AU7152800A - Multilayer synthetic stopper - Google Patents
Multilayer synthetic stopper Download PDFInfo
- Publication number
- AU7152800A AU7152800A AU71528/00A AU7152800A AU7152800A AU 7152800 A AU7152800 A AU 7152800A AU 71528/00 A AU71528/00 A AU 71528/00A AU 7152800 A AU7152800 A AU 7152800A AU 7152800 A AU7152800 A AU 7152800A
- Authority
- AU
- Australia
- Prior art keywords
- stopper
- polymer portion
- polymer
- approximately
- density polyethylene
- Prior art date
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- Granted
Links
- 229920000642 polymer Polymers 0.000 claims description 156
- 238000000034 method Methods 0.000 claims description 37
- 239000000203 mixture Substances 0.000 claims description 29
- 229920005989 resin Polymers 0.000 claims description 27
- 239000011347 resin Substances 0.000 claims description 27
- 229920000554 ionomer Polymers 0.000 claims description 17
- 229920001684 low density polyethylene Polymers 0.000 claims description 16
- 239000004702 low-density polyethylene Substances 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 16
- 229920000098 polyolefin Polymers 0.000 claims description 14
- 239000004604 Blowing Agent Substances 0.000 claims description 13
- 239000011248 coating agent Substances 0.000 claims description 11
- 238000000576 coating method Methods 0.000 claims description 11
- 238000001125 extrusion Methods 0.000 claims description 11
- -1 polypropylene Polymers 0.000 claims description 11
- 229920001577 copolymer Polymers 0.000 claims description 10
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 9
- 239000005977 Ethylene Substances 0.000 claims description 9
- 238000003780 insertion Methods 0.000 claims description 9
- 230000037431 insertion Effects 0.000 claims description 9
- 229920003145 methacrylic acid copolymer Polymers 0.000 claims description 9
- 229920001971 elastomer Polymers 0.000 claims description 8
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 claims description 7
- 229920001903 high density polyethylene Polymers 0.000 claims description 7
- 239000004700 high-density polyethylene Substances 0.000 claims description 7
- 239000004743 Polypropylene Substances 0.000 claims description 6
- 239000000806 elastomer Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 6
- 229920001155 polypropylene Polymers 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 3
- 238000005516 engineering process Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 230000000704 physical effect Effects 0.000 claims 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims 2
- 241000133063 Trixis Species 0.000 claims 1
- 102100036788 Tubulin beta-4A chain Human genes 0.000 claims 1
- 239000010410 layer Substances 0.000 description 28
- 235000014101 wine Nutrition 0.000 description 18
- 239000007799 cork Substances 0.000 description 15
- 239000006260 foam Substances 0.000 description 10
- 239000005038 ethylene vinyl acetate Substances 0.000 description 8
- 238000007789 sealing Methods 0.000 description 7
- 239000003351 stiffener Substances 0.000 description 7
- 239000002023 wood Substances 0.000 description 7
- 229920003023 plastic Polymers 0.000 description 6
- 239000004033 plastic Substances 0.000 description 6
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 description 5
- 230000035882 stress Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 229920003345 Elvax® Polymers 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000006835 compression Effects 0.000 description 4
- 238000007906 compression Methods 0.000 description 4
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 4
- 229920001169 thermoplastic Polymers 0.000 description 4
- 239000004416 thermosoftening plastic Substances 0.000 description 4
- 229920002160 Celluloid Polymers 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000001993 wax Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 102100024133 Coiled-coil domain-containing protein 50 Human genes 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 101000910772 Homo sapiens Coiled-coil domain-containing protein 50 Proteins 0.000 description 2
- 239000004831 Hot glue Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 229920003182 Surlyn® Polymers 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 229910052806 inorganic carbonate Inorganic materials 0.000 description 2
- 239000001282 iso-butane Substances 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 150000003871 sulfonates Chemical class 0.000 description 2
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- 230000037303 wrinkles Effects 0.000 description 2
- RNAMYOYQYRYFQY-UHFFFAOYSA-N 2-(4,4-difluoropiperidin-1-yl)-6-methoxy-n-(1-propan-2-ylpiperidin-4-yl)-7-(3-pyrrolidin-1-ylpropoxy)quinazolin-4-amine Chemical compound N1=C(N2CCC(F)(F)CC2)N=C2C=C(OCCCN3CCCC3)C(OC)=CC2=C1NC1CCN(C(C)C)CC1 RNAMYOYQYRYFQY-UHFFFAOYSA-N 0.000 description 1
- 239000004156 Azodicarbonamide Substances 0.000 description 1
- 229920003941 DuPont™ Surlyn® 1652 Polymers 0.000 description 1
- 241001411320 Eriogonum inflatum Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229920002633 Kraton (polymer) Polymers 0.000 description 1
- 206010063493 Premature ageing Diseases 0.000 description 1
- 208000032038 Premature aging Diseases 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000003679 aging effect Effects 0.000 description 1
- 235000019568 aromas Nutrition 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 description 1
- 235000019399 azodicarbonamide Nutrition 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002666 chemical blowing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- BXOUVIIITJXIKB-UHFFFAOYSA-N ethene;styrene Chemical group C=C.C=CC1=CC=CC=C1 BXOUVIIITJXIKB-UHFFFAOYSA-N 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 125000005313 fatty acid group Chemical group 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000003077 lignite Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- CSMWJXBSXGUPGY-UHFFFAOYSA-L sodium dithionate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)S([O-])(=O)=O CSMWJXBSXGUPGY-UHFFFAOYSA-L 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- CLYZNABPUKUSDX-UHFFFAOYSA-N trichloromethoxybenzene Chemical compound ClC(Cl)(Cl)OC1=CC=CC=C1 CLYZNABPUKUSDX-UHFFFAOYSA-N 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
Landscapes
- Closures For Containers (AREA)
Description
AUSTRALIA
PATENTS ACT 1990 COMPLETE SPECIFICATION NAME OF APPLICANT(S): Neocork Technologies, LLC ADDRESS FOR SERVICE: DAVIES COLLISON CAVE Patent Attorneys 1 Little Collins Street, Melbourne, 3000.
