WO2015069620A1 - Hot-fill container - Google Patents

Hot-fill container Download PDF

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Publication number
WO2015069620A1
WO2015069620A1 PCT/US2014/063812 US2014063812W WO2015069620A1 WO 2015069620 A1 WO2015069620 A1 WO 2015069620A1 US 2014063812 W US2014063812 W US 2014063812W WO 2015069620 A1 WO2015069620 A1 WO 2015069620A1
Authority
WO
WIPO (PCT)
Prior art keywords
base
container
plastic container
features
triangular features
Prior art date
Application number
PCT/US2014/063812
Other languages
English (en)
French (fr)
Inventor
Terry D. Patcheak
David Downing
Frederick C. Beuerle
Walter J. Strasser
Christopher Howe
Luke A. Mast
Original Assignee
Amcor Limited
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
Priority claimed from US14/072,377 external-priority patent/US9394072B2/en
Application filed by Amcor Limited filed Critical Amcor Limited
Priority to ES14859477T priority Critical patent/ES2935582T3/es
Priority to CA2925871A priority patent/CA2925871C/en
Priority to MX2016003964A priority patent/MX2016003964A/es
Priority to BR112016010249-5A priority patent/BR112016010249B1/pt
Priority to EP14859477.3A priority patent/EP3066010B1/en
Priority to BR112016010250A priority patent/BR112016010250A2/pt
Priority to JP2016527341A priority patent/JP6744214B2/ja
Publication of WO2015069620A1 publication Critical patent/WO2015069620A1/en

Links

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
    • B65D79/00Kinds or details of packages, not otherwise provided for
    • B65D79/005Packages having deformable parts for indicating or neutralizing internal pressure-variations by other means than venting
    • B65D79/008Packages having deformable parts for indicating or neutralizing internal pressure-variations by other means than venting the deformable part being located in a rigid or semi-rigid container, e.g. in bottles or jars
    • B65D79/0081Packages having deformable parts for indicating or neutralizing internal pressure-variations by other means than venting the deformable part being located in a rigid or semi-rigid container, e.g. in bottles or jars in the bottom part thereof
    • 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
    • B65D1/00Containers having bodies formed in one piece, e.g. by casting metallic material, by moulding plastics, by blowing vitreous material, by throwing ceramic material, by moulding pulped fibrous material, by deep-drawing operations performed on sheet material
    • B65D1/02Bottles or similar containers with necks or like restricted apertures, designed for pouring contents
    • B65D1/0223Bottles or similar containers with necks or like restricted apertures, designed for pouring contents characterised by shape
    • B65D1/0261Bottom construction
    • 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
    • B65D2501/00Containers having bodies formed in one piece
    • B65D2501/0009Bottles or similar containers with necks or like restricted apertures designed for pouring contents
    • B65D2501/0018Ribs
    • B65D2501/0036Hollow circonferential ribs

Definitions

  • the present disclosure relates to plastic hot-fill containers with bases including features, such as equilateral triangular features, configured to absorb vacuum pressures.
  • PET containers are now being used more than ever to package numerous commodities previously packaged in glass containers.
  • PET containers for various liquid commodities, such as juice and isotonic beverages.
  • Suppliers often fill these liquid products into the containers while the liquid product is at an elevated temperature, typically between 68°C - 96°C (155°F - 205°F) and usually at approximately 85°C (185°F).
  • the hot temperature of the liquid commodity sterilizes the container at the time of filling.
  • the bottling industry refers to this process as hot filling, and containers designed to withstand the process as hot-fill or heat-set containers.
  • the hot filling process is acceptable for commodities having a high acid content, but not generally acceptable for non-high acid content commodities. Nonetheless, manufacturers and fillers of non-high acid content commodities desire to supply their commodities in PET containers as well.
  • Pasteurization and retort are the preferred sterilization process.
  • Pasteurization and retort both present an enormous challenge for manufactures of PET containers in that heat-set containers cannot withstand the temperature and time demands required of pasteurization and retort.
  • Pasteurization and retort are both processes for cooking or sterilizing the contents of a container after filling. Both processes include the heating of the contents of the container to a specified temperature, usually above approximately 70°C (approximately 155°F), for a specified length of time (20 - 60 minutes). Retort differs from pasteurization in that retort uses higher temperatures to sterilize the container and cook its contents. Retort also applies elevated air pressure externally to the container to counteract pressure inside the container. The pressure applied externally to the container is necessary because a hot water bath is often used and the overpressure keeps the water, as well as the liquid in the contents of the container, in liquid form, above their respective boiling point temperatures.
  • PET is a crystallizable polymer, meaning that it is available in an amorphous form or a semi-crystalline form.
  • the ability of a PET container to maintain its material integrity relates to the percentage of the PET container in crystalline form, also known as the "crystallinity" of the PET container.
  • the following equation defines the percentage of crystallinity as a volume fraction:
  • p is the density of the PET material
  • p a is the density of pure amorphous PET material (1 .333 g/cc)
  • p c is the density of pure crystalline material (1 .455 g/cc).
  • Container manufactures use mechanical processing and thermal processing to increase the PET polymer crystallinity of a container.
  • Mechanical processing involves orienting the amorphous material to achieve strain hardening. This processing commonly involves stretching a PET preform along a longitudinal axis and expanding the PET preform along a transverse or radial axis to form a PET container. The combination promotes what manufacturers define as biaxial orientation of the molecular structure in the container.
  • Manufacturers of PET containers currently use mechanical processing to produce PET containers having approximately 20% crystallinity in the container's sidewalk
  • Thermal processing involves heating the material (either amorphous or semi-crystalline) to promote crystal growth.
  • thermal processing of PET material results in a spherulitic morphology that interferes with the transmission of light. In other words, the resulting crystalline material is opaque, and thus, generally undesirable.
  • thermal processing results in higher crystallinity and excellent clarity for those portions of the container having biaxial molecular orientation.
  • the thermal processing of an oriented PET container typically includes blow molding a PET preform against a mold heated to a temperature of approximately 120°C - 130°C (approximately 248°F - 266°F), and holding the blown container against the heated mold for approximately three (3) seconds.
