US20040161560A1 - Closure cap liners having oxygen barrier properties - Google Patents

Closure cap liners having oxygen barrier properties Download PDF

Info

Publication number
US20040161560A1
US20040161560A1 US10/748,561 US74856103A US2004161560A1 US 20040161560 A1 US20040161560 A1 US 20040161560A1 US 74856103 A US74856103 A US 74856103A US 2004161560 A1 US2004161560 A1 US 2004161560A1
Authority
US
United States
Prior art keywords
approximately
parts
closure
thermoplastic elastomer
liner
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
US10/748,561
Inventor
Thomas Baranowski
Richard Cormack
James Taber
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Silgan Holdings Inc
Original Assignee
Amcor White Cap Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Amcor White Cap Inc filed Critical Amcor White Cap Inc
Priority to US10/748,561 priority Critical patent/US20040161560A1/en
Publication of US20040161560A1 publication Critical patent/US20040161560A1/en
Assigned to AMCOR WHITE CAP, INC. reassignment AMCOR WHITE CAP, INC. CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). Assignors: WHITE CAP, INC.
Assigned to SILGAN HOLDINGS INC. reassignment SILGAN HOLDINGS INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: AMCOR WHITE CAP, INC.
Abandoned legal-status Critical Current

Links

Images

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B65CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65DCONTAINERS 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
    • B65D53/00Sealing or packing elements; Sealings formed by liquid or plastics material
    • B65D53/04Discs
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B65CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65DCONTAINERS 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
    • B65D41/00Caps, e.g. crown caps or crown seals, i.e. members having parts arranged for engagement with the external periphery of a neck or wall defining a pouring opening or discharge aperture; Protective cap-like covers for closure members, e.g. decorative covers of metal foil or paper
    • B65D41/32Caps or cap-like covers with lines of weakness, tearing-strips, tags, or like opening or removal devices, e.g. to facilitate formation of pouring openings
    • B65D41/40Caps or cap-like covers adapted to be secured in position by permanent deformation of the wall-engaging parts
    • B65D41/42Caps or cap-like covers adapted to be secured in position by permanent deformation of the wall-engaging parts made of relatively-stiff metallic material, e.g. crown caps
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B65CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65DCONTAINERS 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
    • B65D41/00Caps, e.g. crown caps or crown seals, i.e. members having parts arranged for engagement with the external periphery of a neck or wall defining a pouring opening or discharge aperture; Protective cap-like covers for closure members, e.g. decorative covers of metal foil or paper
    • B65D41/32Caps or cap-like covers with lines of weakness, tearing-strips, tags, or like opening or removal devices, e.g. to facilitate formation of pouring openings
    • B65D41/34Threaded or like caps or cap-like covers provided with tamper elements formed in, or attached to, the closure skirt
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B65CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65DCONTAINERS 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
    • B65D53/00Sealing or packing elements; Sealings formed by liquid or plastics material
    • B65D53/02Collars or rings
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/13Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1352Polymer or resin containing [i.e., natural or synthetic]