INVENTION TITLE: Multilayer synthetic stopper The following statement is a full description of this invention, including the best method of performing it known to me/us:- BACKGROUND OF THE TVENTTON Field of the Tnvention The invention relates to bottle stoppers and more particularly to synthetic stoppers for use in wine bottles and other similarly packaged products.
Descriptij. of Related Art Natural cork is the most common material for making stopper-type bottle closures. The use of cork to finish wine and other food products dates back centuries. Natural cork is a wood product. The disadvantages of the use the natural wood product are well-known. These disadvantages include, inconsistency in structure leading to leakage and premature aging of the bottle contents, susceptibility of the contents to contamination from trichloroanisole (TCA) which gives the bottle contents a musty aroma, and a tendency to dry and crumble with age, storage, or dry environments.
Alternatives to natural cork stoppers have been known for many years. U.S. Patent No. 466,169 issued to Hume discloses a stopper formed of a strip of textile material, such as canvas, filled with rubber and rolled up in the shape of a tapered stopper. The resulting stopper structure consists of a core of textile material surrounded and enveloped with rubber. U.S. Patent No. 512,705 issued to Holmes discloses a method of making a cork-like stopper of fiber pulp by pressing the pulp into proper form in suitable molds. The stopper can be used directly from the mold.
However, in order to render the stopper water and acid proof, the stopper is dipped in melted paraffin wax.
N, Uj-4u O41 OM ~rUni-)4I L L.h ;0VL40U1;Q r ij o r-rijjji Synthetic closures have also been developed to remedy the disadvantages associated with natural wood bark cork.
For example, U.S. Patent No. 281,333 issued to Barrett discloses a method of making a stopper consisting of pressing or forcing suitable plastic material, such as lignite, into a tube in a mold of v-ulcanite, xylonite, celluloid, or like material. The molded stopper produced is of a plastic material with a skin of vulcanite, xylonite, ce'lluloid, or like material. U.S. Patent No. 5,480,915 issued to Burns discloses the use of a thermoplastic elastorner and a commercially available blowing agent injection molded to form a porous cork-like structure. U.S. Patent No. 4,188,457 issued to Throp discloses the use of a foamn plastic injection-molded closure made with an ethylene vinyl acetate (EVA) polymer formed with sodium metabisuilphite. French Patent No. 1,518,450 issued-to Daicel Ltd. describes a closure produced by compressing a mat of thermoplastic fibers to form a porous plug. U.S. Patent No. 4,042,543 issued to Strickran, et al., describes a stopper that combines a polymer with cork particles. European Patent Application 92100058.4 filed by Fantin on January 9, 1991, and published July 29, 1992, describes a plastic stopper with a cylindrical elastic insert made of granulated cork or a high density plastic material with resilient characteristics, or natural or synthetic rubber.
The difficulty with these-prior art structures ar 'e nlumerous. First, the synthetic stoppers are not compatible with conventional cork insertion machinery. A standard wine bottle throat or neck has an inside diameter of approximately 18. 5 mmn 0. 5 mm. Thus, a stopper must have a slightly larger diameter to properly seal the bottle. Cork insertion machinery is used t--o compress the stopper and insert the riU4 -1b-4UUU <U0:i 44pa; r(Ulro-0 IIl Lh -Iu ucVY QV I-44a r, vwve at r-y U i stopper into the neck of the bottle. Upon compression in the cork insertion machinery, the cork's diameter is reduced to approximately 15.0 mm diameter. The prior art stoppers cannot withstand the compression of the corking equipment without cutting, creasing, or wrinkling. This is particularly true with those stoppers whose inner density or elasticity is less than their outer density or elasticity.
In such cases, the compression machinery overcomes the resistance of the outer walls of the stopper, causing the stopper to cut, crease, or wrinkle. A cut, creased, or wrinkled stopper will not completely expand to its desired shape in the bottle and thus will not properly seal the bottle. U.S. Patent No. 4,091,136, issued to O'Brien, et seeks to remedy the problem of creasing or wrinkling by abrading or cutting off the outer, more dense, layer of its extruded polymer foam stopper, then coating the remaining polymer foam with a wax. This necessitates extra process steps and creates a great deal of wasted material and dust particles.
Other difficulties associated with prior art stoppers Sinclude a difficulty in extraction of the stopper from the bottle due to poor closure compressibility; poor compressive and sealing properties; and the possibility of extraction of undesirable taste and aromas from plasticizers and other additives or from a chemical reaction between the stopper and the wine. Finally, a significant obstacle to the use of the thermoplastic stoppers is the relatively high cost associated with producing thermoplastic stoppers by a conventional injection molding process.