  • Manufacturers of PET juice bottles which must be hot-filled at approximately 85 °C (185°F), currently use heat setting to produce PET bottles having an overall crystallinity in the range of approximately 25 - 35%.
  • the heat-set containers After being hot-filled, the heat-set containers are capped and allowed to reside at generally the filling temperature for approximately five (5) minutes at which point the container, along with the product, is then actively cooled prior to transferring to labeling, packaging, and shipping operations.
  • the cooling reduces the volume of the liquid in the container.
  • This product shrinkage phenomenon results in the creation of a vacuum within the container.
  • vacuum pressures within the container range from 1 -300 mm Hg less than atmospheric pressure (i.e., 759 mm Hg - 460 mm Hg). If not controlled or otherwise accommodated, these vacuum pressures result in deformation of the container, which leads to either an aesthetically unacceptable container or one that is unstable.
  • container weight is correlated to the amount of the final vacuum present in the container after this fill, cap and cool down procedure, that is, the container is made relatively heavy to accommodate vacuum related forces.
  • reducing container weight i.e., "Nghtweighting" the container, while providing a significant cost savings from a material standpoint, requires a reduction in the amount of the final vacuum.
  • the amount of the final vacuum can be reduced through various processing options such as the use of nitrogen dosing technology, minimize headspace or reduce fill temperature.
  • nitrogen dosing technology One drawback with the use of nitrogen dosing technology however is that the maximum line speeds achievable with the current technology is limited to roughly 200 containers per minute. Such slower line speeds are seldom acceptable. Additionally, the dosing consistency is not yet at a technological level to achieve efficient operations. Minimizing headspace requires more precession during filling, again resulting in slower line speeds. Reducing fill temperature is equally disadvantageous as it limits the type of commodity suitable for the container.
  • container manufacturers accommodate vacuum pressures by incorporating structures in the container sidewall.
  • Container manufacturers commonly refer to these structures as vacuum panels. Traditionally, these paneled areas have been semi-rigid by design, unable to accommodate the high levels of vacuum pressures currently generated, particularly in lightweight containers.
  • an alternative vacuum absorbing capability is provided within both the container body and base.
  • Traditional hot-fill containers accommodate nearly all vacuum forces within the body (or sidewall) of the container through deflection of the vacuum panels.
  • These containers are typically provided with a rigid base structure that substantially prevents deflection thereof and thus tends to be heavier than the rest of the container.
  • POWERFLEX technology offered by the assignee of the present application, utilizes a lightweight base design to accommodate nearly all vacuum forces.
  • the POWERFLEX base must be designed to invert, which requires a dramatic snap-through from an outwardly curved initial shape to an inwardly curved final shape. This typically requires that the sidewall of the container be sufficiently rigid to allow the base to activate under vacuum, thus requiring more weight and/or structure within the container sidewall. Neither the traditional technology nor POWERFLEX system offers the optimal balance of a thin light-weight container body and base that is capable of withstanding the necessary vacuum pressures.
  • an object of the present teachings is to achieve the optimal balance of weight and vacuum performance of both the container body and base.
  • a hot-fill container is provided that comprises a lightweight, flexible base design that is easily moveable to accommodate vacuum, but does not require a dramatic inversion or snap- through, thus eliminating the need for a heavy sidewall.
  • the flexible base design serves to complement vacuum absorbing capabilities within the container sidewall.
  • an object of the present teachings is to define theoretical light weighting limits and explore alternative vacuum absorbing technologies that create additional structure under vacuum.
  • the container body and base of the present teachings can each be lightweight structures designed to accommodate vacuum forces either simultaneously or in sequence. In any event, the goal is for both the container body and base to absorb a significant percentage of the vacuum.
  • a lightweight base design to absorb a portion of the vacuum forces enables an overall light-weighting, design flexibility, and effective utilization of alternative vacuum absorbing capabilities on the container sidewall. It is therefore an object of the present teachings to provide such a container. It should be understood, however, that in some embodiments some principles of the present teachings, such as the base configurations, can be used separate from other principles, such as the sidewall configurations, or vice versa.
  • the present teachings provide for a plastic container including an upper portion, a base, a plurality of surface features, and a substantially cylindrical portion.
  • the upper portion has a mouth defining an opening into the container.
  • the base is movable to accommodate vacuum forces generated within the container thereby decreasing the volume of the container.
  • the plurality of surface features are included with the base and are configured to accommodate vacuum forces.
  • the substantially cylindrical portion extends between the upper portion and the base.
  • the present teachings further provide for a plastic container including an upper portion, a base, a plurality of adjacent equilateral triangular features, and a substantially cylindrical portion.
  • the base is movable to accommodate vacuum forces generated within the container thereby decreasing the volume of the container.
  • the plurality of adjacent triangular features protrude from the base and are configured to accommodate vacuum forces.
  • the substantially cylindrical portion extends between the upper portion and the base.
  • the present teachings also provide for a plastic container including an upper portion, a base, a plurality of adjacent equilateral triangular features, and a substantially cylindrical portion.
  • the upper portion has a mouth defining an opening into the container.
  • the base is movable to accommodate vacuum forces generated within the container thereby decreasing the volume of the container.
  • the plurality of adjacent equilateral triangular features protrude from about 50% of the base and are configured to accommodate vacuum forces.
  • the triangular features are spaced apart from both a central pushup of the base and a wall of the base.
  • the substantially cylindrical portion extends between the upper portion and the base.
  • the triangular features are formed from a mold including a plurality of peaks and troughs corresponding to the equilateral triangular features. The peaks are aligned along a first plane and the troughs are aligned along a second plane extending parallel to the first plane.
  • FIG. 1 is an elevational view of a plastic container according to the present teachings, the container as molded and empty.
  • FIG. 2 is an elevational view of the plastic container according to the present teachings, the container being filled and sealed.
  • FIG. 3 is a bottom perspective view of a portion of the plastic container of FIG. 1 .
  • FIG. 4 is a bottom perspective view of a portion of the plastic container of FIG. 2.
  • FIG. 5 is a cross-sectional view of the plastic container, taken generally along line 5-5 of FIG. 3.
  • FIG. 6 is a cross-sectional view of the plastic container, taken generally along line 6-6 of FIG. 4.