Definitions

  • the present invention generally relates to improved oxygen barrier liner compositions for plastic closures and more particularly, to homogeneous thermoplastic elastomer liner compositions which provide an effective barrier to oxygen ingress into the containers and which are advantageously characterized by improved physical properties such as increased tensile strength and elongation.
  • This invention also relates to a method for making such liners from such plastic compositions and to closures for containers for food and beverage products which closures include these liner compositions.
  • Closures for use in food and beverage containers include a closure shell formed of metal, plastic or both metal and plastic and are typically provided with a liner on the inner surface of the closure shell end panel.
  • the liner is intended to provide a hermetic seal between the closure member and the container opening.
  • the liners be made of or include a material that is a barrier to oxygen. Efforts to provide a liner that is an effective barrier against oxidation of the food or beverage stored within a container are described in the prior art.
  • U.S. Pat. No. 5,955,163 to White discloses a gasket for closures used with beverage containers.
  • the gasket is formed of a thermoplastic material which includes, for example, a hydrogenated copolymer of styrene and conjugated diene or functionalized derivative thereof and a rubbery polymer such as butyl rubber which, according to this patent, further prevents ingress of oxygen and volatile odors.
  • the gasket is used with metal crown caps.
  • U.S. Pat. No. 4,684,554 to Ou-Yang describes a multi-layered seal that includes a pulpboard backing, a wax coating over the pulpboard, aluminum foil and a heat-sealable polymeric coating over the foil.
  • the aluminum foil acts as an oxygen barrier.
  • the multi-layered seal is mounted inside the closure of a container. The container and the closure (with the seal) is treated in a radio frequency field, such that when the closure is removed from the container, the pulpboard backing twists free from the foil which remains bonded to the lip of the container. The foil is then peeled off the lip of the container when access to the contents is desired. While aluminum foil provides a good barrier to oxygen, from the standpoint of a consumer, such peelable seals are less than desirable because of the difficulty often encountered in removing them from the opening of the container.
  • FIG. 1 Another example of a closure with an oxygen absorbing liner is described in U.S. Pat. No. 5,381,914 to Koyama et al.
  • the liner described therein is made of a resin which is blended with an oxygen absorbing agent.
  • the composition can be applied to the entire inner surface of the closure shell or, more typically, may be incorporated as a layer of a laminated structure.
  • the laminate includes the layer of the oxygen absorbing agent and a layer of resin interposed between the oxygen absorbing layer and the closure shell.
  • the oxygen absorbing layer can be made of a thermoplastic elastomer with the oxygen absorbing agent blended therein. Examples of suitable organic oxygen absorbing agents include phenol-type resins, ascorbic acids, saccharides and the like.
  • U.S. Pat. No. 5,143,763 to Yamada et al. describes a multi-layered seal for use with bottle closures that include a layer of an oxygen absorbent composition and an oxygen permeable film covering the oxygen absorbent composition.
  • the composition includes an asymmetric porous membrane where the outer surface is formed as a dense skin layer. The dense skin layer protects the oxygen absorbent layer from being contacted by the food or beverage stored within the container.
  • liners for use in food or beverage container closures should possess other properties.
  • the liner and the plastic compositions used for such liners must possess good to excellent adhesion to the inner surface of the closure preferably without the use of a separate adhesive.
  • the sealing provided by the liner should not be such that it is difficult for the average user to open the container. Accordingly, the liner must have good “torque removal” properties to allow for easy removal (e.g., by unscrewing) of the cap without having to use excess force.
  • the liner should also be made of a composition that is easy to process.
  • Oil-based plasticizers such as mineral oil
  • plasticizers such as mineral oil have also been known to exhibit an odor and/or affect the taste of the food product.
  • the plastic composition of the present invention and liners made from such plastic compositions address at least all of the above-described objectives.
  • our studies have shown that the preferred single layer liner in accordance with the present invention has an oxygen ingress rate of between approximately 4-8 cc/m 2 /day, a 100% modulus greater than approximately 260 psi, % elongation of greater than approximately 350 and a tensile strength (psi) greater than approximately 500.
  • psi tensile strength
  • excess polybutylene will negatively affect the sealability of the liners in relation to the container opening, whereas too little polybutylene can reduce the adhesion of the liner to the inner surface of the closure cap.
  • An amount of polyisobutylene that is significantly lower than the amount used in the composition of the present invention will reduce the oxygen barrier properties, while too much polyisobutylene can make the composition more difficult to process.
  • the present invention is directed to a closure cap liner or gasket composition comprising a blend of a thermoplastic elastomer, polybutylene and polyisobutylene.
  • the plastic composition can also advantageously include a microcrystalline wax.
  • the present invention is directed to a container closure comprising a plastic shell having an end panel and an integral skirt that extends downwardly from the periphery of the skirt.
  • the end panel has an inner-facing surface and includes a substantially oxygen impermeant liner which is adhered to at least a portion of the inner-facing surface.
  • the liner is made from a material including a thermoplastic elastomer, polybutylene and polyisobutylene.
  • the liner can also advantageously contain a microcrystalline wax.
  • the present invention is also directed to a method for providing a liner for a container closure.
  • the method includes (1) combining and mixing polyisobutylene with a thermoplastic elastomer, (2) adding polybutylene to the mixture of polyisobutylene and thermoplastic elastomer to provide a blend, and (3) forming the blend into a liner.
  • a microcrystalline wax can be advantageously added to the blend of thermoplastic elastomer, polybutylene and polyisobutylene.
  • the liner can be formed into a disc or a ring adhered to the inner-facing surface of the closure.
  • closure caps that include liners made from a composition that comprises a thermoplastic elastomer, polyisobutylene and polybutylene.
  • FIG. 1 is a side view of a plastic closure of the type used in connection with the present invention
  • FIG. 2 is a cross-sectional view of a container closure with a liner embodying the present invention adhered to the inner surface of the closure;
  • FIG. 3 is a plan view of the inner surface of a closure with the liner of FIG. 2 adhered to the inner-facing surface of the closure;
  • FIG. 4 is a plan view of a closure with another embodiment of the liner adhered to the inner-facing surface of the closure.
  • FIG. 5 is a cross-sectional view of the closure of FIG. 1 with the liner of FIG. 4 adhered to the inner surface of the closure end panel.
  • the plastic composition of the present invention will be described below in the context of its preferred use, namely, as a liner for a plastic closure of a food or beverage container. It will be appreciated, however, that the plastic composition of the present invention is not limited to such use.
  • the plastic composition of the present invention can be used in any other application where, for example, a material with oxygen barrier properties is desired, and/or where a material exhibiting excellent adhesion to a plastic substrate is desired.
  • FIG. 1 shows a container 10 with a closure 12 secured over the open mouth of the container.
  • Closure 12 includes a shell generally designated by the reference numeral 14 .
  • Shell 14 includes an end panel 16 and a skirt 18 .
  • closure 12 further includes a tamper-evident band 20 integrally formed with and secured to the base of the skirt by a plurality of frangible bridges 21 .
  • Closure 12 can typically be made by, for example, injection molding from a thermoplastic composition such as, for example, a polyolefin such as polypropylene.
  • Closure 12 can be made of polyethylene or a blend of polyethylene and polypropylene.
  • closure 12 can be made of a plastic/metal composite material or entirely of metal.
  • closure shell 14 seals the open mouth of container 10 defined by end finish 24 .
  • closure shell 14 includes a liner 28 adhered to the inner-facing surface of shell 14 .
  • Liner 28 can be in the shape of a circular disc that covers substantially the entire inner-facing surface of end panel of shell 14 (FIG. 3).
  • liner 14 can be in the shape of a ring which covers only the annular periphery of the inner-facing surface of the shell (FIG. 4).
  • liner 28 should contact the end finish of the container walls to provide a hermetic seal between closure shell 14 and the opening and, thereby, limit oxygen ingress from the outside environment into the container interior.
  • Liners of the type shown in FIGS. 1 - 5 can be made of a composition comprising a thermoplastic elastomer, polyisobutylene and polybutylene and other additives that, among other things, provides an effective barrier to oxygen, has good torque removal properties, and provides good adhesion to the inner surface of the plastic closure shell 14 .
  • the compositions are easy to process by known processing and compounding methods, and moldable into a liner of the type described above.
  • the plastic composition includes a thermoplastic elastomer, a compound for improving the oxygen barrier properties of the composition and one or more compounds to improve adhesion, torque removal and/or processability.
  • the thermoplastic elastomer selected is preferably substantially odorless and tasteless.
  • Thermoplastic elastomers are polymers or blends of polymers that can be processed and recycled in the same way as a conventional thermoplastic material, but that also have a rubber-like quality and performance similar to that of rubber.
  • Thermoplastic elastomers can be obtained by combining a thermoplastic polyolefin with an elastomeric composition in a way such that the elastomer is intimately and uniformly dispersed as a particle phase within a continuous phase of the thermoplastic polyolefin.
  • thermoplastic elastomers which can be included in the plastic composition of the present invention are, for example, a thermoplastic polyolefin homopolymer or co-polymer blended with an olefinic rubber which is fully cross-linked, partially cross-linked or not cross-linked at all.
  • the thermoplastic elastomer composition can be a resinous polymer of propylene and a butyl-based cross-linked rubber of the type described in U.S. Pat. No. 5,843,577 to Ouhadi et al., incorporated by reference herein. As further described in U.S. Pat. No.
  • the thermoplastic elastomer can include other additives, including lubricants such as polyamides and other additives such as, but not limited to, anti-blocking agents.
  • Lubricants are typically added to soften a material and aid in the processing of certain tacky materials. Lubricants can also improve the torque removal properties of a liner made from the composition.
  • thermoplastic elastomers are the thermoplastic elastomers sold by Advanced Elastomer Systems under the product name Trefsin®.
  • Trefsin® is generally described as a thermoplastic resin of the alloyed material of a polypropylene and an isobutylene-isoprene rubber.
