), resilience, and internal cell structure.
- the synthetic closures were found to have a hard external skin.
- Example 3 A composition was formulated by combining two major polymeric components together with an extending oil and minor amounts of processing additives. Specifically, the composition was formulated by combining the following ingredients in the following weight percentages:
- the formulated composition i.e., compound no. 9 having approximately
- Example 4 A composition was formulated by combining three major polymeric components together with an extending oil and minor amounts of processing additives. Specifically, the composition was formulated by combining the following ingredients in the following weight percentages:
- processing additives ⁇ 1.5% Kemamide E, Witco Polymer Chemical Group, United States, and ⁇ 0.1% Irganox 1010, Ciba Specialty Chemicals, Switzerland.
- the formulated composition (i.e., compound no. 2 having approximately 34% PP, 40%) TPE, and 26% ethylene- ⁇ -olefin copolymer) was found to have Shore A hardness 84.
- the formulated composition was then combined with a blowing agent (Hydroceral CT 1 131, B.I. Chemicals, Unites States) and injection molded at a temperature of about 350°F.
- the resulting synthetic closures were found to have good dimensional stability (i.e., no "necking" or shrinkage), resilience, and internal cell structure.
- the synthetic closures were found to have a hard but somewhat thinner external skin.
- Example 5 A composition was formulated by combining three major polymeric components together with an extending oil and minor amounts of processing additives. Specifically, the composition was formulated by combining the following ingredients in the following weight percentages:
- the formulated composition i.e., compound no. 8 having approximately
- compositions associated with Examples 1-5 may be represented in terms of varying ranges associated with the composition, namely; a thermoplastic elastomer component ranging from 25% to 75% (weight basis); an ethylene- ⁇ -olefin copolymer component ranging from 15% to 65% (weight basis); and a polypropylene polymer component ranging from 0% to 50% (weight basis).
- the polymeric materials that comprise the synthetic closures of some embodiments of the present invention may be represented as a compounded polymeric material that includes a thermoplastic elastomer, an ethylene- ⁇ -olefin copolymer. and a polypropylene polymer, wherein the relative amounts on a weight percent basis of the thermoplastic elastomer, the ethylene- ⁇ -olefin copolymer. and the polypropylene polymer vary with one another in the manner as set forth in the expression shown in Figure 10 (wherein the underlying polymeric compositions of Examples 1-5 have been plotted).
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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- Closures For Containers (AREA)
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Abstract
Description
Claims
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU13404/00A AU1340400A (en) | 1998-11-04 | 1999-11-02 | Synthetic closure for bottle-like containers |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US10714598P | 1998-11-04 | 1998-11-04 | |
US60/107,145 | 1998-11-04 |
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WO2000026103A1 WO2000026103A1 (en) | 2000-05-11 |
WO2000026103A9 true WO2000026103A9 (en) | 2000-09-28 |
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PCT/US1999/025862 WO2000026103A1 (en) | 1998-11-04 | 1999-11-02 | Synthetic closure for bottle-like containers |
Country Status (4)
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AR (1) | AR021100A1 (en) |
AU (1) | AU1340400A (en) |
WO (1) | WO2000026103A1 (en) |
ZA (1) | ZA996914B (en) |
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CN106751362A (en) * | 2016-12-05 | 2017-05-31 | 中广核三角洲集团(苏州)特威塑胶有限公司 | A kind of high temperature resistant halogen-free flame-retardant thermoplastic elastomer cable material |
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EP1192090B1 (en) * | 1999-07-05 | 2006-08-30 | Kraton Polymers Research B.V. | Synthetic bottle stopper |
WO2001014219A1 (en) * | 1999-08-20 | 2001-03-01 | Supreme Corq. Inc. | Secondary synthetic closure for sealing corked bottles or containers |