  • FIG. 7 is a cross-sectional view of the plastic container, similar to FIG. 5, according to some embodiments of the present teachings.
  • FIG. 8 is a cross-sectional view of the plastic container, similar to FIG. 6, according to some embodiments of the present teachings.
  • FIG. 9 is a bottom view of an additional embodiment of the plastic container, the container as molded and empty.
  • FIG. 10 is a cross-sectional view of the plastic container, taken generally along line 10-10 of FIG. 9.
  • FIG. 1 1 is a bottom view of the embodiment of the plastic container shown in FIG. 9, the plastic container being filled and sealed.
  • FIG. 12 is a cross-sectional view of the plastic container, taken generally along line 12-12 of FIG. 1 1 .
  • FIG. 13 is a cross-sectional view of the plastic container, similar to FIGS. 5 and 7, according to some embodiments of the present teachings.
  • FIG. 14 is a cross-sectional view of the plastic container, similar to FIGS. 6 and 8, according to some embodiments of the present teachings.
  • FIG. 15 is a bottom view of the plastic container according to some embodiments of the present teachings.
  • FIG. 16 is a cross-sectional view of the plastic container, similar to FIGS. 5 and 7, according to some embodiments of the present teachings.
  • FIG. 17 is a cross-sectional view of the plastic container, similar to FIGS. 6 and 8, according to some embodiments of the present teachings.
  • FIG. 18 is a bottom view of the plastic container according to some embodiments of the present teachings.
  • FIG. 19 is a bottom view of the plastic container according to some embodiments of the present teachings.
  • FIG. 20 is a cross-sectional view of the plastic container of FIG.
  • FIG. 21 is a bottom view of the plastic container according to some embodiments of the present teachings.
  • FIG. 22 is a cross-sectional view of the plastic container of FIG.
  • FIG. 23 is an enlarged bottom view of the plastic container of FIG. 21 .
  • FIG. 24 is a bottom view of the plastic container according to some embodiments of the present teachings.
  • FIG. 25 is a cross-sectional view of the plastic container of FIG.
  • FIG. 26 is a bottom view of the plastic container according to some embodiments of the present teachings.
  • FIG. 27 is a cross-sectional view of the plastic container of FIG.
  • FIG. 28 is a graph illustrating the vacuum response versus displacement for the plastic container of FIG. 19.
  • FIG. 29 is a graph illustrating the vacuum response versus displacement for the plastic container of FIG. 1 .
  • FIG. 30 is a graph illustrating the vacuum response versus displacement for the plastic container of FIG. 8.
  • FIG. 31 is a cross-sectional view of a plastic container according to some embodiments of the present teachings.
  • FIG. 32 is a cross-sectional view of a plastic container according to some embodiments of the present teachings.
  • FIG. 33 is a bottom view of the plastic container according to some embodiments of the present teachings.
  • FIG. 34 is a cross-sectional view of the plastic container of FIG. 33 taken along line P L -PL of FIG. 33.
  • FIG. 35 illustrates an exemplary triangular feature of an inversion ring of the plastic container of FIG. 33.
  • FIG. 36 is a cross-sectional view of a mold for forming the plastic container of FIG. 33.
  • Example embodiments will now be described more fully with reference to the accompanying drawings. Example embodiments are provided so that this disclosure will be thorough, and will fully convey the scope to those who are skilled in the art. Numerous specific details are set forth such as examples of specific components, devices, and methods, to provide a thorough understanding of embodiments of the present disclosure. It will be apparent to those skilled in the art that specific details need not be employed, that example embodiments may be embodied in many different forms and that neither should be construed to limit the scope of the disclosure.
  • containers generally have a series of vacuum panels or ribs around their sidewalk Traditionally, these vacuum panels have been semi-rigid and incapable of preventing unwanted distortion elsewhere in the container, particularly in lightweight containers.
  • a combination of controlled deformation (i.e., in the base or closure) and vacuum resistance in the remainder of the container is required.
  • each of the above examples i.e. traditional vacuum absorbing container having a lightweight and flexible sidewall with a heavy and rigid base, and POWERFLEX container having a lightweight and flexible base with a heavy and rigid sidewall
  • the simple combination of the sidewall of the traditional vacuum absorbing container and the base of the POWERFLEX container would typically lead to a container having a sidewall that is not sufficiently rigid to withstand the snap-through from an outwardly curved initial shape to an inwardly curved final shape.
  • the present teachings provide a plastic container which enables its base portion under typical hot-fill process conditions to deform and move easily while maintaining a rigid structure (i.e., against internal vacuum) in the remainder of the container.
  • the container typically should accommodate roughly 18-24 cc of volume displacement.
  • the base portion accommodates a majority of this requirement.
  • the remaining portions of the plastic container are easily able to accommodate the rest of this volume displacement without readily noticeable distortion.
  • traditional containers utilize a combination of bottle geometry and wall thickness to create a structure that can resist a portion of the vacuum, and movable sidewall panels, collapsible ribs, or moveable bases to absorb the remaining vacuum. This results in two elements of internal vacuum— residual and absorbed.
  • the sum of the residual vacuum and the absorbed vacuum equals the total amount of vacuum that results from the combination of the liquid commodity and the headspace contracting during cooling in a rigid container.
  • the container according to the present teachings combines sidewall vacuum and/or volume compensation panels or collapsible ribs with a flexible base design resulting in a hybrid of previous technologies that results in a lighter weight container than could be achieved with either method individually.
  • the vacuum and/or volume compensation characteristics could be defined as:
  • X the percentage of the total vacuum and/or volume that is absorbed by the sidewall panels, ribs and/or other vacuum and/or volume compensation features
  • Y the percentage of the total vacuum and/or volume that is absorbed by the base movement
  • Z the residual vacuum and/or volume remaining in the container after the compensation achieved by the vacuum and/or volume compensation features in the sidewall and/or base.
  • Y 10 to 90% of the total vacuum and/or volume.
  • the present teachings are operable to achieve vacuum absorption in both the base and the sidewall, thereby permitting, if desired, absorption of the entire internal vacuum. It should be appreciated that in some embodiments a slight remaining vacuum may be desired.