  • the thermoplastic elastomer composition can include an ethylene-propylene copolymer and rubber which can be cross-linked and/or can include a terpolymer of ethylene, propylene and a diene.
  • thermoplastic elastomers include the commercially available Santoprene®. Santoprene® is believed to include an ethylene, propylene and diene terpolymer. Santoprene® and other thermoplastic elastomers like it are available from Advanced Elastomer Systems, L.P. of Akron, Ohio.
  • thermoplastic elastomer used in the composition of the present invention can also be a blend of one or more thermoplastic elastomers.
  • thermoplastic elastomeric block 1.5 copolymers of the saturated A-B-A type based on styrene and butadiene units are also useful.
  • styrene-ethylene butylene-styrene (SEBS) type block copolymers can be used.
  • SEBS styrene-ethylene butylene-styrene
  • Such co-polymers are sold under the trade name Kraton-G® (e.g., Kraton-G 1652 and Kraton-G 2705) and are available from the Shell Chemical Company.
  • thermoplastic elastomers described above may, to some degree, provide a barrier to oxygen, to further enhance such oxygen barrier properties
  • other compounds can be added to the plastic composition.
  • butyl rubbers such as polyisobutylene are desirable because they provide good oxygen barrier properties.
  • the thermoplastic elastomer can be combined with an effective amount of polyisobutylene.
  • Polyisobutylene is available from a variety of suppliers including the Exxon Corporation.
  • thermoplastic elastomers described above can be combined with other additives to improve adhesion of the liner to the closure shell.
  • the shell is made of a thermoplastic polyolefin such as polypropylene
  • improved adhesion is provided by adding an effective amount of other polyolefin.
  • polyolefin is polybutylene, which provides improved adhesion of the plastic composition to the polypropylene shell of a closure.
  • Polybutylene also improves the flow characteristics and overall processability of the plastic composition.
  • An example of a polybutylene that is suitable for inclusion in the plastic composition of the present invention is PB 0400 available from Montell Corporation.
  • polypropylene may be added to the thermoplastic elastomer of the composition.
  • closures for food and beverage containers should also possess good torque removal properties. Accordingly, in addition to the above, a selected amount of a wax material can be added to the plastic composition to improve torque removal.
  • a microcrystalline wax has been found to work particularly well and is preferred. In fact, it has been discovered that addition of a small amount of microcrystalline wax to the plastic composition described above improves the torque removal properties of the closure without significantly affecting the other desirable properties, such as oxygen barrier properties of the composition.
  • Microcrystalline waxes suitable for inclusion in the plastic composition of the present invention can be a highly branched chain hydrocarbon of the aliphatic-alicyclic alkane family. Such waxes are sold under the name Okerin-6080H and are available from Honeywell of Morristown, N.J.
  • an anti-blocking talc can be added to the blend. More specifically, the anti-blocking talc can be combined with polyisobutylene to prevent agglomeration of the polyisobutylene during processing.
  • the plastic composition when formed into a liner for the closure, provides excellent oxygen barrier properties, torque removal properties, adhesion to the polymeric shell and is easy to process.
  • the plastic composition can include between approximately 40-70 parts, by weight, of the thermoplastic elastomer, approximately 15-30 parts, by weight, of the polyisobutylene and approximately 10-35 parts of polybutylene.
  • the plastic composition can include 2-10 parts, by weight, of a wax, preferably a microcrystalline wax.
  • the plastic composition can further include less than approximately 3 parts, by weight, of an anti-blocking talc.
  • the relative proportions described above provide a plastic composition that can be molded into an effective liner for a plastic closure with the properties described above. While adjustments to the above-described proportions are possible, it has been discovered that amounts of the components significantly outside of the ranges described above can result in a liner with certain properties that are inferior to the properties possessed by liners that include the components in the proportions described above. For example, if the amount of polybutylene is significantly below the lower end of the preferred range, the resultant liners may not adhere as well to the inner surface of the closure. If, on the other hand, the amount of polybutylene is significantly greater from the upper limit of the preferred range, the resultant liner may be too hard and, thus, negatively affect sealability of the closure to the container.
  • Too much polyisobutylene can result in a blend that is too soft and viscous and, as a result, is more difficult to process.
  • a lower amount of polyisobutylene on the other hand, will reduce the oxygen barrier properties of the liner.
  • the above described compounds can be combined as follows.
  • the selected amount of polyisobutylene is first mixed with an anti-blocking talc in a Banbury-type mixer for approximately 2-4 minutes.
  • the selected amounts of the thermoplastic elastomer, polybutylene, and microcrystalline are then added.
  • thermoplastic elastomer is processed and mixed in, for example, a twin-screw mixer to a temperature not exceeding 225° C.
  • the selected amount of polyisobutylene can be compounded with the thermoplastic elastomer followed by addition of the polybutylene.
  • the microcrystalline wax is added to the blend while continuing to mix the compounds.
  • thermoplastic elastomer and the polybutylene can be initially combined and mixed to a temperature not exceeding 225° C. This is followed by adding a selected amount of polyisobutylene and finally the microcrystalline wax.
  • a preferred mixing temperature for preparing the plastic composition is less than 225° C. and, preferably, approximately 180° C. It has been discovered that at temperatures approaching approximately 225° C., some breakdown of material is observed.
  • the compounds described above can be blended together in ways that are known to those of skill in the art.
  • the plastic composition of the present invention can be formed into a liner and combined with the closure shell to provide a closure as shown in FIGS. 1 - 5 .
  • Liners of the present invention can be formed into discs or pads which can then be cold punch molded onto the inner surface of the closure shell.
  • liners in a gasket-type shape can be injection molded and placed onto the inner surface of the closure shell.
  • Liners of the present invention which have been formed into discs or pads can have a thickness of approximately 0.005-0.1 inches. More typically, the thickness of such liner discs or pads can be approximately 0.012 inches, except that, as seen in FIG. 2, the thickness of the liner can be greater near or along the annular periphery of the liner where it contacts the end finish of the container. For example, in one embodiment the thickness of the liner near or along the annular periphery can be approximately 0.01-0.05 inches and, more preferably, approximately 0.030-0.035 inches. Such added thickness provides added barrier material where oxygen ingress is most likely to occur, namely, between the closure skirt and the container.
  • Liners of the present invention exhibit good to excellent oxygen barrier properties and are particularly useful liners for food and beverage containers.
  • liners in accordance with the present invention have an oxygen ingress rate of less than approximately 14.0 cc/m 2 /day at normal atmospheric conditions.
  • liners of the present invention typically limit the oxygen ingress rate to between approximately 4-8 cc/m 2 /day at normal atmospheric conditions.
  • equipment of the type described above measures oxygen ingress by introducing nitrogen gas into a vessel sealed with a liner sample (plaque) or a closure fitted with a liner.
  • the nitrogen gas picks up any oxygen present within the sealed vessel.
  • the nitrogen gas exits the vessel through an outlet and the level of captured oxygen is recorded as an electronic signal and reported as cubic centimeters (cc) of oxygen permeating across a square meter (m 2 ) of a plaque or into a package (closure with liner) in a day.)
  • Samples of the plastic composition made in accordance with the present invention were prepared by blending approximately 65 parts of a thermoplastic elastomer that includes a homopolymer or copolymer of polypropylene and a butyl-based rubber, 20 parts polyisobutylene, 15 parts polybutylene and 4 parts microcrystalline wax.
  • the composition was formed into a liner and molded to the inner surface of a polypropylene shell. Oxygen ingress through the closure with the liner was measured using the MOCON® permeation measuring equipment referred to above. Oxygen ingress into the container through a closure having a diameter of approximately 43 mm and including a liner made from the composition described above was measured as approximately 0.0024-0.005 cc/pkg/day/atm.
  • Closures of different sizes (diameters) were also provided with liners made in accordance with the present invention on the one hand and liners made from a SEBS block copolymer, mineral oil and lubricant on the other hand.
  • Table 1 when compared to closures having a liner made from a SEBS block copolymer, mineral oil and lubricant (identified as 615), closures with liners made in accordance with the present invention (identified as 622) consistently displayed superior oxygen barrier properties (i.e., less oxygen ingress).
  • Oxygen ingress through the liner alone (without the closure cap) was also measured.
  • Sample plaques made from the plastic liner composition of Example 1 and measuring approximately 4 ⁇ 4 ⁇ 0.060 inches were prepared and were measured for oxygen ingress using MOCON® permeation measuring equipment.
  • sample plaques made from only the thermoplastic elastomer (without polyisobutylene, polybutylene and microcrystalline wax) were prepared and also measured for oxygen ingress.
  • Oxygen ingress across the plaque made from the liner composition of the present invention was approximately 4.8-7.9 cc/m 2 /day/atm.
  • oxygen ingress across the plaque made from the thermoplastic elastomer alone was approximately 14.4 cc/m 2 /day.
  • liners of the present invention exhibit excellent adhesion to the polypropylene shells often used for beverage containers. Liners of the present invention made from the plastic composition also exhibit excellent mechanical and physical strength. For example, liners made from the preferred plastic compositions described above exhibit a 100% modulus of greater than approximately 260 psi. A percent elongation of greater than approximately 350 and a tensile strength of greater than approximately 500 psi.
  • Samples of the plastic composition were prepared by blending approximately 65 parts thermoplastic elastomer that includes a homopolymer or copolymer of polypropylene and a butyl-based rubber, 20 parts polyisobutylene, 15 parts polybutylene and 4 parts microcrystalline wax. The blend was extruded into a 0.060 ⁇ 6 ⁇ 6 (inch) plaque from which samples were die cut in accordance with ASTM D412 procedures. The samples were tested for 100% modulus psi percent elongation and tensile strength psi (ASTM D412). Three lots of the composition made in accordance with the present invention were prepared and average values are set forth below in Table II.
  • thermoplastic elastomer alone (without the polybutylene, polyisobutylene and microcrystalline wax) was similarly tested for 100% modulus psi, elongation and tensile strength psi.
  • the results of such testing are likewise reported in Table II under the heading “TPE.”
  • TPE the plastic composition of the present invention (identified as 622) was also superior in these mechanical and physical properties.