ES2169992B1 (en) * | 2000-04-06 | 2003-05-01 | Aycart Eduardo Ortiz | PROCEDURE FOR THE MANUFACTURE OF PLUGS FOR BOTTLES AND PLUGS MANUFACTURED BY MEANS OF THIS PROCEDURE. |
ATE266515T1 (en) * | 2000-04-06 | 2004-05-15 | Aycart Eduardo Ortiz | METHOD FOR PRODUCING BOTTLE STOPPERS AND BOTTLE STOPPERS PRODUCED BY SUCH METHOD |
FR2821609A1 (en) * | 2001-03-01 | 2002-09-06 | Eric Albert Rodius | Elastomeric stopper suitable for wine bottles, is made from elastomer base including clear reinforcing additives, colorants and plasticizers |
FR2840846B1 (en) * | 2002-06-14 | 2005-06-03 | C Q F D | METHOD AND DEVICE FOR MANUFACTURING A PLUG FROM POLYMERS BY DIRECT INJECTION OF GAS |
US7037979B2 (en) | 2002-09-04 | 2006-05-02 | Delphi Technologies, Inc. | Thermoplastic polyolefin compositions and methods of preparing thermoplastic polyolefin compositions for soft sheet applications |
FR2845665B1 (en) | 2002-10-15 | 2005-06-24 | Eric Rodius | PLUG FOR FILLING CONTAINERS AND ESPECIALLY BOTTLES OF STILL OR SMALL WINES THE ACTIVE PART OF WHICH ENABLES SEALING IS CARRIED OUT IN TWO PARTS |
WO2004035408A1 (en) | 2002-10-15 | 2004-04-29 | Eric Rodius | Cork with prestressed elastomer skin |
EP1631504A1 (en) * | 2003-05-26 | 2006-03-08 | Nicola Fantin | Structure of closure for closing liquid containers |
DE60331530D1 (en) * | 2003-06-27 | 2010-04-15 | Kraton Polymers Res Bv | Foamable polymer compositions and articles containing foamed compositions |
ES2257128B1 (en) * | 2003-10-07 | 2007-07-01 | Victor Javier Boldova Hernandez (Titular Al 50%) | COMPOSITION OF A PLASTIC MATERIAL FOR PLUGS AND PLUG AS OBTAINED. |
EP1541482A1 (en) * | 2003-12-09 | 2005-06-15 | Vintec S.r.l | Low permeability device for closure of barrels |
BRPI0415116A (en) * | 2004-09-03 | 2006-11-28 | Kraton Polymers Res Bv | foamable compositions, foamed articles, and premixtures for the preparation of foamable compositions |
EP1746037A1 (en) * | 2005-07-22 | 2007-01-24 | Microcell S.r.L. | Stopper for bottle for wine and similar drinks and process for production of said stopper |
KR100856166B1 (en) | 2006-04-24 | 2008-09-03 | 크레이튼 폴리머즈 리서치 비.브이. | Foamable polymeric compositions and articles containing foamed compositions |
EP2292685B1 (en) | 2009-09-07 | 2012-06-27 | The Procter & Gamble Company | Bottle cap made from a material comprising polypropylene, particulate calcium carbonate and additives |
US8973781B2 (en) | 2009-09-30 | 2015-03-10 | Kuraray Co., Ltd. | Container stopper comprising foam-molded article |
CN104220341B (en) | 2011-11-11 | 2017-11-28 | 诺玛科公司 | Closeouts for product holding container |
AU2013205007B2 (en) * | 2013-02-02 | 2016-05-26 | Nomacorc Llc | Closure for a product-retaining container |
AU2013204542A1 (en) | 2013-04-05 | 2014-10-23 | Nomacorc Llc | Closure for a Product-Retaining Container |
WO2016020361A1 (en) * | 2014-08-07 | 2016-02-11 | Nomacorc Llc | Closure for a product-retaining container |
CN110903629A (en) * | 2019-12-21 | 2020-03-24 | 惠安伟盛鞋业有限公司 | High-elasticity wear-resistant polyurethane foamed shoe material and preparation method thereof |
IT202100030356A1 (en) * | 2021-11-30 | 2023-05-30 | Flon Project S R L | A CAP MADE OF A CLOSED CELL POLYMER COMPOSITE MATERIAL PROVIDED WITH AN AIR PASSAGE DUCT OBSTRUCTED BY AN e-PTFE MATERIAL |
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1999
- 1999-11-02 AU AU13404/00A patent/AU1340400A/en not_active Abandoned
- 1999-11-02 WO PCT/US1999/025862 patent/WO2000026103A1/en active Application Filing
- 1999-11-03 ZA ZA9906914A patent/ZA996914B/en unknown
- 1999-11-05 AR ARP990105601A patent/AR021100A1/en unknown
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106751362A (en) * | 2016-12-05 | 2017-05-31 | 中广核三角洲集团(苏州)特威塑胶有限公司 | A kind of high temperature resistant halogen-free flame-retardant thermoplastic elastomer cable material |
CN106751362B (en) * | 2016-12-05 | 2019-05-10 | 中广核三角洲集团(苏州)特威塑胶有限公司 | A kind of high temperature resistant halogen-free flame-retardant thermoplastic elastomer cable material |
Also Published As
Publication number | Publication date |
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AR021100A1 (en) | 2002-06-12 |
WO2000026103A1 (en) | 2000-05-11 |
ZA996914B (en) | 2000-05-17 |
AU1340400A (en) | 2000-05-22 |
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