SUMMARY OF THE TNVENTION A stopper for use in substantially cylindrical bottle opening is disclosed. The stopper has a substantially cylindrical shape to seal the bottle opening and includes a first polymer portion and a second polymer portion, wherein the second polymer portion coaxially overlies the first polymer portion. In one embodiment, the first polymer portion includes a polyolefin. In another embodiment, the first polymer portion includes a mixture of polymers, for example ethylene/methacrylic acid co-polymer based ionomer resin, and low density polyethylene. In one embodiment, the 00 second polymer portion is an ionomer resin, for example, ethylene/methacrylic acid co-polymer based ionomer resin, or an elastomeric resin, such as ethylene vinyl acetate (EVA) copolymer. The second polymer portion may function as a tough, cut-resistant outer skin such as in the ionomer example, or a flexible, elastomeric skin, such as in the EVA example, that provides an excellent seal against the bottle neck.
In another embodiment, the stopper includes a third polymer portion wherein the first polymer portion coaxially overlies the third polymer portion and wherein the third S" polymer portion is one of a high density polyethylene polymer and a high density polypropylene polymer. In this embodiment, the third polymer portion acts as a center core of a relatively stiff polymer that is overcoated with a more resilient polymer, which is in turn overcoated with either a cut-resistant skin layer, such as an ionomer, or a flexible, elastomeric skin, such as EVA, for improved sealing properties.
Also disclosed is a method of protecting liquid in a bottle with a substantially cylindrical bottle opening. The 1 -1 1 method includes providing a stopper having a substantially cylindrical shape to seal the bottle opening and closing off the bottle by insertion of the stopper into the bottle opening. The stopper has a first polymer portion and a second polymer portion, wherein the second polymer portion overlies the first polymer portion.
Further disclosed is a method of producing a stopper for use in a substantially cylindrical bottle opening. In one embodiment, the method includes extruding a first polymer portion through an extrusion die, coaxially coating the first polymer portion with a second polymer portion to form a body, and forming the body into a shape to substantially seal the bottle opening. The first polymer portion and the second material portion may be formed by coextrusion in a coaxial manner or in a step-wise manner utilizing cross-head or other known extrusion techniques.
In a second embodiment of a method of producing a stopper for use in a substantially cylindrical bottle opening, the method includes extruding a first polymer portion through an extrusion die, coaxially coating the first polymer portion with a second polymer portion, coaxially coating the second polymer portion with a third polymer portion to form a body, and forming the body into a shape to substantially seal the bottle opening. Once again, the coaxial extrusion may be performed simultaneously or in a step-wise manner utilizing cross-head or other known techniques.
These and other aspects of the invention will become evident upon reference to the following detailed description and attached drawings.
IHUV-3IB'J l. j Ji H r I U I 1 .r uu< i+ i BRIEF DESCRIPTION OF TJE DRAWINGS Figure 1 is a planar side view of a bottle with the multi-layer stopper of the invention inserted in the.
substantially cylindrical bottle opening.
Figure 2 is a front perspective view of an embodiment of the stopper of the invention illustrating a shape of the stopper body.
Figure 3 is a perspective cut-away view of the stopper shape of Figure 2 illustrating a first embodiment of the multi-layer structure of the stopper taken through line A-A of Figure 2.
Figures 4-6 demonstrate a method of forming the multilayer stopper in accordance with the invention, specifically the embodiment wherein the stopper is comprised of two layer portions and is formed in a step-wise manner.
Figure 4 is a planar side view of a formed first polymer portion being fed into a cross-head die along with a second polymer portion.
Figure 5 is a planar side view wherein a formed first polymer portion is brought into contact with a second polymer portion in the cross-head die.
Figure 6 is a planar side view of a multi-layer stopper rod leaving the cross-head die.
Figures 7-9 demonstrate a method of forming the multilayer stopper in accordance with the invention, specifically an embodiment wherein the multiple layers are extruded simultaneously.
Figure 7 is a planar side view of a first polymer portion and a second polymer portion inserted into a coextrusion die.
Figure 8 is a planar side view wherein the first polymer portion is brought into contact with the second polymer portion.
Figure 9 is a planar side view of the multi-layer stopper rod as it leaves the co-extrusion apparatus.
Figure 10 is a perspective cut-away view of the stopper shape of Figure 2 illustrating a second embodiment of the multi-layer structure of the stopper taken through line A-A of Figure 2.
Figures 11-13 demonstrate a method of forming a multilayer stopper in accordance with the invention, specifically i* the embodiment wherein the stopper includes three layer S. portions, each having different properties.
Figure 11 is a planar side view of a first polymer portion, and being coaxially coated by a second polymer portion.
Figure 12 is a planar side view of a multi-layer portion being coaxially coated by a third polymer portion.
Figure 13 is a planar side view of a stopper rod leaving the co-extrusion die and being comprised of three layer portions.
Figure 14 is a perspective cut-away view of the stopper shape of Figure 2 illustrating a third embodiment of the multi-layer structure of the stopper taken through line A-A of Figure 2.
Figure 15 is a perspective cut-away view of the stopper shape of Figure 2 illustrating a fourth embodiment of the multi-layer structure of the stopper taken through line A-A of Figure 2.
NL'V-IJW'V -Ui riuIrl' i t Lh DETAILED DESCRIPTTON OF THE INVENTION A multi-layer stopper, a method for making a multilayer stopper, and a method for using a multi-layer Stopper to protect liquid in a bottle is described. In the following detailed description, numerous specific details are set forth, such as specific materials, forms, and properties, as well as specific methods of manufacture, in order to provide a thorough understanding of the invention.
It will be clear to one skilled in the art, however, that these specific details need not be employed to practice the invention.
In one aspect of the invention, there is provided a multi-layer stopper for use in a bottle opening as a suitable replacement for natural wood bark cork.
Accordingly, the invention features a stopper for use in a substantially cylindrical bottle opening, preferably a wine bottle opening, having a substantially cylindrical shape to be disposed in the bottle opening, thereby preventing spillage of the bottle contents and preventing passage of e1 •oxygen from the atmosphere to the contents, wine. In one embodiment, the body is made up of a first polymer portion and a second polymer portion that overlies the first polymer portion in a coaxial alignment. In another embodiment, the stopper is made up of a "core" of one polymer, coaxially surrounded by another polymer having properties different than the core polymer, and coaxially surrounded by a third polymer portion. The multi-layer embodiments highlighted provide the stopper with superior compressive and sealing properties compared to other synthetic stoppers or natural wood bark corks.
Figure 1 illustrates a planar side view of a bottle with a stopper 100 of the invention inserted in the substantially cylindrical bottle opening of the bottle Figure 1 illustrates that the stopper 100 functions similar to natural wood bark corks to finish wine.
Figure 2 illustrates a perspective view of a contemplated shape of stopper 100 of the invention. Stopper 100 is formed of multi-layer portions. Figure 2 shows an embodiment where letters are printed on the stopper body.
In this embodiment, stopper 100 can retain printed matter on the surface that contacts the container. For example, a producer's or manufacturer's name, logo, or other trademark may be displayed on stopper 100.
Figure 3 shows an embodiment of stopper 100 taken through line A-A of Figure 2. The embodiment shown in Figure 3 includes a first polymer portion 110 and a second polymer portion 120 overlying, in a coaxial alignment, polymer portion 110. In this embodiment, polymer portion 110 is, for example, a mixture of a polyolefin blend of metallocene co-polymers and high melt strength (low melt index), low density polyethylene (LDPE). Typically, preferred low density polyethylene resins have a melt index of from 0.5 to 10 and a density of from about 0.910 to 0.935 gm/cc. An example of a polyolefin blend of metallocene copolymers include, but are not limited to, those manufactured by The Dow Chemical Co., Midland, Michigan, and bearing the trademark Dow Affinity PF1140®. A suitable low density -7 polyethylene includes, but is not limited to, one manufactured by Dow Company, and bearing the trademark Dow 6621®. Other suitable components for polymer portion 110 include, but are not limited to, ethylene vinyl acetate (EVA), such as manufactured by E.I. du Pont de Nemours Co., Wilmington, Delaware, and bearing the trademark ELVAX I1;t V 4U 6 kou;4UJLJI rI L'z Ia* U110 4 6t% 56001D, and blends of polyolef ins and styrene- butadiene copolymer, such as manufactured by Shell Chemical Co. under the trademark X-ATON 1010. Generally, polyethylenes.polypropylenes, and blends of the samne or blends with styrene ethylene butadiJene styrene (SEBS).
To form polymer portion 110, a polyolefin blend of metallocene co-polymers, such as Dcw Affinity 11400 and a low density polyethylene such as Dow 6621I® are mixed and processed by standard foam extrusion mneans to form a foamed polymer profile of slightly smaller diameter than the desired final diameter of the stopper. A closed-cell foamed 4. polymer portion 110 can be formed with the desired suppleness and resiliency with the proper selection of polymer blending ratios and control of the foam density. in one embodiment, the blend consists of a 3:1. ratio of metallocene co-polymers Dow Affinity EPF1140@) to low density polyethylene Dow 6621®"), by weight. Polymer portion 110 may further contain a small amount of an ionomi 1resin. lonomer resins increase the toughness, the resiliency, and the barrier properties of stopper 100.
Suitable iononier resins include, but are not limited to, those derived from ethylene/methacrylic acid co-polymers.
They are generally known as SURLYN@ ionomers. SURLYN is a registered trademark off E.I. du Pont de Neimours, Co.
StJRLYN ionomer resins are compatible with polyolef ins and may be used in amounts ranging from 0.2% to 50% by weight of polymer portion 110. One embodiment con~temnpflates ionomer resin in the range of 0.5-5% by weight of polymer portion 110.
In another lembodiment of the invention, polymer portion 1110 is combined with 3ne or more blowing agents. The combination of a blowing agent with a pol~ymer is well-known in the plastics processing art. The blowing agent provides calls in the polymer body which give the stopper additional flexibility. The blowing agent is generally present in an amount less than 10% of the total polymer composition, and, in one embodiment, is in the range from about 1% to about 3% of the polymer composition. Of course, the precise amount of blowing agent may be determined by one skilled in the art taking into account the precise polymer, blowing agent, and other ingredients uzed, as well as the molding conditions.