Abstract

Liners with improved oxygen barrier properties for use with closure caps are disclosed. The liners are made of a composition that includes a thermoplastic elastomer, polyisobutylene and polybutylene. The liner is adhered to the inner facing surface of a closure cap.

Description

  • The present invention generally relates to improved oxygen barrier liner compositions for plastic closures and more particularly, to homogeneous thermoplastic elastomer liner compositions which provide an effective barrier to oxygen ingress into the containers and which are advantageously characterized by improved physical properties such as increased tensile strength and elongation. This invention also relates to a method for making such liners from such plastic compositions and to closures for containers for food and beverage products which closures include these liner compositions. [0001]
  • BACKGROUND OF THE INVENTION
  • Closures for use in food and beverage containers include a closure shell formed of metal, plastic or both metal and plastic and are typically provided with a liner on the inner surface of the closure shell end panel. The liner is intended to provide a hermetic seal between the closure member and the container opening. [0002]
  • Notwithstanding the lined closure, oxygen can permeate the closure shell or enter through spaces between the closure shell and the container. Oxygen can adversely affect beverage and food products stored within a container since a small amount of oxygen can alter the taste of the beverage or food product or cause spoilage of the product. Accordingly, it is desirable that the liners be made of or include a material that is a barrier to oxygen. Efforts to provide a liner that is an effective barrier against oxidation of the food or beverage stored within a container are described in the prior art. [0003]
  • U.S. Pat. No. 5,955,163 to White discloses a gasket for closures used with beverage containers. The gasket is formed of a thermoplastic material which includes, for example, a hydrogenated copolymer of styrene and conjugated diene or functionalized derivative thereof and a rubbery polymer such as butyl rubber which, according to this patent, further prevents ingress of oxygen and volatile odors. The gasket is used with metal crown caps. [0004]
  • U.S. Pat. No. 4,684,554 to Ou-Yang describes a multi-layered seal that includes a pulpboard backing, a wax coating over the pulpboard, aluminum foil and a heat-sealable polymeric coating over the foil. The aluminum foil acts as an oxygen barrier. The multi-layered seal is mounted inside the closure of a container. The container and the closure (with the seal) is treated in a radio frequency field, such that when the closure is removed from the container, the pulpboard backing twists free from the foil which remains bonded to the lip of the container. The foil is then peeled off the lip of the container when access to the contents is desired. While aluminum foil provides a good barrier to oxygen, from the standpoint of a consumer, such peelable seals are less than desirable because of the difficulty often encountered in removing them from the opening of the container. [0005]
  • Another example of a closure with an oxygen absorbing liner is described in U.S. Pat. No. 5,381,914 to Koyama et al. The liner described therein is made of a resin which is blended with an oxygen absorbing agent. The composition can be applied to the entire inner surface of the closure shell or, more typically, may be incorporated as a layer of a laminated structure. The laminate includes the layer of the oxygen absorbing agent and a layer of resin interposed between the oxygen absorbing layer and the closure shell. The oxygen absorbing layer can be made of a thermoplastic elastomer with the oxygen absorbing agent blended therein. Examples of suitable organic oxygen absorbing agents include phenol-type resins, ascorbic acids, saccharides and the like. [0006]
  • U.S. Pat. No. 5,143,763 to Yamada et al. describes a multi-layered seal for use with bottle closures that include a layer of an oxygen absorbent composition and an oxygen permeable film covering the oxygen absorbent composition. The composition includes an asymmetric porous membrane where the outer surface is formed as a dense skin layer. The dense skin layer protects the oxygen absorbent layer from being contacted by the food or beverage stored within the container. [0007]
  • While the liners or seals described above may be effective in limiting the amount of oxygen ingress into the container, further improvements in the field of oxygen barrier liners for closures are desirable. [0008]
  • For example, it would be desirable to provide a liner which acts as an oxygen barrier and can be used in association with resealable plastic closures. It would also be desirable that such liners not require peeling or removal by the consumer. [0009]
  • In addition to providing a barrier to oxygen, liners for use in food or beverage container closures should possess other properties. For example, the liner and the plastic compositions used for such liners must possess good to excellent adhesion to the inner surface of the closure preferably without the use of a separate adhesive. [0010]
  • Also, the sealing provided by the liner should not be such that it is difficult for the average user to open the container. Accordingly, the liner must have good “torque removal” properties to allow for easy removal (e.g., by unscrewing) of the cap without having to use excess force. [0011]
  • The liner should also be made of a composition that is easy to process. Oil-based plasticizers, such as mineral oil, have been included in liner compositions to improve the processability of the composition. However, under certain conditions, extractable compounds from the mineral oil have been known to migrate from the liner composition to the stored food product. Plasticizers such as mineral oil have also been known to exhibit an odor and/or affect the taste of the food product. Thus, it would be desirable to provide a liner that is easy to process but (1) does not include an oil or other plasticizer, (2) does not affect the taste of the stored food product, and (3) is substantially odorless. [0012]
  • It would also be desirable to provide a liner that can be easily formed into flat liners by known techniques such as injection molding and cold punch molding, and that can otherwise be easily incorporated into the closure. [0013]
  • The plastic composition of the present invention and liners made from such plastic compositions address at least all of the above-described objectives. For example, our studies have shown that the preferred single layer liner in accordance with the present invention has an oxygen ingress rate of between approximately 4-8 cc/m[0014] 2/day, a 100% modulus greater than approximately 260 psi, % elongation of greater than approximately 350 and a tensile strength (psi) greater than approximately 500. Also, we have observed that the desirable properties described above can be affected by the relative proportions of the compounds used in the liner composition. For example, excess polybutylene will negatively affect the sealability of the liners in relation to the container opening, whereas too little polybutylene can reduce the adhesion of the liner to the inner surface of the closure cap. An amount of polyisobutylene that is significantly lower than the amount used in the composition of the present invention will reduce the oxygen barrier properties, while too much polyisobutylene can make the composition more difficult to process.
  • SUMMARY OF THE INVENTION
  • There are several different aspects to the present invention. In one aspect, the present invention is directed to a closure cap liner or gasket composition comprising a blend of a thermoplastic elastomer, polybutylene and polyisobutylene. In another aspect of the present invention, the plastic composition can also advantageously include a microcrystalline wax. [0015]
  • Plastic compositions of the type described above exhibit excellent oxygen barrier properties and, therefore, are useful in closures for food or beverage containers. Accordingly, in another aspect, the present invention is directed to a container closure comprising a plastic shell having an end panel and an integral skirt that extends downwardly from the periphery of the skirt. The end panel has an inner-facing surface and includes a substantially oxygen impermeant liner which is adhered to at least a portion of the inner-facing surface. The liner is made from a material including a thermoplastic elastomer, polybutylene and polyisobutylene. In another aspect of the present invention, the liner can also advantageously contain a microcrystalline wax. [0016]
  • The present invention is also directed to a method for providing a liner for a container closure. The method includes (1) combining and mixing polyisobutylene with a thermoplastic elastomer, (2) adding polybutylene to the mixture of polyisobutylene and thermoplastic elastomer to provide a blend, and (3) forming the blend into a liner. A microcrystalline wax can be advantageously added to the blend of thermoplastic elastomer, polybutylene and polyisobutylene. The liner can be formed into a disc or a ring adhered to the inner-facing surface of the closure. [0017]
  • The objects of this invention are achieved with closure caps that include liners made from a composition that comprises a thermoplastic elastomer, polyisobutylene and polybutylene.[0018]
  • DETAILED DESCRIPTION OF THE DRAWINGS
  • FIG. 1 is a side view of a plastic closure of the type used in connection with the present invention; [0019]
  • FIG. 2 is a cross-sectional view of a container closure with a liner embodying the present invention adhered to the inner surface of the closure; [0020]
  • FIG. 3 is a plan view of the inner surface of a closure with the liner of FIG. 2 adhered to the inner-facing surface of the closure; [0021]
  • FIG. 4 is a plan view of a closure with another embodiment of the liner adhered to the inner-facing surface of the closure; and [0022]
  • FIG. 5 is a cross-sectional view of the closure of FIG. 1 with the liner of FIG. 4 adhered to the inner surface of the closure end panel.[0023]
  • DETAILED DESCRIPTION OF THE INVENTION
  • The plastic composition of the present invention will be described below in the context of its preferred use, namely, as a liner for a plastic closure of a food or beverage container. It will be appreciated, however, that the plastic composition of the present invention is not limited to such use. The plastic composition of the present invention can be used in any other application where, for example, a material with oxygen barrier properties is desired, and/or where a material exhibiting excellent adhesion to a plastic substrate is desired. [0024]
  • Turning now to the drawings, FIG. 1 shows a [0025] container 10 with a closure 12 secured over the open mouth of the container. Closure 12 includes a shell generally designated by the reference numeral 14. Shell 14 includes an end panel 16 and a skirt 18. In the illustrated embodiment closure 12 further includes a tamper-evident band 20 integrally formed with and secured to the base of the skirt by a plurality of frangible bridges 21. Closure 12 can typically be made by, for example, injection molding from a thermoplastic composition such as, for example, a polyolefin such as polypropylene. Closure 12 can be made of polyethylene or a blend of polyethylene and polypropylene. Alternatively, closure 12 can be made of a plastic/metal composite material or entirely of metal.
  • As best shown in FIG. 2, shell [0026] 14 seals the open mouth of container 10 defined by end finish 24. As further shown in FIGS. 2 and 3, closure shell 14 includes a liner 28 adhered to the inner-facing surface of shell 14. Liner 28 can be in the shape of a circular disc that covers substantially the entire inner-facing surface of end panel of shell 14 (FIG. 3). Alternatively, liner 14 can be in the shape of a ring which covers only the annular periphery of the inner-facing surface of the shell (FIG. 4). In any event, liner 28 should contact the end finish of the container walls to provide a hermetic seal between closure shell 14 and the opening and, thereby, limit oxygen ingress from the outside environment into the container interior.
  • Liners of the type shown in FIGS. [0027] 1-5 can be made of a composition comprising a thermoplastic elastomer, polyisobutylene and polybutylene and other additives that, among other things, provides an effective barrier to oxygen, has good torque removal properties, and provides good adhesion to the inner surface of the plastic closure shell 14. The compositions are easy to process by known processing and compounding methods, and moldable into a liner of the type described above.
  • In one particular embodiment, the plastic composition includes a thermoplastic elastomer, a compound for improving the oxygen barrier properties of the composition and one or more compounds to improve adhesion, torque removal and/or processability. The thermoplastic elastomer selected is preferably substantially odorless and tasteless. [0028]
  • Thermoplastic elastomers are polymers or blends of polymers that can be processed and recycled in the same way as a conventional thermoplastic material, but that also have a rubber-like quality and performance similar to that of rubber. Thermoplastic elastomers can be obtained by combining a thermoplastic polyolefin with an elastomeric composition in a way such that the elastomer is intimately and uniformly dispersed as a particle phase within a continuous phase of the thermoplastic polyolefin. [0029]
  • Examples of thermoplastic elastomers which can be included in the plastic composition of the present invention are, for example, a thermoplastic polyolefin homopolymer or co-polymer blended with an olefinic rubber which is fully cross-linked, partially cross-linked or not cross-linked at all. In a preferred embodiment, the thermoplastic elastomer composition can be a resinous polymer of propylene and a butyl-based cross-linked rubber of the type described in U.S. Pat. No. 5,843,577 to Ouhadi et al., incorporated by reference herein. As further described in U.S. Pat. No. 5,843,577, the thermoplastic elastomer can include other additives, including lubricants such as polyamides and other additives such as, but not limited to, anti-blocking agents. Lubricants are typically added to soften a material and aid in the processing of certain tacky materials. Lubricants can also improve the torque removal properties of a liner made from the composition. [0030]
  • Other examples of suitable thermoplastic elastomers are the thermoplastic elastomers sold by Advanced Elastomer Systems under the product name Trefsin®. In U.S. Pat. No. 6,062,269, Trefsin® is generally described as a thermoplastic resin of the alloyed material of a polypropylene and an isobutylene-isoprene rubber. [0031]