  • the residual vacuum (Z) should be as close as possible to 0% of the total vacuum and the combined movements of the vacuum absorbing features would be designed to absorb basically 100% of the volume contraction that occurs inside of the container as the contents cool from the filling temperature to the point of maximum density under the required service conditions. At this point external forces such as top load or side load would result in a pressurization of the container that would help it to resist those external forces. This would result in a container weight that is dictated by the requirements of the handling and distribution system, not by the filling conditions.
  • the present teachings provide a significantly round plastic container that does not ovalize below 5% total vacuum absorption that consists of a movable base and a movable sidewall at an average wall thickness less than 0.020".
  • the present teachings can provide a plastic container that comprises a base that absorbs between 10 and 90% of the total vacuum in conjunction with a sidewall that absorbs between 90 and 10% of the total vacuum absorbed.
  • the base and the sidewall can activate simultaneously.
  • the base and the sidewall can activate sequentially.
  • a significantly round plastic container is provided that provides a movable base and a movable sidewall that both activate simultaneously or sequentially at a vacuum level less than that of 5% of the total vacuum absorption of the container.
  • a combination of controlled deformation (i.e., in the base or closure) and vacuum resistance in the remainder of the container is required. Accordingly, the present teaching provides for a plastic container which enables its base portion under typical hot-fill process conditions to deform and move easily while maintaining a rigid structure (i.e., against internal vacuum) in the remainder of the container.
  • a plastic container 10 of the invention includes a finish 12, a neck or an elongated neck 14, a shoulder region 16, a body portion 18, and a base 20.
  • the neck 14 can have an extremely short height, that is, becoming a short extension from the finish 12, or an elongated neck as illustrated in the figures, extending between the finish 12 and the shoulder region 16.
  • the plastic container 10 has been designed to retain a commodity during a thermal process, typically a hot-fill process.
  • bottlers For hot-fill bottling applications, bottlers generally fill the container 10 with a liquid or product at an elevated temperature between approximately 155°F to 205 °F (approximately 68 °C to 96°C) and seal the container 10 with a closure 28 before cooling. As the sealed container 10 cools, a slight vacuum, or negative pressure, forms inside causing the container 10, in particular, the base 20 to change shape.
  • the plastic container 10 may be suitable for other high-temperature pasteurization or retort filling processes, or other thermal processes as well.
  • the plastic container 10 of the present teaching is a blow molded, biaxially oriented container with a unitary construction from a single or multi-layer material.
  • a well-known stretch-molding, heat-setting process for making the hot-fillable plastic container 10 generally involves the manufacture of a preform (not illustrated) of a polyester material, such as polyethylene terephthalate (PET), having a shape well known to those skilled in the art similar to a test-tube with a generally cylindrical cross section and a length typically approximately fifty percent (50%) that of the container height.
  • PET polyethylene terephthalate
  • a machine places the preform heated to a temperature between approximately 190°F to 250 °F (approximately 88 °C to 121 °C) into a mold cavity (not illustrated) having a shape similar to the plastic container 10.
  • the mold cavity is heated to a temperature between approximately 250°F to 350°F (approximately 121 °C to 177°C).
  • a stretch rod apparatus (not illustrated) stretches or extends the heated preform within the mold cavity to a length approximately that of the container thereby molecularly orienting the polyester material in an axial direction generally corresponding with a central longitudinal axis 50.
  • air having a pressure between 300 PSI to 600 PSI (2.07 MPa to 4.14 MPa) assists in extending the preform in the axial direction and in expanding the preform in a circumferential or hoop direction thereby substantially conforming the polyester material to the shape of the mold cavity and further molecularly orienting the polyester material in a direction generally perpendicular to the axial direction, thus establishing the biaxial molecular orientation of the polyester material in most of the container.
  • material within the finish 12 and a sub-portion of the base 20 are not substantially molecularly oriented.
  • the pressurized air holds the mostly biaxial molecularly oriented polyester material against the mold cavity for a period of approximately two (2) to five (5) seconds before removal of the container from the mold cavity.
  • the inventors employ an additional stretch-molding step substantially as taught by U.S. Patent No. 6,277,321 which is incorporated herein by reference.
  • the finish 12 of the plastic container 10 includes a portion defining an aperture or mouth 22, a threaded region 24, and a support ring 26.
  • the aperture 22 allows the plastic container 10 to receive a commodity while the threaded region 24 provides a means for attachment of the similarly threaded closure or cap 28 (shown in FIG. 2).
  • Alternatives may include other suitable devices that engage the finish 12 of the plastic container 10.
  • the closure or cap 28 engages the finish 12 to preferably provide a hermetical seal of the plastic container 10.
  • the closure or cap 28 is preferably of a plastic or metal material conventional to the closure industry and suitable for subsequent thermal processing, including high temperature pasteurization and retort.
  • the support ring 26 may be used to carry or orient the preform (the precursor to the plastic container 10) (not shown) through and at various stages of manufacture.
  • the preform may be carried by the support ring 26, the support ring 26 may be used to aid in positioning the preform in the mold, or an end consumer may use the support ring 26 to carry the plastic container 10 once manufactured.
  • the elongated neck 14 of the plastic container 10 in part enables the plastic container 10 to accommodate volume requirements. Integrally formed with the elongated neck 14 and extending downward therefrom is the shoulder region 16.
  • the shoulder region 16 merges into and provides a transition between the elongated neck 14 and the body portion 18.
  • the body portion 18 extends downward from the shoulder region 16 to the base 20 and includes sidewalls 30.
  • the specific construction of the base 20 of the container 10 allows the sidewalls 30 for the heat-set container 10 to not necessarily require additional vacuum panels or pinch grips and therefore, can be generally smooth and glass-like. However, a significantly lightweight container will likely include sidewalls having vacuum panels, ribbing, and/or pinch grips along with the base 20.
  • the base 20 of the plastic container 10, which extends inward from the body portion 18, can comprise a chime 32, a contact ring 34 and a central portion 36.
  • the contact ring 34 is itself that portion of the base 20 that contacts a support surface 38 that in turn supports the container 10.
  • the contact ring 34 may be a flat surface or a line of contact generally circumscribing, continuously or intermittently, the base 20.
  • the base 20 functions to close off the bottom portion of the plastic container 10 and, together with the elongated neck 14, the shoulder region 16, and the body portion 18, to retain the commodity.