Suitable blowing agents include, but are not limited to, chemical blowing agents including 51F40, commercially available from BI Chemicals, Montelaire, New Jersey, SPElCTR~ATECOi FM215Oli, commercially available from Quantum Chemical Corp., USI Division, Cincinnati, Ohio, azodicarbonamide, azodecarbonoxide, inorganic carbonates like sodium bicarbonate, inorganic sulfonates, sodium metabisulfate, and 2,2' -dialkoxy-2,2 '-azopropanes sulfonyl *semicarbizides, adsulfazides.
The properties of the stopper body associated with the 00 blowing agent can also be obtained by the use of direct pressurization of the polymer in the mold or extruder barrel by physical blowing agents, including but not limited to, nitrogen, CFCs, C02, sulfur hexafluiorides, carbon dioxide, HFCs, butane, or isobutane. Cell formation is assisted by the presence of nucleating agents suc.,h as talc or CELOGENO, manufactured by Uniroyal Chemical, Middlebury, Corznecticutt.
In one embodiment, the density of polymer portion 110 is 15 pounds per cubic feet Cib./cu.ft.), with a cell size of 0.5 millimeters (mm) or less. Further, the outer diameter of polymer portion 110 is approximately 0.5-1.0 mun WU- LU-j. u p uijII! rnuI- Ltru Ln j vd v W V I-UO r.viu/uw t r-U ui smaller than the desired final diameter of stopper 100 (22mm).
In one embodiment, presented schematically in Figures 4-6, polymer portion 110 is fed into a cross-head die (Figure where an outer polymer portion 120 of a tough, cut-resistant polymer foam, such as an ionomer resin, is coaxially coated over the profile (Figure For example, a low melt flow resin such as an ionomer resin like SURLYN 1652®, is coated over polymer portion 110 to a thickness of approximately 2 mn.
Powder or liquid pigments may be added to outer material portion 120 to give the stopper a desired color or tint. The powder or liquid pigments generally constitute less than 1% of the total composition. Other additives may also be included to impart various desired properties.
These additives include hardening or crosslinking agents, surfactants, and viscosity modifiers. Further, a lubricant such as a fatty acid, a silicone, an alcohol, or water (including mineral water) may be added before or after extrusion. The lubricant facilitates the insertion and removal of the stopper into or from the bottle opening, respectively. Preferably the lubricant is a fatty acid and comprises less than about 0.5% of the total composition.
Figure 6 shows a multi-layer stopper rod exiting the cross-head die. The stopper rod includes polymer portion 110 coaxially covered with polymer portion 120. Once the stopper rod exits the die, the stopper rod may be cut into appropriate stopper lengths.
In another embodiment, presented schematically in Figures 7-9, the multiple layers, polymer portion 110 and polymer portion 120 may be extruded simultaneously. As I4QVTUV_4UQ q4. .tupjw rivavuzlI~ Lr V y I r.0 i J% r-w4 i shown in F'igure 7, both a polyolefin blend as described above arnd an ionomez resin are added to the crossheadi die approximately simultaneously. The jonomer resin forms an outer layer coaxially over the polyolofin blend in Figure 8.
In Figure 9, a multi-layer stopper rod is extruded from the crosshead die.
The embodiment described above with reference to Figures 3-9 illustrates a stopper having polymer portion 120 that. is an outer skin of a tough, cut-resistant polymer.
Other components can be used to achieve other desired skin properties, such as frictional or sealing properties beneficial for the use of a synthetic 'cork in a wine bottle.
For example, foamed polymer portion '110, as in the previous embodiment, can be similarly fed into a cross-head coating die, wherein polymer portion 110 is coaxially coated with a 0.5-1.0 mm layer of a soft hot-melt adhesive system. An exemplary soft hot-melt adhesive system is a polyolefin wax such as BAYMEL 0 D. BAYMELO is a trademiark of International 0Group, Inc., Wayne, Pennsylvania. The adhesive system is an elastomer that provides an excellent seal against a glass bottle neck and is sufficiently flowable so as to 9 heal" any cuts or wrinkles resulting from insertion operation, e.g., such as may develop through the "use of the cork insertion machinery. Examples of other componEnts for polymer portion 120 include materials with an elastic modulus and recovery properties that include, but are not limited to, elastomers such as the styrene-butadiene KRATON®) XRATONG® manufactured by Shell Chemical Co., Houston, Texast SEBS (e.g.e SEBS 0117-50, a compound off SEBS with polyp ropylene) m-anufactured by M.A. Hanna, North Rid~geville, Ohio, and ELVAx 4500 EVA manufactured by E.I. dlu Pont de Nemours Co.
Pigments or other additives may be added to these alternative material portion 120 components as noted above.
One embodiment includes a 0.880 inch diameter foamed polymer portion 110 of Dow 6621 LDPBE and Dow PF 1140 Affinity resin in a weight ratio of 25% LDPS to 75% resin.
A butane blowing agent is used to yield a density of 22 pounds per cubic foot. The stopper has an outer elastomeric po2.ymer portion 120 having a thickness of approximately" 0.005 inches is Hlanna XL0117-5 that coaxially overlies polymer portion 110.