  • In another example, the thermoplastic elastomer composition can include an ethylene-propylene copolymer and rubber which can be cross-linked and/or can include a terpolymer of ethylene, propylene and a diene. Examples of such thermoplastic elastomers include the commercially available Santoprene®. Santoprene® is believed to include an ethylene, propylene and diene terpolymer. Santoprene® and other thermoplastic elastomers like it are available from Advanced Elastomer Systems, L.P. of Akron, Ohio. [0032]
  • The thermoplastic elastomer used in the composition of the present invention can also be a blend of one or more thermoplastic elastomers. [0033]
  • Also useful are thermoplastic elastomeric block 1.5 copolymers of the saturated A-B-A type based on styrene and butadiene units. For example, styrene-ethylene butylene-styrene (SEBS) type block copolymers can be used. Such co-polymers are sold under the trade name Kraton-G® (e.g., Kraton-G 1652 and Kraton-G 2705) and are available from the Shell Chemical Company. [0034]
  • Although some of the thermoplastic elastomers described above may, to some degree, provide a barrier to oxygen, to further enhance such oxygen barrier properties, other compounds can be added to the plastic composition. For example, butyl rubbers such as polyisobutylene are desirable because they provide good oxygen barrier properties. Accordingly, the thermoplastic elastomer can be combined with an effective amount of polyisobutylene. Polyisobutylene is available from a variety of suppliers including the Exxon Corporation. [0035]
  • The thermoplastic elastomers described above can be combined with other additives to improve adhesion of the liner to the closure shell. Where the shell is made of a thermoplastic polyolefin such as polypropylene, improved adhesion is provided by adding an effective amount of other polyolefin. One such polyolefin is polybutylene, which provides improved adhesion of the plastic composition to the polypropylene shell of a closure. Polybutylene also improves the flow characteristics and overall processability of the plastic composition. An example of a polybutylene that is suitable for inclusion in the plastic composition of the present invention is PB 0400 available from Montell Corporation. Alternatively, or in addition to polybutylene, polypropylene may be added to the thermoplastic elastomer of the composition. [0036]
  • As discussed above, closures for food and beverage containers should also possess good torque removal properties. Accordingly, in addition to the above, a selected amount of a wax material can be added to the plastic composition to improve torque removal. A microcrystalline wax has been found to work particularly well and is preferred. In fact, it has been discovered that addition of a small amount of microcrystalline wax to the plastic composition described above improves the torque removal properties of the closure without significantly affecting the other desirable properties, such as oxygen barrier properties of the composition. Microcrystalline waxes suitable for inclusion in the plastic composition of the present invention can be a highly branched chain hydrocarbon of the aliphatic-alicyclic alkane family. Such waxes are sold under the name Okerin-6080H and are available from Honeywell of Morristown, N.J. [0037]
  • Other additives may also be included to improve the processability of the composition blend. In one embodiment, an anti-blocking talc can be added to the blend. More specifically, the anti-blocking talc can be combined with polyisobutylene to prevent agglomeration of the polyisobutylene during processing. [0038]
  • The above described compounds can be combined in proportions so that the plastic composition, when formed into a liner for the closure, provides excellent oxygen barrier properties, torque removal properties, adhesion to the polymeric shell and is easy to process. Accordingly, in one preferred embodiment, the plastic composition can include between approximately 40-70 parts, by weight, of the thermoplastic elastomer, approximately 15-30 parts, by weight, of the polyisobutylene and approximately 10-35 parts of polybutylene. Additionally, the plastic composition can include 2-10 parts, by weight, of a wax, preferably a microcrystalline wax. The plastic composition can further include less than approximately 3 parts, by weight, of an anti-blocking talc. [0039]
  • The relative proportions described above provide a plastic composition that can be molded into an effective liner for a plastic closure with the properties described above. While adjustments to the above-described proportions are possible, it has been discovered that amounts of the components significantly outside of the ranges described above can result in a liner with certain properties that are inferior to the properties possessed by liners that include the components in the proportions described above. For example, if the amount of polybutylene is significantly below the lower end of the preferred range, the resultant liners may not adhere as well to the inner surface of the closure. If, on the other hand, the amount of polybutylene is significantly greater from the upper limit of the preferred range, the resultant liner may be too hard and, thus, negatively affect sealability of the closure to the container. [0040]
  • Too much polyisobutylene can result in a blend that is too soft and viscous and, as a result, is more difficult to process. A lower amount of polyisobutylene, on the other hand, will reduce the oxygen barrier properties of the liner. [0041]
  • In accordance with the method for making the plastic composition, the above described compounds can be combined as follows. In one embodiment, the selected amount of polyisobutylene is first mixed with an anti-blocking talc in a Banbury-type mixer for approximately 2-4 minutes. The selected amounts of the thermoplastic elastomer, polybutylene, and microcrystalline are then added. [0042]
  • In another embodiment, the thermoplastic elastomer is processed and mixed in, for example, a twin-screw mixer to a temperature not exceeding 225° C. After mixing, the selected amount of polyisobutylene can be compounded with the thermoplastic elastomer followed by addition of the polybutylene. Finally, the microcrystalline wax is added to the blend while continuing to mix the compounds. [0043]
  • Alternatively, the thermoplastic elastomer and the polybutylene can be initially combined and mixed to a temperature not exceeding 225° C. This is followed by adding a selected amount of polyisobutylene and finally the microcrystalline wax. A preferred mixing temperature for preparing the plastic composition, as set forth above, is less than 225° C. and, preferably, approximately 180° C. It has been discovered that at temperatures approaching approximately 225° C., some breakdown of material is observed. The compounds described above can be blended together in ways that are known to those of skill in the art. [0044]
  • After compounding, the plastic composition of the present invention can be formed into a liner and combined with the closure shell to provide a closure as shown in FIGS. [0045] 1-5. Liners of the present invention can be formed into discs or pads which can then be cold punch molded onto the inner surface of the closure shell. Alternatively, liners in a gasket-type shape can be injection molded and placed onto the inner surface of the closure shell.
  • Liners of the present invention which have been formed into discs or pads can have a thickness of approximately 0.005-0.1 inches. More typically, the thickness of such liner discs or pads can be approximately 0.012 inches, except that, as seen in FIG. 2, the thickness of the liner can be greater near or along the annular periphery of the liner where it contacts the end finish of the container. For example, in one embodiment the thickness of the liner near or along the annular periphery can be approximately 0.01-0.05 inches and, more preferably, approximately 0.030-0.035 inches. Such added thickness provides added barrier material where oxygen ingress is most likely to occur, namely, between the closure skirt and the container. [0046]
  • Liners of the present invention exhibit good to excellent oxygen barrier properties and are particularly useful liners for food and beverage containers. For example, using an oxygen permeability measuring apparatus, Model Ox-Tran Ten.Fifty, available from MOCON® of Minneapolis, Minn., liners in accordance with the present invention have an oxygen ingress rate of less than approximately 14.0 cc/m[0047] 2/day at normal atmospheric conditions. Indeed, liners of the present invention typically limit the oxygen ingress rate to between approximately 4-8 cc/m2/day at normal atmospheric conditions. (Briefly, equipment of the type described above measures oxygen ingress by introducing nitrogen gas into a vessel sealed with a liner sample (plaque) or a closure fitted with a liner. The nitrogen gas picks up any oxygen present within the sealed vessel. The nitrogen gas exits the vessel through an outlet and the level of captured oxygen is recorded as an electronic signal and reported as cubic centimeters (cc) of oxygen permeating across a square meter (m2) of a plaque or into a package (closure with liner) in a day.)
  • Further details regarding liners made from the compositions and the advantages provided by the present invention will become apparent from the following illustrative working examples. [0048]
  • EXAMPLE 1
  • Samples of the plastic composition made in accordance with the present invention were prepared by blending approximately 65 parts of a thermoplastic elastomer that includes a homopolymer or copolymer of polypropylene and a butyl-based rubber, 20 parts polyisobutylene, 15 parts polybutylene and 4 parts microcrystalline wax. The composition was formed into a liner and molded to the inner surface of a polypropylene shell. Oxygen ingress through the closure with the liner was measured using the MOCON® permeation measuring equipment referred to above. Oxygen ingress into the container through a closure having a diameter of approximately 43 mm and including a liner made from the composition described above was measured as approximately 0.0024-0.005 cc/pkg/day/atm. [0049]
  • Closures of different sizes (diameters) were also provided with liners made in accordance with the present invention on the one hand and liners made from a SEBS block copolymer, mineral oil and lubricant on the other hand. As shown in Table 1, when compared to closures having a liner made from a SEBS block copolymer, mineral oil and lubricant (identified as 615), closures with liners made in accordance with the present invention (identified as 622) consistently displayed superior oxygen barrier properties (i.e., less oxygen ingress). [0050]
  • Also, as shown in Table I, oxygen ingress through a plastic bottle (i.e., either a mono-layered PET or multi-layered bottle) with closures of different size having liners of different shapes was also measured. Again, bottles fitted with closures that included liners made in accordance with the present invention (identified as 622) consistently exhibited lower oxygen ingress than bottles fitted with closures having liners made from other plastic compositions. [0051]
    TABLE I
    COMPARISON OF OXYGEN INGRESS THROUGH DIFFERENT LINERS
    MOCON Oxygen Ingress (ppm/1 Year)
    (cc/package/day/atm.) Mono-layer
    Size Closure Liner Profile Liner Material High Low Average PET*** Multi-layered****
    38 mm Flat 615 0.0150 35 13
    38 mm Flat 622 0.0019 0.0011 0.0015 27 6
    38 mm Plug 622 0.0069 0.0044 0.0058 30 8
    38 mm Plug 615 0.0219 0.0180 0.0193 37 16
    38 mm Plug 622 0.0111 0.0090 0.0104 32 12
    38 mm Aseptic 615 0.0150 35 13
    38 mm Aseptic 622 0.0036 0.0032 0.0035 28 7
    43 mm Flat 615 0.0240 0.0160 0.018 36 15
    43 mm Flat 622 0.0060 0.0018 0.003-0.005 28 7
    63 mm Full Pad 615 0.0520 0.0350 0.036-0.042 46 25
    63 mm Full Pad 622 0.0144 0.0107 0.0130 33 12
    63 mm Ring Lined 615 0.0430 50 29
    63 mm Ring Lined 622 0.0160 0.0130 0.0140 34 13
    82 mm** Ring Lined 615 0.0452 0.0392 0.0410 49 28
    82 mm** Ring Lined 622 0.0401 0.0243 0.0319 44 22
  • EXAMPLE 2
  • Oxygen ingress through the liner alone (without the closure cap) was also measured. Sample plaques made from the plastic liner composition of Example 1 and measuring approximately 4×4×0.060 inches were prepared and were measured for oxygen ingress using MOCON® permeation measuring equipment. For comparison, sample plaques made from only the thermoplastic elastomer (without polyisobutylene, polybutylene and microcrystalline wax) were prepared and also measured for oxygen ingress. Oxygen ingress across the plaque made from the liner composition of the present invention was approximately 4.8-7.9 cc/m[0052] 2/day/atm. By comparison, oxygen ingress across the plaque made from the thermoplastic elastomer alone was approximately 14.4 cc/m2/day.
  • In addition to the above, liners of the present invention exhibit excellent adhesion to the polypropylene shells often used for beverage containers. Liners of the present invention made from the plastic composition also exhibit excellent mechanical and physical strength. For example, liners made from the preferred plastic compositions described above exhibit a 100% modulus of greater than approximately 260 psi. A percent elongation of greater than approximately 350 and a tensile strength of greater than approximately 500 psi. [0053]
  • EXAMPLE 3 Modulus, Elongation and Tensile Strength
  • Samples of the plastic composition were prepared by blending approximately 65 parts thermoplastic elastomer that includes a homopolymer or copolymer of polypropylene and a butyl-based rubber, 20 parts polyisobutylene, 15 parts polybutylene and 4 parts microcrystalline wax. The blend was extruded into a 0.060×6×6 (inch) plaque from which samples were die cut in accordance with ASTM D412 procedures. The samples were tested for 100% modulus psi percent elongation and tensile strength psi (ASTM D412). Three lots of the composition made in accordance with the present invention were prepared and average values are set forth below in Table II. For comparison, a lot of the thermoplastic elastomer alone (without the polybutylene, polyisobutylene and microcrystalline wax) was similarly tested for 100% modulus psi, elongation and tensile strength psi. The results of such testing are likewise reported in Table II under the heading “TPE.” As seen from Table II, the plastic composition of the present invention (identified as 622) was also superior in these mechanical and physical properties. [0054]
    TABLE II
    622 TPE
    100% Modulus 337 255
    Elongation % 460 332
    Tensile psi 667 481
  • The above described closures were also tested for adhesion to the polypropylene shell. In general, liners made in accordance with the present invention exhibited excellent adhesion to the shell. [0055]
  • The present invention has been described in the context of its preferred embodiments. It will be apparent to those skilled in the art, however, that modifications and variations therefrom can be made without departing from the spirit and scope of this invention. Accordingly, this invention is to be construed by the scope of the appended claims. [0056]