  • the plastic container 10 is preferably heat-set according to the above-mentioned process or other conventional heat- set processes. In some embodiments, o accommodate vacuum forces while allowing for the omission of vacuum panels and pinch grips in the body portion innovative construction.
  • the central portion 36 of the base 20 can comprise a central pushup 40 and an inversion ring 42.
  • the inversion ring 42 can include an upper portion 54 and a lower portion 58.
  • the base 20 can include an upstanding circumferential wall or edge 44 that forms a transition between the inversion ring 42 and the contact ring 34.
  • the central pushup 40 when viewed in cross section, is generally in the shape of a truncated cone having a top surface 46 that is generally parallel to the support surface 38. Side surfaces 48, which are generally planar in cross section, slope upward toward the central longitudinal axis 50 of the container 10.
  • the exact shape of the central pushup 40 can vary greatly depending on various design criteria. However, in general, the overall diameter of the central pushup 40 (that is, the truncated cone) is at most 30% of generally the overall diameter of the base 20.
  • the central pushup 40 is generally where the preform gate is captured in the mold.
  • the sub-portion of the base 20 which includes polymer material that is not substantially molecularly oriented.
  • the inversion ring 42 when initially formed, completely surrounds and circumscribes the central pushup 40. As formed, the inversion ring 42 can protrude outwardly, below a plane where the base 20 would lie if it was flat. The transition between the central pushup 40 and the adjacent inversion ring 42 can be rapid in order to promote as much orientation as near the central pushup 40 as possible. This serves primarily to ensure a minimal wall thickness 66 for the inversion ring 42, in particular at the lower portion 58 of the base 20.
  • the wall thickness 66 of the lower portion 58 of the inversion ring 42 is between approximately 0.008 inch (0.20 mm) to approximately 0.025 inch (0.64 mm), and preferably between approximately 0.010 inch to approximately 0.014 inch (0.25 mm to 0.36 mm) for a container having, for example, an approximately 2.64-inch (67.06 mm) diameter base.
  • Wall thickness 70 of top surface 46 depending on precisely where one takes a measurement, can be 0.060 inch (1 .52 mm) or more; however, wall thickness 70 of the top surface 46 quickly transitions to wall thickness 66 of the lower portion 58 of the inversion ring 42.
  • the wall thickness 66 of the inversion ring 42 must be relatively consistent and thin enough to allow the inversion ring 42 to be flexible and function properly.
  • the inversion ring 42 may alternatively feature a small indentation, not illustrated but well known in the art, suitable for receiving a pawl that facilitates container rotation about the central longitudinal axis 50 during a labeling operation.
  • the circumferential wall or edge 44, defining the transition between the contact ring 34 and the inversion ring 42 can be, in cross section, an upstanding substantially straight wall approximately 0.030 inch (0.76 mm) to approximately 0.325 inch (8.26 mm) in length.
  • the circumferential wall 44 can measure between approximately 0.140 inch to approximately 0.145 inch (3.56 mm to 3.68 mm) in length.
  • the circumferential wall 44 could be as large as 0.325 inch (8.26 mm) in length.
  • the circumferential wall or edge 44 can be generally at an angle 64 relative to the central longitudinal axis 50 of between approximately zero degree and approximately 20 degrees, and preferably approximately 15 degrees. Accordingly, the circumferential wall or edge 44 need not be exactly parallel to the central longitudinal axis 50.
  • the circumferential wall or edge 44 is a distinctly identifiable structure between the contact ring 34 and the inversion ring 42.
  • the circumferential wall or edge 44 provides strength to the transition between the contact ring 34 and the inversion ring 42. In some embodiments, this transition must be abrupt in order to maximize the local strength as well as to form a geometrically rigid structure. The resulting localized strength increases the resistance to creasing in the base 20.
  • the contact ring 34 for a 2.64-inch (67.06 mm) diameter base container, can have a wall thickness 68 of approximately 0.010 inch to approximately 0.016 inch (0.25 mm to 0.41 mm). In some embodiments, the wall thickness 68 is at least equal to, and more preferably is approximately ten percent, or more, than that of the wall thickness 66 of the lower portion 58 of the inversion ring 42.
  • a dimension 52 measured between the upper portion 54 of the inversion ring 42 and the support surface 38 is greater than or equal to a dimension 56 measured between the lower portion 58 of the inversion ring 42 and the support surface 38.
  • the central portion 36 of the base 20 and the inversion ring 42 will slightly sag or deflect downward toward the support surface 38 under the temperature and weight of the product.
  • the dimension 56 becomes almost zero, that is, the lower portion 58 of the inversion ring 42 is practically in contact with the support surface 38.
  • the central portion 36 of the base 20 exhibits a substantially conical shape having surfaces 60 in cross section that are generally planar and slope upward toward the central longitudinal axis 50 of the container 10, as shown in FIGS. 6, 8, 14 and 17.
  • This conical shape and the generally planar surfaces 60 are defined in part by an angle 62 of approximately 7° to approximately 23°, and more typically between approximately 10° and approximately 17°, relative to a horizontal plane or the support surface 38.
  • angle 62 of approximately 7° to approximately 23°, and more typically between approximately 10° and approximately 17°, relative to a horizontal plane or the support surface 38.
  • planar surfaces 60 are substantially straight (particularly as illustrated in FIGS. 8 and 14), those skilled in the art will realize that planar surfaces 60 will often have a somewhat rippled appearance.
  • a typical 2.64-inch (67.06 mm) diameter base container, container 10 with base 20, has an as molded base clearance dimension 72, measured from the top surface 46 to the support surface 38, with a value of approximately 0.500 inch (12.70 mm) to approximately 0.600 inch (15.24 mm) (see FIGS. 7, 13 and 16).
  • base 20 has an as filled base clearance dimension 74, measured from the top surface 46 to the support surface 38, with a value of approximately 0.650 inch (16.51 mm) to approximately 0.900 inch (22.86 mm) (see FIGS. 8, 14 and 17).
  • the value of the as molded base clearance dimension 72 and the value of the as filled base clearance dimension 74 may be proportionally different.
  • the difference in wall thickness between the base 20 and the body portion 18 of the container 10 is also of importance.
  • the wall thickness of the body portion 18 must be large enough to allow the inversion ring 42 to flex properly.
  • the wall thickness of the body portion 18 must be at least 15%, on average, greater than the wall thickness of the base 20.
  • the wall thickness of the body portion 18 is between two (2) to three (3) times greater than the wall thickness 66 of the lower portion 58 of inversion ring 42. A greater difference is required if the container must withstand higher forces either from the force required to initially cause the inversion ring 42 to flex or to accommodate additional applied forces once the base 20 movement has been completed.
  • the above-described alternative hinges or hinge points may take the form of a series of indents, dimples, or other features that are operable to improve the response profile of the base 20 of the container 10.
  • the vacuum response profile of base 20 may define abrupt flexural responses that produce a segmented, non-continuous vacuum curve (see FIG. 29) defining a pair of vertical sections 302, 304, indicative of abruptly reduced internal vacuum pressure.
  • this response may be suitable for some embodiments, in other embodiments a more gradual and smooth vacuum curve may be desired (see FIGS. 28 and 30 which will be discussed herein).
  • the inversion ring 42 may include a series of indents, dimples, or other features 102 formed therein and throughout. As shown (see FIGS. 16-20), in some embodiments, the series of features 102 are generally circular in shape. However, it should be appreciated that features 102 can define any one of a number of shapes, configurations, arrangements, distributions, and profiles
  • the features 102 are generally spaced equidistantly apart from one another and arranged in a series of rows and columns that completely cover the inversion ring 42.
  • the series of features 102 can generally and completely surround and circumscribe the central pushup 40 (see FIG. 18). It is equally contemplated that the series of rows and columns of features 102 may be continuous or intermittent.
  • the features 102 when viewed in cross section, can be in the shape of a truncated or rounded cone having a lower most surface or point and side surfaces 104. Side surfaces 104 are generally planar and slope inward toward the central longitudinal axis 50 of the container 10.
  • the exact shape of the features 102 can vary greatly depending on various design criteria. While the above-described geometry of the features 102 is preferred, it will be readily understood by a person of ordinary skill in the art that other geometrical arrangements are similarly contemplated.
  • the features 102 are illustrated as a similarly shaped series of dimples spaced equidistantly apart from one another as a plurality of radial row or columns extending from the central pushup 40 on inversion ring 42. Although illustrated as being inwardly directed within container 10, it should be appreciated that features 102 can be outwardly directed in some embodiments. It should also be understood that the particular size, shape, and distribution of dimples can vary depending upon the vacuum curve performance desired and provides control over base flexibility and movement under vacuum providing smooth actuation. As particularly illustrated in FIG. 28, it can be seen that under vacuum pressure load, base 20 and container 10, employing the base of FIGS.
  • the features 102 are illustrated as a similarly shaped series of triangularly intersecting dimples spaced equidistantly apart from one another as a plurality of row or columns extending from the central pushup 40 on ring 42.
  • Features 102 of the present embodiment are inwardly directed and define common boundaries with adjacent features 102 along edges of the inverted triangle. It should also be understood that the particular size, shape, and distribution of dimples can vary depending upon the vacuum curve performance desired and provides control over base flexibility and movement under vacuum providing smooth actuation.
  • the features 102 are illustrated as a spider web of radially extending creases 400 spaced equidistantly apart from one another extending from the central pushup 40 on ring 42.
  • Creases 400 can be joined by a series of interconnecting creases 402, such as arcuate creases, extending between adjacent creases 400 forming a series of concentrically spaced circumferential rings extending about pushup 40.
  • interconnecting creases 402 such as arcuate creases, extending between adjacent creases 400 forming a series of concentrically spaced circumferential rings extending about pushup 40.
  • the particular size, shape, and distribution of creases 400 and interconnecting creases 402 can vary depending upon the vacuum curve performance desired and provides control over base flexibility and movement under vacuum providing smooth actuation.
  • the features 102 are illustrated as a similarly shaped series of circumferentially-extending creases 500 being spaced equidistantly apart from one another extending from the central pushup 40 on inversion ring 42.
  • Circumferential creases 500 can be joined by a series of radially-extending, interconnecting creases 502 extending between adjacent circumferential creases 500.
  • Circumferential creases 500 and radially-extending, interconnecting creases 502 together form a rotated brick design.
  • radially-extending, interconnecting creases 502 can extending continuously from pushup 40 each as a single continuous crease or can be staggered to form the brick design.
  • the features 102 can be a series of triangular features, which may be equilateral in which all sides 1 12 thereof have the same length J, isosceles in which only two sides 1 12 have the same length J, or scalene in which none of the sides 1 12 have the same length J.
  • the triangular features 102 can be arranged in any suitable manner, such as in a plurality of rows and/or columns. Neighboring triangular features 102 can be adjacent to one another, such that they share sidewalls or boundaries as illustrated.
  • the triangular features 102 can be configured such that centers 1 10 thereof protrude outward from the base 20, as generally illustrated.
  • the triangular features 102 are offset from both the wall 44 and the central pushup 40 of the base 20. Any suitable offset can be provided.
  • an outermost edge 106 of the triangular features 102 can have a diameter of 67.78mm or about 67.78mm, and an innermost edge 108 of the triangular features 102 can occupy a diameter of 23.55mm or about 23.55mm as measured through the central longitudinal axis 50.
  • the base 20 can have an outermost diameter of 87.5mm or about 87.5mm, as measured through the central longitudinal axis 50.
  • the triangular features 102 can occupy any suitable portion of the surface area of the base 20, such as from about 30% to about 70%, about 50%, or 50% of the surface area of the base 20.
  • the triangular features 102 can occupy or cover a surface area of the base 20 of 3,172mm 2 , or about 3,172mm 2 , out of a total surface area of 6,013mm 2 or about 6,013mm 2 of the base 20.
  • the triangular features 102 can be present on any suitable portion of the base 20, such as at any suitable portion of the inversion ring 42 between the wall 44 and the side surfaces 48 of the central push up 40, for example.
  • the inversion ring 42 including the triangular features 102 present thereon between the wall 44 and the side surfaces 48 of the central push up 40 can have a radius R of between about 10mm and about 30mm, such as about 20mm, or 20.6mm.
  • the wall 44 can be angled inward towards the central longitudinal axis 50 at an angle D of 9.5°, or about 9.5°, relative to the sidewall 30.
  • the top surface 46 of the pushup 40 can have a diameter E as measured through the central longitudinal axis 50 of 10.13mm or about 10.13mm.
  • the top surface 46 can be spaced apart from the support surface 38 to provide a base clearance F of 15.5mm or about 15.5mm.
  • the inversion ring 42 can be spaced apart from the support surface 38 at a minimum distance G of 2.27mm or about 2.27mm. In other words, at a portion of the inversion ring 42 closest to the support surface 38 prior to the plastic container 10 being hot-filled, the inversion ring 42 is spaced apart from the support surface 38 at a distance of 2.27mm or about 2.27mm.
  • the contact ring 34 includes a diameter H of 67.41 mm or about 67.41 mm, which can decrease to 66.41 mm or about 66.41 mm after the plastic container 10 is hot-filled.
  • each triangular feature 102 when the triangular features 102 are equilateral triangles each triangular feature 102 can have a height I of 3mm or about 3mm, each side 1 12 can have a suitable corresponding length J, and each triangular feature 102 can define a depth within the inversion ring 42 between the triangular features 102 at sides 1 12 of 1 mm or up to about 1 mm as measured from an outer surface of the inversion ring 42.
  • the triangular features 102 can each have any suitable height I and define any suitable depth, and the sides 1 12 can have any suitable length J.
  • the height I, depth, and/or length J of each one of the triangular features 102 can be the same or different.
  • the particular size, shape, number, and distribution of each one of the triangular features 102 can vary depending on the vacuum curve performance desired, and to provide control over flexibility of the base 20 and movement under vacuum to provide smooth actuation of the base 20.
  • the triangular features 102 can be formed in any suitable manner, such as with mold 150 of Figure 36.
  • the mold 150 includes a plurality of peaks 152 and troughs 154 formed therein to define triangular recesses that are configured to provide the base 30 with the triangular features 102.
  • neighboring peaks 152 can be spaced apart at a distance K of 3mm or about 3mm to provide the triangular features 102 with the height I of 3mm or about 3mm.
  • the troughs 154 can be recessed within the mold 150 at a distance L from the peaks 152 of 1 mm or about 1 mm, thereby providing a blow mold ratio of 3:1 or about 3:1 width (or height) to depth of the triangular features 102, which can be optimal in some applications.
  • Each of the peaks 152 can be aligned along a first plane P-i, and each of the troughs 154 can be aligned along a second plane P 2 .
  • the first and second planes Pi and P 2 can extend parallel to one another.
  • the portion of the base 20 to become the inversion ring 42 can be positioned against the mold 150, such that the base 20 extends generally parallel to each of the first and second planes Pi and P 2 .
  • the PET material from which the plastic container 10 may be formed extends towards the troughs 154.
  • the triangular recesses defined by the peaks 152 and troughs 154 project the triangular features 102 onto and into the inversion ring 42, which is formed as a curved surface.
  • the triangular features 102 can be formed in any other suitable manner as well.
  • the above-described base designs cause initiation of movement and activation of the inversion ring 42 more easily by at least increasing the surface area of the base 20 and, in some embodiments, decreasing the material thickness in these areas.
  • the alternative hinges or hinge points also cause the inversion ring 42 to rise or push upward more easily, thereby displacing more volume. Accordingly, the alternative hinges or hinge points retain and improve the initiation and degree of response ease of the inversion ring 42 while optimizing the degree of volume displacement.
  • the alternate hinges or hinge points provide for significant volume displacement while minimizing the amount of vacuum related forces necessary to cause movement of the inversion ring 42.
  • container 10 when container 10 includes the above-described alternative hinges or hinge points, and is under vacuum related forces, the inversion ring 42 initiates movement more easily and planar surfaces 60 can often achieve a generally larger angle 62 than what otherwise is likely, thereby displacing a greater amount of volume.
  • base 20 can comprise three grooves 80 substantially parallel to side surfaces 48. As illustrated in FIGS. 9 and 10, grooves 80 are equally spaced about central pushup 40. Grooves 80 have a substantially semicircular configuration, in cross section, with surfaces that smoothly blend with adjacent side surfaces 48. Generally, for container 10 having a 2.64-inch (67.06 mm) diameter base, grooves 80 have a depth 82, relative to side surfaces 48, of approximately 0.1 18 inch (3.00 mm), typical for containers having a nominal capacity between 16 fl. oz and 20 fl. oz.
  • the central pushup 40 having grooves 80 may be suitable for engaging a retractable spindle (not illustrated) for rotating container 10 about central longitudinal axis 50 during a label attachment process. While three (3) grooves 80 are shown, and is the preferred configuration, those skilled in the art will know and understand that some other number of grooves 80, i.e., 2, 4, 5, or 6, may be appropriate for some container configurations.
  • grooves 80 may help facilitate a progressive and uniform movement of the inversion ring 42. Without grooves 80, particularly if the wall thickness 66 is not uniform or consistent about the central longitudinal axis 50, the inversion ring 42, responding to vacuum related forces, may not move uniformly or may move in an inconsistent, twisted, or lopsided manner. Accordingly, with grooves 80, radial portions 84 form (at least initially during movement) within the inversion ring 42 and extend generally adjacent to each groove 80 in a radial direction from the central longitudinal axis 50 (see FIG. 1 1 ) becoming, in cross section, a substantially straight surface having angle 62 (see FIG. 12).
  • planar surfaces 60 will likely become somewhat rippled in appearance.
  • the exact nature of the planar surfaces 60 will depend on a number of other variables, for example, specific wall thickness relationships within the base 20 and the sidewalls 30, specific container 10 proportions (i.e., diameter, height, capacity), specific hot-fill process conditions and others.
  • the plastic container 10 may include one or more horizontal ribs 602. As shown in FIG. 31 , horizontal ribs 602 further include an upper wall 604 and a lower wall 606 separated by an inner curved wall 608. Inner curved wall 608 is in part defined by a relatively sharp innermost radius n. In some embodiments, sharp innermost radius n lies within the range of about 0.01 inches to about 0.03 inches. The relatively sharp innermost radius ⁇ of inner curved wall 608 facilitates improved material flow during blow molding of the plastic container 10 thus enabling the formation of relatively deep horizontal ribs 602.
  • Horizontal ribs 602 each further include an upper outer radius r 2 and a lower outer radius r 3 .
  • both the upper outer radius r 2 and the lower outer radius r3 each lie within the range of about 0.07 inches to about 0.14 inches.
  • the upper outer radius r 2 and the lower outer radius r 3 may be equal to each other or differ from one another.
  • Preferably the sum of the upper outer radius r 2 and the lower outer radius r 3 will be equal to or greater than about 0.14 inches and less than about 0.28 inches.
  • horizontal ribs 602 further include an upper inner radius r 4 and a lower inner radius r 5 .
  • the upper inner radius r 4 and the lower inner radius r 5 each lie within the range of about 0.08 inches to about 0.1 1 inches.
  • the upper inner radius r 4 and the lower inner radius r 5 may be equal to each other or differ from one another.
  • Preferably the sum of the upper inner radius r 4 and the lower inner radius r 5 will be equal to or greater than about 0.16 inches and less than about 0.22 inches.
  • Horizontal ribs 602 have a rib depth RD of about 0.12 inches and a rib width RW of about 0.22 inches as measured from the upper extent of the upper outer radius r 2 and the lower extent of the lower outer radius r 3 . As such, horizontal ribs 602 each have a rib width RW to rib depth RD ratio. The rib width RW to rib depth RD ratio is, in some embodiments, in the range of about 1 .6 to about 2.0. [0105] Horizontal ribs 602 are designed to achieve optimal performance with regard to vacuum absorption, top load strength and dent resistance.
  • Horizontal ribs 602 are designed to compress slightly in a vertical direction to accommodate for and absorb vacuum forces resulting from hot- filling, capping and cooling of the container contents. Horizontal ribs 602 are designed to compress further when the filled container is exposed to excessive top load forces.
  • the above-described horizontal rib 602 radii, walls, depth and width in combination form a rib angle A.
  • the rib angle A of an unfilled plastic container 10 may be about 58 degrees.
  • the resultant vacuum forces cause the rib angle A to reduce to about 55 degrees.
  • the rib angle A will be reduced by at least about 3% and no more than about 8% as a result of vacuum forces.
  • horizontal ribs 602 are designed so that the rib angle A may be further reduced to absorb top load forces.
  • horizontal ribs 602 are designed so that the upper wall 604 and the lower wall 606 never come into contact with each other as a result of vacuum or top load forces. Instead horizontal ribs 602 are designed to allow the plastic container 10 to reach a state wherein the plastic container 10 is supported in part by the product inside when exposed to excessive top load forces thereby preventing permanent distortion of the plastic container 10. In addition, this enables horizontal ribs 602 to rebound and return substantially to the same shape as before the top load forces were applied, once such top load forces are removed.
  • Horizontal lands 610 are generally flat in vertical cross-section as molded. When the plastic container 10 is subjected to vacuum and/or top load forces, horizontal lands 610 are designed to bulge slightly outward in vertical cross-section to aid the plastic container 10 in absorbing these forces in a uniform way.
  • ribs 602 may not be parallel to the base 20, as illustrated in FIG. 32.
  • the ribs 602 may be arcuate in one or more directions about the periphery of the container 10 and the sidewall 30 of the container 10. More specifically, the ribs 602 may be arced such that a center of the ribs 602 is arced upward toward the neck 18. Such may be the case for all of the ribs 602 in the container 10 when viewed from the same side of the container 10. However, the ribs 602 may be arched in a different, opposite, downward direction, such as toward a bottom of the container 10. More specifically, a center of the ribs 602 may be closer to the base 20 than either of sides. In rotating the container 10 and following the ribs 602 for 360 degrees around the container 10, the ribs 602 may have two (2) equally high, highest points, and two (2) equally low, lowest points.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Ceramic Engineering (AREA)
  • Containers Having Bodies Formed In One Piece (AREA)
  • Packages (AREA)
  • Constitution Of High-Frequency Heating (AREA)
  • Devices For Use In Laboratory Experiments (AREA)
  • Secondary Cells (AREA)
PCT/US2014/063812 2013-11-05 2014-11-04 Hot-fill container WO2015069620A1 (en)

Priority Applications (7)

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ES14859477T ES2935582T3 (es) 2013-11-05 2014-11-04 Recipiente de llenado en caliente
CA2925871A CA2925871C (en) 2013-11-05 2014-11-04 Hot-fill container
MX2016003964A MX2016003964A (es) 2013-11-05 2014-11-04 Recipiente de llenado en caliente.
BR112016010249-5A BR112016010249B1 (pt) 2013-11-05 2014-11-04 Embalagem de envase a quente
EP14859477.3A EP3066010B1 (en) 2013-11-05 2014-11-04 Hot-fill container
BR112016010250A BR112016010250A2 (pt) 2013-11-05 2014-11-04 recipiente enchido a quente
JP2016527341A JP6744214B2 (ja) 2013-11-05 2014-11-04 高温充填容器

Applications Claiming Priority (2)

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US14/072,377 US9394072B2 (en) 2003-05-23 2013-11-05 Hot-fill container
US14/072,377 2013-11-05

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BR (2) BR112016010249B1 (pt)
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US10773940B2 (en) 2015-12-07 2020-09-15 Amcor Rigid Packaging Usa, Llc Method of applying top load force

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EP1328443B1 (en) * 2000-08-31 2011-02-23 C02PAC Limited Method of compensating for vacuum pressure within a container generated by cooling
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EP3066010B1 (en) 2022-11-23
BR112016010249A8 (pt) 2021-03-30
MX2016003964A (es) 2016-10-21
JP6744214B2 (ja) 2020-08-19
ES2935582T3 (es) 2023-03-08
BR112016010250A2 (pt) 2017-08-08
EP3066010A1 (en) 2016-09-14
BR112016010249B1 (pt) 2022-01-11
CA2925871C (en) 2021-05-18
CA2925871A1 (en) 2015-05-14
JP2016534950A (ja) 2016-11-10
BR112016010249A2 (pt) 2017-08-08
EP3066010A4 (en) 2017-05-17

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