Figure 10 illustrates another embodiment of the :invention. Figures 11-13 present a riethod of producing this embodiment. Figure 10 shows an embodiment created with the p-urpose of minimizing ".stress creep" In stopper technology, "stress creep" i~s the tendency of the stopper to lose its holding force against the wine bottle throat over a period of time. Ideally, stress creep should be minimized so that the stopper maintains its mtaximum holding force over time. in the embodiment shown in Figure 10, and the process .presented in Figures 11-13, a center "core" 130 of a relatively stiff, low stress creep foam, for example, foamed high density polyethylene (EDPE), is inserted into a crosshead die (Figure 12.) and coaxialIly overcoated as above (as shown in Figure 12) with a more resilient polymer 140, such as a ffoamed mixture of a polyolefin blend of motallocene copolymers and a low density polyethylene as described above with reference to polymer portion 110 of Figure 3. As shown i.n Figure 13, polymer core 130 and polymer second layer 140 are in turn coaxially o'Jercoated with a cut-resistant skin layer 150, such as a SURLYN6 ionorner or an elastomer such as ELVAX 560® EVA or ELVAX 4500 EVA.
1~4. 1 h0fl V4 .I .lV Q.4 I vu., r In one embodiment, a generic high density polyethylene, such as for example, PETROTHENEO, manufactured by U.S.
industrial Chemicals Company, New York, New York, is-foamed with a chemical or physical foamning agent, that can include, but is not limited to, azodicarbainides, inorganic carbonates, inorganic sulfonates, 2,2 '-dialkoxy-2, 2'azopropanes sulfonyl semicarbaziies, sulfazides, carbon dioxide, HFCs, and isobutane. In one embodiment, the foam diameter of core 130 is 12 mm with a density of 22-25 lb./cu.ft. Core foam 130 is co-extruded with a first coaxial coating layer 140 consisting of a polyolefin blend Dow Affinity 1140) and low density polyethylene Dow 6621) in a proportion of 85:15. The thickness of polymer layer 140 is 9-12 mm and has a density of V lb./cu.ft. A second coaxial coating layer 150 is coextruded to form an outer skin layer 150 that is either tough and cut-resistant (such as an ionomer resin) or that maximizes frictional or zealing properties (such as a polyolefin wax) Figures 14 and 15 illustrate still other embodiments of *the multi-layer stopper of the invention. Figure 14 and Figure 15 are side perspective view of distinct embodiments of the stopper of the invention taken throu~gh line A-A of Figure 2. Figures 14 and 15 show emnbodiments where a resilient polymer foam is co-extruded with a stiffener geometry 160 and 180, respectively. Stiffeners 160 and 180 may be a more dense foam or solid, and may take the form of either a cylinder, Figure 14, or a "pinwheel" or similar configuration that has at least three-fold radial symmetry, Figure 15. The embodiment shown in Figure has the advantage that its stiffener geometry may be !.uvru-(uuu I;.LIii rflUi-olai LA 4IUOBualaeo 1-4w I.UI/Uj4 chosen so as to form a spring-like tension for maintaining proper sealing force against the inside of the bottle neck over extended periods of storage, minimal stress creep.
The stiffener 160 or 180 of Figure 14 or Figure respectively, is coaxially coated with a resilient polymer portion 170 or 190, respectively, that is, for example, a mixture of a polyolefin blend of metallocene co-polymers and a low density polyethylene. In the embodiment shown in Figure 14, polymer portion 170 coaxially covers stiffener 160 and is extruded to fill the substantially cylindrical opening of stiffener 160. The embodiment shown in Figure is coaxially overcoated with a skin 200, as described above, specifically with reference to Figure One example of a stopper 100 as shown in Figure 15 is formed as follows. First, a stiffener portion 180 of polypropylene, such as Amoco 8410® is co-extruded with a polymer 190 consisting of a 85:15 blend of polyolefin a Dow Affinity 1140®) and low density polyethylene Dow 6621®). The resulting structure is coaxially overcoated with a material portion 200 that is a 0.5 mm skin of an elastomer.
It is to be appreciated that the embodiments of the multi-layer stopper of the invention discussed herein, may be formed simultaneously, via co-extrusion, or sequentially by a series of coating steps. Both methods have been presented with respect to alternative stopper embodiments.
The stopper described in each of the above embodiments of the invention is inert in wine and other food products and will not absorb gases or other components from the l-biul I*W. hV V r l I I Vll r .U L hI I .wb f r gU i bottle contents or the head space within, for example, a wine bottle between the stopper and the contents. The stopper will also not allow significant amounts of air to reach the interior of the bottle. The stopper may be used over an extended period as, for example, in accordance with the desired aging properties of many wines. The stopper resists reaction of solvaticn and alcohol, acid, or base and does not taint the wine with any chemical or smell.
The stopper of the invention is compatible with cork insertion machinery. The invention contemplates that the stopper can withstand the compression of the machinery without cutting, creasing, or wrinkling.
The stopper of the invention seals the standard wine bottle and permits the wine bottle to be stored immediately in any position, including on the bottle's side or inverted.
The sealing properties of the stopper will allow it to withstand typical bottle head space pressure changes. For example, wines are often bottled at approximately 50-55"F but can be exposed to 80-100'F during shipping and storage.
This temperature change can create head space pressure changes in the bottles. The sealing properties of the stopper of the invention can withstand such head space pressure changes. Further, many wines are bottled with a slight "fizz" of C02 that remains in the bottle after the stopper is installed in the bottle opening. The stopper of t the invention can withstand head space pressure changes due to residual C02 in the bottle.
The stopper of the invention is easily extractable with conventional corkscrews. The stopper can be removed with a conventional corkscrew without substantial expansion, crumbling, or disintegration.
NOV-0y-UUl" L:ZIPm roIm-SIL LA 1lUotuUcw U I-Ue r.Uv&i Ua r-o a The stopper of the invention retains its resiliency against the bottle wall over time thus maintaining the same seal as when bottled. This allows wines to be aged .for many years without being exposed to environmental oxygen.
The stopper of the invention can resemble natural wood bark corks although other colors are contemplated. Further, the stopper is printable to allow a company's name or logo to be imprinted on the side of the stopper.
In the preceding detailed description, the invention is described with reference to specific exemplary embodiments thereof. It will, however, be evident that various modifications and changes may be made thereto without departing from the broader spirit and scope of the invention as set forth in the claims. The specification and figures are, accordingly, to be regarded in an illustrative rather than a restrictive sense.
Throughout this specification and the claims which follow, unless the context requires otherwise, the word "comprise", and variations such as "comprises" and "comprising", will be understood to imply the inclusion of a stated integer or step or group of integers or steps but not the exclusion of any other integer or step or group of integers or steps.
The reference to any prior art in this specification is not, and S. should not be taken as, an acknowledgment or any form of suggestion that that prior art forms part of the common general knowledge in Australia.
Claims (6)
- 2. The stopper of claim 1, wherein said first polymer portion includes a polyolefin.
- 31. The stopper of claim 1, wherein said first polymer portion includes a mixture of metlloene co-polymers. and low density polyethylene. ~2 4. The stopper of claim 3, wherein said weight ratio of said mixture of said metallocene co-polymers and said low density polyethylene is approximately 3:1. The stopper of claim 3, wherein said first polymer portion further includes 0.2 percent to 50 percent of an ethylene/methacrylic acid co-polymer b~ased i'onorner resin. 6. The stopper of claim 1, wherein said second polymer portion is one of an jionomer resin and an elastomer. 7. The stopper of claim 6, wherein said second polymer portion is an ethylene/methacrylic acid co-polymer based ionomer resin. 8. The stopper of claim 1, wherein said second polymer portion includes one of a styrene-butadiene elastomer, a styrene-ethylene-butadiene-styrene-elastomer, and a ethylene vinyl acetate elastomer. 9. The stopper of claim 1, wherein said stopper is comprised of approximately 95-99% of said first polymer portion. 10. The stopper of claim 1, further comprising a third polymer portion, wherein said first polymer portion coaxially overlies said third polymer portion. 11. The stopper of claim 10, wherein said third polymer is one of a high density polyethylene polymer and a high density polypropylene polymer. 12. The stopper of claim 11, wherein said third polymer portion has a density of 22-25 lb/cu. ft. 13. The stopper of claim 11, wherein said third polymer portion has an outside diameter of approximately 12 mm. 14. The stopper of claim 11, wherein said third polymer portion has one of a substantially cylindrical shape, a substantially cylindrical shape having an opening extending about its axis, and at least a three-fold radially symmetrical shape extending about its axis. rv-ub-4ujiJ UO: 4dUT1 rruai-oiL LA 1-000 r 4i o r*uw The stopper of claim 11, wherein said first polymer is a mixture of an ethylene/methacrylic acid Co-polymer based ionomer resin and a low density polyethylene in a weight ratio of 85:15 and having a density of approximately lb/cu. ft. and a diameter of 9-12 mm, wherein said second polymer portion is a colloidal alumina having a thickness of 0.2-0.8 rm wherein said third polymer portion is a high density polyethylene polymer having a density of 22-25 lb,'cu. ft., and a diameter of approximately 12 mm. 16. A method of protecting liquid in a bottle with a substantially cylindrical bottle opening, comprising: providing a stopper having a substantially cylindrical shape to seal the bottle opening and including a first polymer portion and a second polymer portion, said first polymer portion having a first physica~l property and said second polymer portion having a second physical property different from said first physical property, said second polymer portion configured to coaxially overly said first polymer portion; and closing off the bottle by insertion of said stopper into said bottle opening. 17. The method of claim 16, wherein :said first polymer portion of said stopper includes a mixture of metallocene cc-polymers and low density polyethylene. 18. The method of claim 1.7, wherein said weight ratio of said mixture of said metallocene co-polymners and said low density poJlyethylenei is approximately 3:1. 19. The method of claim 17, wherein saz;d first polymer portion of said stopper further includes 0.2 percent to percent of an ethylene/iriethacrylic aci±d co-polymer based ionomer resin. The method of claim 17, wherein said second polymer Portion of said stopper is one of an ionomer resin and an las toruer. 21. The stopper of claim 20, wherein said second material :portion of said stopper includes an ethylene/rnethacrylic acid co-polymer based ioriomer resin, 22. The method 'of claim 16, wherein said stopper- is comprised of approximately 95-99% of said first polymer portion. 23. The meth-od of claim 16, wherein said stopper further ccmprises a third polymer portion, wherein said first polymer portion of said stopper overlies said third polymer portion. 24. The method of claim 23, wherein said third polymer is one of a high density polyethylene polymer and a high density polypropylene polymer. The method of claim 24, wherein said third polymer portion of said stopper has a densicy of 22-25 lb/cu. ft. rUv lu -LUJV 3UY O;JfnI rILUI041L Lb% JIVL4Q% I 4 r W&Vi V,4 I~l 2.The mnethod of claim 24, wherein said third polymer portion of said stopper has an outside diameter of approximately 12 n. 27. The mnethod of claim 24, wherein said third polymer portion of said stopper has one of a substantially. cylindrical shape, a substantially cylindrical shape havirng an opening extending about its axis, and at least a three- fold radially symmetrical shape extending about its axis. 28. The method of claim 24, wherein said first polymer of said stopper is a mixture of an athylene/methacrylic acid co-polymer based ionomer resin and a low density polyethylene in a weight ratio of 85:1.5 and having a density of approximately 15 lb/cu. ft. and a diameter of 9-12 mm, wherein said second polymer portion of said stopper is a colloidal alumina having a thickness of 0.2-0.8 mun, and wherein said third polymer portion of said stopper is a high density polyethylene polymer having a density of 22-25 lb/cu. ft., and a diameter of approximately 12 mm. 29.1 A method of producing a tpe Eruei a substantially cylindrical bottle openiLng, comprising: extruding a first polymer portion having a first physical property throu~gh an extrusion die; coaxially coating said first polymer portion with a second polymer portion having a second physical property that is different from said first physical property to form a body; and forming said body into a shape to substantially seal said bot.4le opening. IIUv to Uv 40 U 0 r i unroo i i 1- 4.0 1 -WIti 604 S. *1 CI *4~ 4* *4 The method of claim 29, said method further comprising, prior to the step of coating said first polymer portion, blending said first polymer portion with a blowing agent. 31. The method of claim 29, wherein said first polymer portion incl:udes a mixture of a low density polyethylene and 0.2 percent to 50 percent of an ethytlene/methacrylic acid co-polymer based ionorner resin, and wherein said second polymer portion includes one of an ethylene/methacrylic acid co-polymer based ionomer resin and an elastorner
- 32. The method of claim 29, wherein said body of said stopper is comprised of 95-99% of said first polymer portion.
- 33. A method of producing a stopper for use in a substantially cylindrical bottle opening, comprising: extruding a first polymer portion through an extrusion die; coaxially coating said first polymer portion with a second polymer portion; coaxially coating said second polymer portion with a third polymer- portion to form a body; and forming said body into a shape to substantially seal said bottle opening.
- 34. The method of claim 33, said m~ethod Further comprising, prior to the step of coating said first polymer portion, blending said first polymer portion with a blowing agent. The method of claim 34, wherein said first polymer portion is extruded with one of a sFubstantially cylindrical 11 UIV W b- t. U u %j QP j I Pm r i U111-0-2 I L Lh J"Q&V; Vqu I -130 r vt w j34 r-vrj I shape, a substantially cylindrical s hape having an opening extending about its axis, and at least a three-fold radially symmetrical shape extending about its axis. U. U. S S S Ue C. S S S.t. S S. S 555 555S S S SS S*. SS 5@ S S SS 26
- 36. A stopper and/or method of producing same and/or method of protecting liquid substantially as hereinbefore described with reference to the drawings and/or Examples. 37' The steps, features, compositions and compounds disclosed herein or referred to or indicated in the specification and/or claims of this application, individually or collectively, and any and all combinations of any two or more of said steps or features. see DATEDthis TENTH day of NOVEMBER 2000 Neocork Technologies, LLC g by DAVIES COLLISON CAVE Patent Attorneys for the applicant(s)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AU71528/00A AU749676B2 (en) | 2000-11-10 | 2000-11-10 | Multilayer synthetic stopper |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AU71528/00A AU749676B2 (en) | 2000-11-10 | 2000-11-10 | Multilayer synthetic stopper |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| AU7152800A true AU7152800A (en) | 2002-05-16 |
| AU749676B2 AU749676B2 (en) | 2002-07-04 |
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ID=3754381
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU71528/00A Ceased AU749676B2 (en) | 2000-11-10 | 2000-11-10 | Multilayer synthetic stopper |
Country Status (1)
| Country | Link |
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| AU (1) | AU749676B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7997439B2 (en) | 2003-06-06 | 2011-08-16 | Jamak Fabrication-Tex, Llc | Flexible bakeware having a multi-piece carrier system |
| US7966970B2 (en) | 2005-07-19 | 2011-06-28 | M Management-Tex, Llc | Dairy inflation |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2549404A (en) * | 1946-05-07 | 1951-04-17 | Harold W Williams | Bottle stopper |
| IT1247147B (en) * | 1991-01-09 | 1994-12-12 | Lino Fantin | SEALING CAP FOR LIQUID CONTAINERS |
| US5904965A (en) * | 1997-04-24 | 1999-05-18 | Nomaco, Inc. | Synthetic closure |
-
2000
- 2000-11-10 AU AU71528/00A patent/AU749676B2/en not_active Ceased
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| AU749676B2 (en) | 2002-07-04 |
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Owner name: NEOCORK TECHNOLOGIES, INC. Free format text: FORMER OWNER WAS: NEOCORK TECHNOLOGIES, LLC |