Claims (32)

That which is claimed:
1. A substantially oil-free closure cap liner or gasket composition comprising a blend of a thermoplastic elastomer, polybutylene and polyisobutylene.
2. The composition of claim 1 further comprising a microcrystalline wax.
3. The composition of claim 1 wherein said blend comprises, by weight, between approximately 40 to 70 parts thermoplastic elastomer, approximately 15 to 30 parts polyisobutylene and approximately 10 to 35 parts polybutylene.
4. The composition of claim 1 wherein said blend comprises, by weight, approximately 65 parts thermoplastic elastomer, approximately 20 parts polyisobutylene and approximately 15 parts polybutylene.
5. The composition of claim 2 wherein said blend comprises, by weight, approximately 65 parts thermoplastic elastomer, approximately 20 parts polyisobutylene, approximately 15 parts polybutylene and approximately 4 parts microcrystalline wax.
6. The composition of claim 1 wherein said thermoplastic elastomer comprises a polyolefin, a butyl-based rubber and a lubricant.
7. The composition of claim 1, wherein said composition exhibits a 100% modulus of greater than approximately 280 psi, a percent elongation of greater than approximately 400 and a tensile strength of greater than approximately 500 psi.
8. A closure comprising;
a plastic shell having an end panel and an integral skirt downwardly extending from the periphery thereof;
said end panel having an inner surface;
a substantially oxygen impermeant liner adhered to at least a portion of said inner surface, wherein said liner comprises a blend of a thermoplastic elastomer, polybutylene and polyisobutylene.
9. The closure of claim 8 wherein said thermoplastic elastomer comprises a polyolefin, a butyl-based rubber and a lubricant.
10. The closure of claim 8 wherein said thermoplastic elastomer comprises a block copolymer.
11. The closure of claim 8 wherein said blend comprises, by weight, approximately 40 to 70 parts thermoplastic elastomer, approximately 15 to 30 parts polyisobutylene and approximately 10 to 35 parts polybutylene.
12. The closure of claim 11 wherein said blend comprises, by weight, approximately 65 parts thermoplastic elastomer, approximately 20 parts polyisobutylene and approximately 15 parts polybutylene.
13. The closure of claim 8 wherein said blend further comprises a microcrystalline wax.
14. The closure of claim 13 wherein said blend comprises, by weight, approximately 65 parts thermoplastic elastomer, approximately 20 parts polyisobutylene, approximately 15 parts polybutylene and approximately 4 parts microcrystalline wax.
15. The closure of claim 8 wherein said liner comprises a flat disk disposed over substantially the entire inner surface of said end panel.
16. The closure of claim 8 wherein said liner comprises an annular ring disposed over the peripheral portion of the inner surface of said end panel.
17. The closure of claim 15 wherein said liner comprises an interior portion and a peripheral portion, said peripheral portion having a thickness greater than said interior portion.
18. The closure of claim 17 wherein said peripheral portion has a thickness of approximately 0.030-0.035 inches.
19. The closure of claim 17 wherein said interior portion has a thickness of approximately 0.010-0.015 inches.
20. The closure of claim 8 wherein said liner exhibits an average oxygen ingress rate of less than 14.0 cc/m2/day.
21. The container closure of claim 8 wherein said liner exhibits an average oxygen ingress rate of approximately 4.0-8.0 cc/m2/day.
22. A method for providing a liner for a container closure comprising:
combining a thermoplastic elastomer with selected amounts of polyisobutylene and polybutylene;
mixing said thermoplastic elastomer with said polyisobutylene and said polybutylene to provide a blend; and
forming said blend into a circular liner.
23. The method of claim 22 further comprising adding a microcrystalline wax prior to forming said blend into said liner.
24. The method of claim 22 comprising combining said thermoplastic elastomer with said polybutylene prior to adding said polyisobutylene.
25. The method of claim 22 comprising:
providing a thermoplastic elastomer;
combining polyisobutylene with said elastomer;
adding said polybutylene to said combination of elastomer and polyisobutylene.
26. The method of claim 22 wherein said combining and mixing are carried out at a temperature not exceeding 225° C.
27. The method of claim 26 wherein said combining and mixing are carried out at a temperature of approximately 180° C.
28. The method of claim 22 comprising combining, by weight, approximately 40 to 70 parts thermoplastic elastomer with approximately 15 to 30 parts polyisobutylene and approximately 10 to 35 parts polybutylene.
29. The method of claim 22 comprising adding approximately 4 parts of said microcrystalline wax to said blend.
30. The method of claim 29 comprising combining, by weight, approximately 65 parts thermoplastic elastomer, approximately 20 parts polyisobutylene, approximately 15 parts polybutylene and approximately 4 parts microcrystalline wax.
31. The method of claim 22 further comprising forming said blend into said liner by injection molding or cold punch molding.
32. The method of claim 22 comprising first combining polyisobutylene with an anti-blocking talc prior to adding said thermoplastic elastomer and said polybutylene.
US10/748,561 2000-08-14 2003-12-30 Closure cap liners having oxygen barrier properties Abandoned US20040161560A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US10/748,561 US20040161560A1 (en) 2000-08-14 2003-12-30 Closure cap liners having oxygen barrier properties

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US09/638,240 US6677397B1 (en) 2000-08-14 2000-08-14 Closure cap liners having oxygen barrier properties
US10/748,561 US20040161560A1 (en) 2000-08-14 2003-12-30 Closure cap liners having oxygen barrier properties

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
US09/638,240 Division US6677397B1 (en) 2000-08-14 2000-08-14 Closure cap liners having oxygen barrier properties

Publications (1)

Publication Number Publication Date
US20040161560A1 true US20040161560A1 (en) 2004-08-19

Family

ID=24559198

Family Applications (2)

Application Number Title Priority Date Filing Date
US09/638,240 Expired - Fee Related US6677397B1 (en) 2000-08-14 2000-08-14 Closure cap liners having oxygen barrier properties
US10/748,561 Abandoned US20040161560A1 (en) 2000-08-14 2003-12-30 Closure cap liners having oxygen barrier properties

Family Applications Before (1)

Application Number Title Priority Date Filing Date
US09/638,240 Expired - Fee Related US6677397B1 (en) 2000-08-14 2000-08-14 Closure cap liners having oxygen barrier properties

Country Status (13)

Country Link
US (2) US6677397B1 (en)
EP (1) EP1322526A1 (en)
JP (1) JP2004505864A (en)
KR (1) KR20030038700A (en)
CN (1) CN1452579A (en)
AU (2) AU2001273557B2 (en)
BR (1) BR0113225A (en)
CA (1) CA2419135A1 (en)
HU (1) HUP0301589A2 (en)
MX (1) MXPA03001301A (en)
PL (1) PL359925A1 (en)
WO (1) WO2002014171A1 (en)
ZA (1) ZA200301068B (en)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040191445A1 (en) * 2003-03-27 2004-09-30 Baranowski Thomas R. Transparent closure cap liner having oxygen barrier properties
US20050284837A1 (en) * 2004-06-18 2005-12-29 James Taber Composite closure with barrier end panel
US20070187352A1 (en) * 2005-12-28 2007-08-16 Stephen Kras Retortable package with plastic closure cap
US20080153952A1 (en) * 2006-12-20 2008-06-26 Owens-Illinois Closure Inc. Closure liner for high-temperature applications
US20080160388A1 (en) * 2006-12-27 2008-07-03 Stmicroelectronics S.A. Package for a miniature fuel cell
US20110139670A1 (en) * 2009-12-14 2011-06-16 Dean Intellectual Property Services, Inc. Food packaging closure with an oxygen scrubbing function
US20170246649A1 (en) * 2016-02-29 2017-08-31 Albea Le Treport Product Dispensing System for a Bottle

Families Citing this family (40)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
USD245490S (en) * 1976-01-19 1977-08-23 Klitzner William S Zodiac charm
US20060229402A1 (en) * 2001-02-13 2006-10-12 Varma Rajesh K Essentially gas-impermeable thermoplastic sealant
US6874648B2 (en) * 2001-09-21 2005-04-05 Owens-Illinois Closure Inc. Closure with gas-barrier liner and package incorporating same
MXNL06000041A (en) * 2006-06-26 2008-01-07 Fabricas Monterrey Sa De Cv Corrosion-inhibiting coating for metallic substrates and corrosion-resistant article.
US20100176134A1 (en) * 2008-07-22 2010-07-15 Cramer Kenneth M Retortable Closures and Containers
EP2208684A1 (en) * 2009-01-19 2010-07-21 Guglielmo Ferrari Air intake valve for containers containing liquid products
US20110253666A1 (en) * 2010-03-19 2011-10-20 Keller Timothy P Liner-stretching bottle closure body recess and reinforcing insert
US9801969B2 (en) 2011-03-25 2017-10-31 Szent Bev Co. Scented attachment for containers
US10744223B2 (en) 2011-03-25 2020-08-18 Szent Co. Scented material compositions and articles for use with food and beverage
KR101707081B1 (en) * 2011-05-11 2017-02-15 악테가 데에스 게엠베하 Sterilizable pvc-free caps
FI3699251T3 (en) 2011-05-11 2023-10-13 Actega Ds Gmbh Pvc-free closures
CN104302726A (en) * 2012-03-01 2015-01-21 格雷斯公司 Closure liner composition with improved oxygen reduction
US20130341339A1 (en) * 2012-06-22 2013-12-26 Ryan Savage Beverage Container Kit
US9428292B2 (en) * 2013-03-13 2016-08-30 Silgan White Cap LLC Fluid injection system and method for supporting container walls
US8893906B2 (en) 2013-03-15 2014-11-25 Silgan White Cap LLC Metal closure and seal combination for maintaining the shape of a plastic container neck
PL3024888T3 (en) * 2013-07-22 2020-02-28 Actega Ds Gmbh Sealing compounds with barrier properties
US20150121807A1 (en) * 2013-11-04 2015-05-07 Silgan White Cap LLC Fluid injection system and method for scavenging oxygen in a container
CN104309910A (en) * 2014-09-29 2015-01-28 无锡华鹏瓶盖有限公司 Production process of TPE (thermoplastic elastomer) claw-type unscrew cap
US9969913B2 (en) 2014-10-27 2018-05-15 Teknor Apex Company Sealing element compositions having biorenewable content
WO2016138930A1 (en) * 2015-03-02 2016-09-09 Actega Ds Gmbh Container closure made of metal or plastic
US20160332783A1 (en) 2015-05-11 2016-11-17 Silgan White Cap LLC Lightweight Closure with Tamper Band
USD826047S1 (en) 2017-03-29 2018-08-21 Szent Co. Bottle ring
USD827435S1 (en) 2017-03-29 2018-09-04 Szent Co. Bottle ring
USD885906S1 (en) * 2017-03-31 2020-06-02 Szent Bev Co. Bottle cap
USD885902S1 (en) * 2018-01-29 2020-06-02 Betapack, S.A.U. Cap (for bottles)
GB2583637B (en) * 2018-02-19 2022-06-08 Suntory Holdings Ltd Container lid having oxygen shielding properties
USD885904S1 (en) * 2018-05-01 2020-06-02 Silgan White Cap LLC Venting closure
USD950384S1 (en) 2018-05-16 2022-05-03 Szent Co. Bottle
US11097877B2 (en) 2018-05-31 2021-08-24 Szent Co. Scent delivery and preservation systems and methods for beverage containers
DE102018128283B4 (en) * 2018-07-23 2023-04-27 Silgan White Cap Manufacturing Gmbh Vessel closure with sealing element
USD883783S1 (en) * 2018-11-29 2020-05-12 Codiplas Cap for a bottle
USD884474S1 (en) * 2018-11-29 2020-05-19 Codiplas Cap for a bottle
US11312528B2 (en) 2019-10-07 2022-04-26 Szent Co. Scented attachments for beverage cartons
US11059633B2 (en) 2019-10-31 2021-07-13 Cheer Pack North America Flip-top closure for container
US20230076229A1 (en) * 2020-03-27 2023-03-09 Mitsui Chemicals, Inc. Thermoplastic elastomer composition and shaped article thereof
CA3126215A1 (en) 2020-06-23 2021-12-23 Silgan White Cap LLC Sealing structures for closure
USD962767S1 (en) 2020-07-24 2022-09-06 Bocks Inc Plant based cap assembly for soap carton
EP4267481A1 (en) 2020-12-22 2023-11-01 Silgan White Cap LLC Venting closure liner
USD996967S1 (en) * 2021-05-17 2023-08-29 Closure Systems International Inc. Closure
USD996968S1 (en) * 2021-05-17 2023-08-29 Closure Systems International Inc. Closure

Citations (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2194958A (en) * 1939-12-08 1940-03-26 American Anode Inc Aqueous dispersion of polymerized hydrocarbon material and method of preparing the same
US2557169A (en) * 1948-03-18 1951-06-19 Armstrong Cork Co Container closure adhesive comprising an aqueous dispersion of albumin and an isobutylene-diolefin copolymer
US3897260A (en) * 1971-06-25 1975-07-29 Nippon Zeon Co Novel coating composition
US3924051A (en) * 1970-09-08 1975-12-02 American Can Co Oriented saran coextrudate
US4151924A (en) * 1977-11-07 1979-05-01 Owens-Illinois, Inc. Liner element for closure cap
US4198369A (en) * 1976-02-09 1980-04-15 Mitsui Petrochemical Industries Ltd. Process for lining container caps
US4235953A (en) * 1978-03-16 1980-11-25 Tremco, Incorporated Waterproofing sheet material
US4253580A (en) * 1978-08-22 1981-03-03 Toyo Seikan Kaisha, Ltd. Container cover with peelable liner
US4360120A (en) * 1980-09-25 1982-11-23 W. R. Grace & Co. Sealing compositions
US4468254A (en) * 1982-04-20 1984-08-28 Nippon Oil Co., Ltd. Wax emulsion
US4684554A (en) * 1985-04-12 1987-08-04 Minnesota Mining And Manufacturing Company Polymeric coating for container induction innerseal
US5018632A (en) * 1990-06-29 1991-05-28 Continental White Cap Inc. Tamper evident closure
US5060818A (en) * 1988-08-08 1991-10-29 Japan Crown Cork Co., Ltd. Heat-resistant liner-provided vessel closure and process for preparation thereof
US5143763A (en) * 1990-07-13 1992-09-01 Toray Industries, Inc. Oxygen scavenger
US5289932A (en) * 1992-04-15 1994-03-01 Canada Plastic Containers Limited Closure cap with plastic liner
US5296129A (en) * 1990-11-30 1994-03-22 Bridgestone Corporation Paraffin wax compositions and rubber compositions into which paraffin wax compositions are incorporated
US5381914A (en) * 1991-05-09 1995-01-17 Toyo Seikan Kaisha, Ltd. Container closure with liner
US5685443A (en) * 1995-03-06 1997-11-11 White Cap, Inc. Composite closure and method of making same
US5772076A (en) * 1996-07-26 1998-06-30 White Cap, Inc. Hot fill dispensing closure
US5843577A (en) * 1994-03-29 1998-12-01 Advanced Elastomer Systems, L.P. Thermoplastic elastomers having improved surface properties
US5849418A (en) * 1993-08-18 1998-12-15 The Dow Chemical Company Gaskets made from homogeneous linear olefin polymers
US5855836A (en) * 1995-09-27 1999-01-05 3D Systems, Inc. Method for selective deposition modeling
US5955163A (en) * 1991-06-05 1999-09-21 W.R. Grace & Co.-Conn. Gasket composition for crown caps
US6140418A (en) * 1996-10-04 2000-10-31 Kuraray Co., Ltd. Thermoplastic polymer composition
US20040191445A1 (en) * 2003-03-27 2004-09-30 Baranowski Thomas R. Transparent closure cap liner having oxygen barrier properties

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4957968A (en) * 1988-08-09 1990-09-18 Monsanto Company Adhesive thermoplastic elastomer blends

Patent Citations (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2194958A (en) * 1939-12-08 1940-03-26 American Anode Inc Aqueous dispersion of polymerized hydrocarbon material and method of preparing the same
US2557169A (en) * 1948-03-18 1951-06-19 Armstrong Cork Co Container closure adhesive comprising an aqueous dispersion of albumin and an isobutylene-diolefin copolymer
US3924051A (en) * 1970-09-08 1975-12-02 American Can Co Oriented saran coextrudate
US3897260A (en) * 1971-06-25 1975-07-29 Nippon Zeon Co Novel coating composition
US4198369A (en) * 1976-02-09 1980-04-15 Mitsui Petrochemical Industries Ltd. Process for lining container caps
US4151924A (en) * 1977-11-07 1979-05-01 Owens-Illinois, Inc. Liner element for closure cap
US4235953A (en) * 1978-03-16 1980-11-25 Tremco, Incorporated Waterproofing sheet material
US4253580A (en) * 1978-08-22 1981-03-03 Toyo Seikan Kaisha, Ltd. Container cover with peelable liner
US4360120A (en) * 1980-09-25 1982-11-23 W. R. Grace & Co. Sealing compositions
US4468254A (en) * 1982-04-20 1984-08-28 Nippon Oil Co., Ltd. Wax emulsion
US4684554A (en) * 1985-04-12 1987-08-04 Minnesota Mining And Manufacturing Company Polymeric coating for container induction innerseal
US5060818A (en) * 1988-08-08 1991-10-29 Japan Crown Cork Co., Ltd. Heat-resistant liner-provided vessel closure and process for preparation thereof
US5018632A (en) * 1990-06-29 1991-05-28 Continental White Cap Inc. Tamper evident closure
US5143763A (en) * 1990-07-13 1992-09-01 Toray Industries, Inc. Oxygen scavenger
US5296129A (en) * 1990-11-30 1994-03-22 Bridgestone Corporation Paraffin wax compositions and rubber compositions into which paraffin wax compositions are incorporated
US5381914A (en) * 1991-05-09 1995-01-17 Toyo Seikan Kaisha, Ltd. Container closure with liner
US5955163A (en) * 1991-06-05 1999-09-21 W.R. Grace & Co.-Conn. Gasket composition for crown caps
US5289932A (en) * 1992-04-15 1994-03-01 Canada Plastic Containers Limited Closure cap with plastic liner
US5849418A (en) * 1993-08-18 1998-12-15 The Dow Chemical Company Gaskets made from homogeneous linear olefin polymers
US5843577A (en) * 1994-03-29 1998-12-01 Advanced Elastomer Systems, L.P. Thermoplastic elastomers having improved surface properties
US5685443A (en) * 1995-03-06 1997-11-11 White Cap, Inc. Composite closure and method of making same
US5855836A (en) * 1995-09-27 1999-01-05 3D Systems, Inc. Method for selective deposition modeling
US5772076A (en) * 1996-07-26 1998-06-30 White Cap, Inc. Hot fill dispensing closure
US6140418A (en) * 1996-10-04 2000-10-31 Kuraray Co., Ltd. Thermoplastic polymer composition
US20040191445A1 (en) * 2003-03-27 2004-09-30 Baranowski Thomas R. Transparent closure cap liner having oxygen barrier properties

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040191445A1 (en) * 2003-03-27 2004-09-30 Baranowski Thomas R. Transparent closure cap liner having oxygen barrier properties
US20050284837A1 (en) * 2004-06-18 2005-12-29 James Taber Composite closure with barrier end panel
US20070187352A1 (en) * 2005-12-28 2007-08-16 Stephen Kras Retortable package with plastic closure cap
US8596477B2 (en) 2005-12-28 2013-12-03 Silgan White Cap LLC Retortable package with plastic closure cap
US20080153952A1 (en) * 2006-12-20 2008-06-26 Owens-Illinois Closure Inc. Closure liner for high-temperature applications
US20080160388A1 (en) * 2006-12-27 2008-07-03 Stmicroelectronics S.A. Package for a miniature fuel cell
FR2911009A1 (en) * 2006-12-27 2008-07-04 St Microelectronics Sa CASE FOR MINIATURE FUEL CELL
US7662500B2 (en) 2006-12-27 2010-02-16 Stmicroelectronics S.A. Package for a miniature fuel cell
US20110139670A1 (en) * 2009-12-14 2011-06-16 Dean Intellectual Property Services, Inc. Food packaging closure with an oxygen scrubbing function
US20170246649A1 (en) * 2016-02-29 2017-08-31 Albea Le Treport Product Dispensing System for a Bottle
US11123759B2 (en) * 2016-02-29 2021-09-21 Albea Le Treport Product dispensing system for a bottle

Also Published As

Publication number Publication date
CA2419135A1 (en) 2002-02-21
WO2002014171A1 (en) 2002-02-21
AU7355701A (en) 2002-02-25
BR0113225A (en) 2003-07-08
AU2001273557B2 (en) 2005-07-21
US6677397B1 (en) 2004-01-13
CN1452579A (en) 2003-10-29
MXPA03001301A (en) 2004-07-30
EP1322526A1 (en) 2003-07-02
ZA200301068B (en) 2004-02-07
JP2004505864A (en) 2004-02-26
KR20030038700A (en) 2003-05-16
HUP0301589A2 (en) 2003-08-28
PL359925A1 (en) 2004-09-06

Similar Documents

Publication Publication Date Title
US6677397B1 (en) Closure cap liners having oxygen barrier properties
AU2001273557A1 (en) Closure cap liners having oxygen barrier properties
US8460771B2 (en) Retortable liners and containers
US7056971B2 (en) Essentially gas-impermeable thermoplastic elastomer
JPH0688608B2 (en) Heat-resistant liner-equipped container lid and manufacturing method thereof
US11639434B2 (en) Container closure made of metal or plastic
US7021478B1 (en) Plastic closure with compression molded sealing/barrier liner
EP2820101B1 (en) Closure liner composition with improved oxygen reduction
JP4493149B2 (en) Capable of heat sterilization
US20060024460A1 (en) Transparent closure cap liner having oxygen barrier properties
JP2000281117A (en) Cap liner
US20220298346A1 (en) Tpe based liners for pressurized containers
JP3973279B2 (en) Cap suitable for aseptic filling
AU614854B2 (en) Container closures, sealed containers and sealing compositions for them
JP3811218B2 (en) Cap suitable for aseptic filling
JP2002284219A (en) Cap with liner
JPH1170965A (en) Cap liner material composition and cap molded article
MXPA99000242A (en) Closure of plastic with interior coating of barrier molded by compres
JPH04114870A (en) Cap material for glass container and its sealing method

Legal Events

Date Code Title Description
AS Assignment

Owner name: SILGAN HOLDINGS INC., CONNECTICUT

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:AMCOR WHITE CAP, INC.;REEL/FRAME:018087/0609

Effective date: 20060601

Owner name: AMCOR WHITE CAP, INC., ILLINOIS

Free format text: CHANGE OF NAME;ASSIGNOR:WHITE CAP, INC.;REEL/FRAME:018087/0252

Effective date: 20020910

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION