Polyester resin closures for containers

Abstract

Provided herein is a thermoformed polyester resin closure for closing a container, the polyester resin comprising polyethylene terephthalate ("PET"), polyethylene furan dicarboxylate ("PEE"), or a copolymer comprising PET and PEE. Further provided is a method for producing the thermoformed closure. Further provided is a method for sterilizing the thermoformed closure.

Description

[Technical field]

[0001] The present disclosure relates to a closure for a container. [Background technology]

[0002] Pharmaceutical, beverage, and many other containers are traditionally prepared from polyethylene terephthalate ("PET"), while container closures are traditionally prepared by injection molding from high density polyethylene ("HOPE") or polypropylene ("PP"). Injection molding of closures can limit the thinness of the closure parts due to flow rate limitations and the ability to eject the closure from the mold. Additionally, HOPE and PP are incompatible with PET recycling streams, requiring the closures to be separated from their associated containers by post-consumer recycling processing facilities. The incompatibility causes undesirable loss and contamination to the PET recycling stream, which is exacerbated by the use of automated sensors that detect caps that have been re-arced or attached to otherwise valuable PET bottles, which are sent to mixed plastics or olefins recycling streams. Thus, there is a need in the art for closures formed from more readily recyclable materials. Summary of the Invention

[0003] In one embodiment, the present disclosure provides a thermoformed polyester resin closure. The closure includes an annular wall that lies against an upper surface of the rim of the finish of the container. The closure further includes an outer cylindrical wall extending downwardly from the annular wall, the outer cylindrical wall including an outer skirt configured to be spaced outwardly from the outer surface of the rim of the finish to provide clearance between the closure and the outer surface of the finish. The closure further includes an inner cylindrical wall extending downwardly from the annular wall, the inner cylindrical wall configured such that the outward facing surface of the inner cylindrical wall has an interference fit with the inward facing surface of the finish of the container for sealing against the inward facing surface of the finish. The closure further includes a lower wall extending across a bottom of the inner cylindrical wall.

[0004] In another embodiment, the present disclosure provides a thermoformed resin closure for closing a container comprising polyester, the closure including a top wall that lies against an upper surface of a rim of a finish of the container, the closure further including a cylindrical wall extending downwardly from the top wall, the inwardly facing surface of the cylindrical wall configured to have an interference fit with the outwardly facing surface of the rim for sealing against the outwardly facing surface of the rim.

[0005] In yet another embodiment, the present disclosure provides an injection molded polyester resin closure for closing a container comprising a polyester, the polyester resin comprising polyethylene furan dicarboxylate ("PEF").

[0006] In yet another embodiment, the present disclosure provides a thermoformed polyester resin closure for closing a container comprising a polyester. The closure includes an outer layer and an inner layer. The outer layer includes an outer layer annular wall. The outer layer further includes an outer layer outer cylindrical wall extending downwardly from the outer layer annular wall. The outer layer further includes an outer layer inner concave wall extending downwardly from the outer layer annular wall. The outer layer further includes an outer layer lower wall extending across a bottom of the outer layer inner concave wall, the outer layer lower wall including a lower concave portion of a first shape. The inner layer includes an inner layer annular wall. The inner layer includes an inner layer outer cylindrical wall extending downwardly from the inner layer annular wall. The inner layer includes an inner layer inner concave wall extending downwardly from the inner layer annular wall, the inner layer concave wall configured such that an outwardly facing surface of the inner layer inner concave wall has an interference fit with an outwardly facing surface of the finish for sealing against the outwardly facing surface of the finish. The inner layer includes an inner layer lower wall extending across a bottom of the inner layer inner recess wall, the inner layer lower wall including a lower recess of a second shape that receives the lower recess of the first shape, the lower surface of the lower recess of the first shape being configured to face and lock into the upper surface of the lower recess of the second shape.

[0007] Further areas of applicability will become apparent from the description provided herein. It should be understood that the description and specific examples are intended for purposes of illustration only and are not intended to limit the scope of the present disclosure.

[0008] In order that the present disclosure may be fully understood, various forms thereof, given by way of example only, will now be described with reference to the accompanying drawings, in which elements are not necessarily drawn to scale. Moreover, like reference numerals in the drawings designate corresponding parts throughout the different views. [Brief description of the drawings]

[0009] [Figure 1] 1 shows a partial diametric cross-sectional side view of an example closure attached to an example container finish. [Diagram 2] 13 shows a diametrical cross-sectional view of another example of a closure including an exterior seal for sealing to another example of a container finish. [Diagram 3] 13 shows a perspective view of yet another example of a closure. [Figure 4A] 13 shows a perspective view of yet another example of a closure formed around the finish of a container but not completely processed. [Figure 4B] 4B shows a perspective view of the example closure of FIG. 4A completely processed around the finish of the container. [Diagram 5] 13 shows a diametrical cross-sectional view of yet another example closure including a plurality of internal knurls around the periphery of the inner surface of the tamper evidence feature. [Figure 6] 6 shows a partial diametrical cross-section of the example closure of FIG. 5 processed with yet another example of a container finish. [Figure 7] 13 shows a side view of yet another example of a closure including multiple threads. [Figure 8A] 13 shows a side view of yet another example of a closure including one thread and multiple circumferentially distributed knurls. [Figure 8B] 13 shows a side view of yet another example of a closure including three separate threads and multiple circumferentially distributed knurls. [Figure 9] 13 shows a side view of yet another example of a closure including multiple threads. [Figure 10A]13 shows a perspective view of yet another example of a closure including two separate thermoformable layers that are subsequently combined. [Figure 10B] FIG. 10B shows a diametric cross-sectional perspective view of the example closure shown in FIG. 10A. [Figure 10C] 10A and 10B show diametric cross-sections of the example closures of FIGS. [Figure 11A] 13A-13C show perspective views of yet another example closure and example seal; [Figure 11B] 11B shows a perspective view of the closure-seal combination of the example closure and seal shown in FIG. 11A. [Figure 11C] 13 shows a perspective view of an example closure-seal combination in yet another example of a finish. [Figure 12] 13 shows a perspective diametrical cross-sectional view of yet another example of a closure in yet another example of a finish, showing the peripheral edge of the top wall of the closure ultrasonically or thermally bonded to the top surface of the finish. [Figure 13] 13 shows a perspective view of yet another example of a closure including branding features on the top wall. [Figure 14] 1 shows a plot of average thread depth vs. pressure retention for 25 sample closures. [Figure 15] Shown is a plot of the ability of 25 sample closures to hold pressure when applied to the finish of a container. [Figure 16A] 1 shows a partial cross-sectional view of the top of an example injection molded closure. [Figure 16B] 16B shows a partial cross-sectional view of the example closure shown in FIG. 16A attached to yet another example of a finish.

[0010] The figures described herein are for illustration purposes only and are not intended to limit the scope of the present disclosure in any way. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] The following description is merely exemplary in nature and is in no way intended to limit the disclosure, application, or uses. It should be understood that throughout the drawings, corresponding reference numerals indicate like or corresponding parts and features.

[0012] In one embodiment, the present disclosure provides a closure formed from a polymer that can be recycled in the same recycle stream as the container that is closed by the closure. Examples of suitable polymers from which the closures described herein can be formed include polyester resins, including biomodified polyesters, such as copolymers of PET and polyethylene furan dicarboxylate (also referred to as "PEF", "polyethylene 2.5-furan dicarboxylate", "polyethylene 2.5-furanoate" or "polyethylene furanoate"), which can include 0-100 mole percent of each of PET and PET (e.g., up to 100 mole percent PET, the remainder, if any, being PEF), and copolymers modified with isophthalic acid ("IPA") or other additives or comonomers. In certain embodiments, the closures can be made from polyester resins that include up to 90 mole percent (0.90 mole fraction) PEF of the polyester resin. In other embodiments, the PEF can be derived from the reaction of furan dicarboxylate ("FDCA") with ethylene glycol, polyethylene glycol ("PEG") and / or diethylene glycol ("DEG"). In yet another embodiment, the closure may be made from a polyester resin having a total comonomer content of the reaction products of FDCA and ethylene glycol, PEG, and / or DEG of up to 50 mole percent (0.5 mole fraction) of the polyester resin. The polyester resin may be prepared by a process including melt blending PEF with PET or by a process including reacting ethylene glycol with FDCA. In yet another embodiment, the closure may be made by injection molding or compression molding a polyester resin having a total comonomer content of the reaction products of FDCA and ethylene glycol, PEG, and / or DEG of up to 90 mole percent (0.90 mole fraction) of the polyester resin, or up to 50 mole percent (0.50 mole fraction) of the polyester resin, or 5-25 mole percent (0.05-0.25 mole fraction) of the polyester resin, or 12-15 mole percent (0.12-0.15 mole fraction) of the polyester resin.In yet another embodiment, the closure may be made by thermoforming a polyester resin having a total comonomer content of the reaction product of FDCA with ethylene glycol, PEG, and / or DEG up to 50 mole percent (0.50 mole fraction) of the polyester resin, or 0.5 to 20 mole percent (0.05 to 0.20 mole fraction) of the polyester resin, or 1 to 8 mole percent (0.01 to 0.08 mole fraction) of the polyester resin. In yet another embodiment, the container may be made of a polyester or polyester resin as described herein. A closure comprising a polyester or polyester resin as described herein may be shrunk or heat or ultrasonically bonded to the finish of a container comprising a polyester or polyester resin as described herein. Alternatively, the closure may be heat shrunk to the finish.

[0013] In another example, the closure may include multiple layers of polyester resin. In certain examples, an inner layer of the multiple layers may be more flexible than an outer layer of the multiple layers, and may deform more easily into the finish and provide a better seal. Additionally or alternatively, the outer layer may provide more aesthetic appeal than the inner layer, which may be more functional than the outer layer. Examples of techniques for preparing a closure including multiple layers of polyester resin may include thermoforming, compression molding, and injection molding.

[0014] Examples of closures made from polyester resins such as PET and / or PEF as described herein may have many advantages over closures made from traditional materials such as HDPE and / or PP. For example, polyester resin closures described herein may help avoid contamination of recycling streams and may be made from recycled polyester resins such as high percentage recycled PET ("rPET"). The supply of rPET may be cleaner and more readily accessible than the supply of HDPE. In certain examples, bio-based PET ("bio-PET") or virgin PET may be added to the polyester resin. Additionally or alternatively, another advantage of the polyester resin closures described herein may be that the polyester resin closures may enhance the oxygen and carbon dioxide barrier compared to HDPE and PP, thereby enhancing the shelf life of the beverage due to the improved barrier. In certain examples, the oxygen barrier of a closure comprising PET may be at least 10 times greater than that of a closure made from HDPE. In other examples, if the closure also comprises FDCA, the oxygen barrier of the closure may be further increased. Additionally or alternatively, another advantage of the polyester resin closures described herein may be that they do not become floating, reducing the tendency of the closures to pollute the environment.

[0015] Additionally or alternatively, another advantage of the polyester resin closures described herein may be that they can provide a lighter container finish, which can reduce material costs and the amount of material wasted. Additionally or alternatively, another advantage of the polyester resin closures described herein may be that the coefficient of thermal expansion of the described polyester resin closures may closely match the coefficient of thermal expansion of the PET finish of the container, improving the ability to successfully seal the lighter finish. Additionally or alternatively, another advantage of the polyester resin closures described herein is that during deformation caused by external forces, such as during storage or transportation, the closure and the finish remain intact due to the similarity of the materials of the closure and the finish.

[0016] Additionally or alternatively, another advantage of the polyester resin closures described herein is that because the polyester resin closures are made from a similar or the same material as the container, e.g., PET, the closures can be heat welded or ultrasonically welded to the finish of the container. In some examples, the polyester resin closures described herein can be welded to the PET finish at one or more locations. In certain examples, the closure can be welded to the top rim of the finish to provide an additional seal between the closure and the finish. Other examples can include one or more spot welds to provide evidence of tampering. The ability to weld the closure to a PET container can also provide a unique way to meet tethering requirements in the European Union and can be considered in the United States. In still other examples, the polyester resin closures described herein can include other features such as tamper evident ("TE") bands, spiral tethers, or hinges that are spot welded at one or more end points to the container to provide a tether of controlled strength.

[0017] In one embodiment, the closures described herein may require a force of 10N to 20N for removal.

[0018] In one embodiment, the polyester resin closures described herein can be made via a thermoforming process. The thermoformed closures can be designed to balance wall thickness and adjustment of the interference fit of the container finish within the elastic limits of PET or any of the other polymers described herein, such as by including a plug seal or an external seal. Due to the relatively high stiffness of polyester resins such as PET compared to HDPE and PP (e.g., about two times higher), seal designs for conventional HDPE and PP closures may not be effective for the thermoformed polyester resin closures described herein, because they rely on relatively high levels of elastic deformation that are generally unattainable with the thermoformed polyester resin closures described herein. Thus, in certain embodiments, the seal configuration of the thermoformed polyester resin closures can be tailored to provide sufficient sealing with less material strain.

[0019] In one embodiment, the closures described herein may be made by vacuum forming. In certain embodiments, the closures described herein may be made by pressure assisted vacuum forming at pressures up to 4 bar, preferably up to 24 bar, and more preferably up to 40 bar. In other embodiments, the thermoformed polyester resin closures with plug seals may include a relatively large sealing surface that may be designed to fill imperfections (e.g., scratches) that may be present in the finish of the container. In contrast, the plug seals of conventional HDPE and PP closures take advantage of the relative flexibility of the HDPE and PP materials and are designed with a relatively high level of elastic deformation, resulting in a relatively small sealing area in contact with the finish. In yet another embodiment, the polyester resin closures described herein, such as the thermoformed polyester resin disclosures, may include a sealing surface of the plug seal with a width of 0.7 millimeters that may be configured for a finish having an inner diameter of 26 millimeters, and a width of 1.5 millimeters that may be configured for a finish having an inner diameter of 48 millimeters.

[0020] In one embodiment, the plug seal of the closure described herein may be configured to provide an interference fit with the finish, such that the sealing surface of the closure provides sufficient pressure and provides sufficient sealing against the mating surface of the finish to contain the pressurized contents, such as, for example, a carbonated liquid. The amount of interference may refer to the difference between the radius of the sealing surface of the closure and the corresponding sealing surface of the finish. The amount of interference may vary depending on the diameter of the finish and the wall thickness of the closure. In certain embodiments, the amount of interference may range from 0.02 millimeters to 0.2 millimeters for material thicknesses ranging from 0.2 millimeters to 0.5 millimeters. In other embodiments, the amount of interference for a closure thermoformed from a sheet of PET having a thickness of 0.5 millimeters may be 0.05 millimeters. The amount of interference may be adjusted by altering the behavior of the polyester resin, such as by including FDCA and / or DEG, whereby a softer polymer may result in a larger interference fit and / or a larger thickness. The interference values ​​disclosed herein are nominal interference values ​​provided as examples and manufacturing variations may result in variations from the disclosed values.

[0021] In one embodiment, a polyester resin closure as described herein may be thermoformed from a sheet of a polyester resin as described herein having a thickness of between 0.20 millimeters and 2.00 millimeters. In certain embodiments, the polyester resin sheet has a thickness of 0.20 mm to 1.95 mm, or ~1.90 mm, or ~1.85 mm, or ~1.80 mm, or ~1.75 mm, or ~1.70 mm, or ~1.65 mm, or ~1.60 mm, or ~1.55 mm, or ~1.50 mm, or ~1.45 mm, or ~1.40 mm, or ~1.35 mm, or ~1.30 mm, or ~1.25 mm, or ~1.20 mm, or ~1.15 mm, or ~1.10 mm, or ~1.05 mm, or ~1.00 mm, or ~0.95 mm, or ~0.90 mm, or ~0.85 mm, or ~0.80 mm, or ~0.75 mm, or ~0.70 mm, or ~0.65 mm, or ~0.60 mm, or is ~0.55 mm, or ~0.50 mm, or ~0.45 mm, or ~0.40 mm, or ~0.35 mm, or ~0.30 mm, or ~0.25 mm; or 0.25 mm~, or 0.30 mm~, or 0.35 mm~, or 0.40 mm~, or 0.45 mm~, or 0.50 mm~, or 0.55 mm~, or 0.60 mm~, or 0.65 mm~, or 0.70 mm~, or 0.75 mm~, or 0.80 mm~, or 0.85 mm~, or 0.90 mm~, or 0.95 mm~, or 1.00 mm~, or 1.05 mm~, or 1.10 mm~, or 1.15 mm~, or 1.20 mm~, or 1.25 mm~, or 1.30 mm~, or 1.35 mm~, or 1.The thickness may be any range formed from any two of the aforementioned numbers, including 40 mm to 1.45 mm to 1.50 mm to 1.55 mm to 1.60 mm to 1.65 mm to 1.70 mm to 1.75 mm to 1.80 mm to 1.85 mm to 1.90 mm to 1.95 mm to 2.00 mm, or any subrange therebetween. Preferably, the polyester resin sheet may have a thickness of 0.50 mm to 0.90 mm, including any of 0.50 mm, 0.55 mm, 0.60 mm, 0.65 mm. 0.70 mm, 0.75 mm, 0.80 mm, 0.85 mm, or 0.90 mm (including any range or subrange therebetween). In other examples, the desired or preferred thickness of a sheet of the polyester resin described herein used to prepare a polyester resin closure described herein can be a determinable function of the diameter of the polyester resin closure.

[0022] In one embodiment, a thermoformed polyester resin closure as described herein may be configured to have sufficient radial clearance between the outer surface of the finish and the outer wall of the closure to enclose the outer surface of the finish such that the plug seal of the closure may deform when engaged with the finish. Without radial clearance, the plug seal of the closure may not be fully inserted into the finish or may be subject to high stresses on the closure that may result in failure.

[0023] In one embodiment, the thermoformed polyester resin closure described herein may be configured with an exterior seal that seals with the exterior surface of the mouth of the finish. The exterior seal may be achieved by an interference fit with the finish. The amount of interference may depend on the application. The interference and wall thickness examples disclosed above for the plug seal may be used for the exterior seal. In certain embodiments, the sealing of the exterior seal may be enhanced by taking advantage of the polyester resin's ability to heat shrink by heat shrinking the closure after capping.

[0024] To achieve the proper interference between a seal, such as a plug seal and / or an exterior seal, and the finish, and in certain embodiments, the proper clearance between the outer wall of the closure and the finish, the interference and clearance dimensions can be well controlled during manufacturing by thermoforming the closure using a male mold that matches the shape of the desired interference with the finish, while taking shrinkage into account. Features of the closure that can provide the interference and clearance with the finish can be contacted with the mold.

[0025] Because thermoformed polyester resin is relatively hard, the sealing surface of the polyester resin closure may have a relatively low surface roughness. In certain embodiments, the low surface roughness may be achieved by polishing the areas of the thermoform mold that form the sealing surface. In other embodiments, the portions of the thermoform mold that do not form the sealing surface of the closure are not polished or are not polished to the same extent as the portions that form the sealing surface to avoid the closure sticking to the mold and making demolding difficult. An example of the roughness of the sealing surface(s) of the closure may include about 0.2 microns (Ra value of 0.2 or N4 finish).

[0026] In various embodiments, the seals, thread engagements, and / or TE bands of the polyester resin closures described herein may be configured to provide an opening torque in the range of 0.45 Nm to 1.24 Nm, preferably 1.02 Nm. In various embodiments, the closures may be configured to provide a pressure retention of 2 bar or less, preferably 10 bar or less.

[0027] In one embodiment, the polyester resin used in the thermoformed closures described herein may include some amount of FDCA and / or DEG, which may provide a number of benefits. For example, FDCA and DEG may hinder crystal formation, so that the resulting material may have a longer processing window for forming features on the closure. Additionally, the inclusion of FDCA and / or DEG may allow the material of the closure to be sufficiently different from the material of the finish, so that the closure dock does not fuse to the container during storage. Additionally, the inclusion of FDCA and / or DEG may reduce the stress of the material of the closure, which may allow for higher material strains, which may be useful for enhancing the seal between the closure and the finish.

[0028] In one embodiment, the closure may be made by injection or compression molding a polymer resin. In certain embodiments, the polyester resin may contain some amount of FDCA and / or DEG. The FDCA and / or DEG content may reduce the stress of the material sufficiently so that the closure may be easily ejected from various cavities of a mold. For example, the stress of the amorphous phase of the material may range from 1 to 3 GPa. As the FDCA content increases, the processing window may increase and the closure may be easier to eject, since the polyester resin may remain flexible for a longer period of time. The amount of FDCA and / or DEG in the polyester resin subjected to injection or compression molding may be relatively higher than the amount of FDCA and / or DEG in the thermoformed closure due to the need for higher compliance in injection molding or compression. In certain embodiments, the ability of the material to flow during injection or compression molding may be increased by limiting the intrinsic viscosity of the material. An example of a method for limiting the intrinsic viscosity of the material includes limiting the duration of solid-state polymerization of the polyester resin after the polyester resin is synthesized. In certain examples, the inherent viscosity may range from 0.4 dL / g to 0.7 dL / g. The higher the inherent viscosity, the stiffer the final closure may be. In certain examples, inherent viscosities in the range of 0.8 dL / g to 1.2 dL / g may be beneficial for toughness. Bimodal resins may provide benefits from both low and high viscosity polyesters to impart both beneficial flow and toughness properties. As with thermoformed closures, the inclusion of FDCA and / or DEG in the polyester resin closures described herein may make the closure material sufficiently different from the finish material so that the closure does not fuse to the container during storage. Additionally, the inclusion of FDCA and / or DEG in the polyester resin closures described herein may reduce the stress of the closure material, which may allow for higher strains in the material, which may improve the seal between the closure and the finish.Additionally, the inclusion of FDCA and / or DEG in the polyester resin closure agents described herein also reduces the melting point, allowing the use of less energy for bonding or intentional sealing using the heat used in induction sealing on metallized films.

[0029] In one embodiment, a moveable core component may be used in injection or compression molding to reduce the need for worm threads to remove stiff PET as traditionally done with injection molded HDPE. In certain embodiments, FDCA-modified, PEG-modified, and / or DEG-modified polyester resins may be used in combination with the moveable core.

[0030] In certain examples, the closure may be colored using a dye or dyeing process that is compatible with recycling. For example, the dye used to color the closure may be compatible with recycling. In other examples, the dye or ink may be removable by washing. In yet other examples, a nanocoating may be deposited on the surface of the closure.

[0031] The closure may be configured to fit custom or industry standard finishes. Examples of industry standard thread finishes may include 26 / 22, 29 / 25, 29 / 21, 28PCO1881, 30 / 25, 38 / 33, and 48mm.

[0032] Closure made from a copolymer of PET and PEF ("PETF") In one embodiment, the closure may be made from a PET-based copolymer that may be particularly suitable for injection molding and / or thermoforming. PET-based copolymers incorporate comonomers to control crystallization and reduce melt processing temperatures. In certain embodiments, the present disclosure provides copolymers of PET and PET (also referred to as FDCA-modified PET copolymers, or "PETF"). In other embodiments, FDCA may be incorporated in amounts to improve the reaction rate of the polymer during both melt and solid state polymerization, and in amounts ranging to allow the performance of the polymer to be comparable to conventional PET, controlled by adding an amount of IPA. In yet other embodiments, FDCA may be added to PET instead of PET or in addition to IPA to make PETF. In still other embodiments, FDCA may be added in low fractions, and the PETF copolymer product may be made following the same process to make PET.

[0033] In one embodiment, the present disclosure provides a FDCA modified PET copolymer incorporating FDCA in an amount that can adequately delay crystal formation in PET during closure formation. In certain embodiments, the PETF can contain less than 10 mol% FDCA, less than 9 mol% FDCA, or less than 8 mol% FDCA, or less than 7 mol% FDCA, or less than 6 mol% FDCA, or 5 mol% FDCA, or less than 4 mol% FDCA, or less than 3 mol% FDCA, or less than 2 mol%, or less than 1 mol% FDCA, or an amount within a range formed from any two of the foregoing numbers (including all ranges and subranges therebetween). In other embodiments, the PETF can contain as little as 0.5 mol% FDCA to adequately delay crystal formation. In yet other embodiments, the PETF may contain 0.5 mol% to 5 mol% FDCA, or 0.5 mol% to 4 mol% FDCA, or 0.5 mol% to 3 mol% FDCA, or 0.5 mol% to 2 mol% FDCA, or 1 mol% to 5 mol% FDCA, or 1 mol% to 4 mol% FDCA, or 1 mol% to 3 mol% FDCA, or 1 mol% to 2 mol% FDCA; or about 1.1 mol% FDCA, or about 1.2 mol% FDCA, or about 1.3 mol% FDCA, or about 1.4 mol% FDCA, or about 1.5 mol% FDCA, or about 1.7 mol% FDCA, or about 1.8 mol% FDCA, or about 1.9 mol% FDCA, or about 2 mol% FDCA, or an amount within a range formed by any two of the foregoing numbers (including all ranges and subranges therebetween).

[0034] In one example, the copolymers provided herein can include repeat units (L), (M), and (N), or any salt thereof: [ka]

[0035] The repeat unit (L) may be a repeat unit of polyethylene furanoate ("PEF") based on furandicarboxylic acid (FDCA). In one embodiment, the repeat unit (L) is present in an amount of from 0.5 mol% to 90.0 mol%, or from 85.0 mol%, or from 80.0 mol%, or from 75.0 mol%, or from 70.0 mol%, or from 65.0 mol%, or from 60.0 mol%, or from 55.0 mol%, or from 50.0 mol%, or from 45.0 mol%, or from 40.0 mol%, or from 35.0 mol%, or from 30.0 mol%, or from 25.0 mol%, or from 20.0 mol%, or from 15.0 mol%, or from 10.0 mol%, or from 9.5 mol%, or from 9.0 mol%, or from 8.5 mol%, or from 8.0 mol%, or from 7.5 mol%, or from 7.0 mol%, or from 6.5 mol%, or from 6.0 mol% of the copolymer; or It may be present in an amount of from 6.5 mol%, or from 7.0 mol%, or from 7.5 mol%, or from 8.0 mol%, or from 8.5 mol%, or from 9.0 mol%, or from 9.5 mol%, or from 10.0 mol%, or from 15.0 mol%, or from 20.0 mol%, or from 25.0 mol%, or from 30.0 mol%, or from 35.0 mol%, or from 40.0 mol%, or from 45.0 mol%, or from 50.0 mol%, or from 55.0 mol%, or from 60.0 mol%, or from 65.0 mol%, or from 70.0 mol%, or from 75.0 mol%, or from 80.0 mol%, or from 85.0 mol% to 90.0 mol%, or in any range consisting of any two of the aforesaid numbers (including any subranges therebetween). In certain embodiments, the repeating units (L) may be present in an amount of 0.5 mole % to 6.0 mole % of the copolymer, including all subranges therebetween. In other embodiments, the repeating units (L) may be present in an amount up to 90.0 mole % of the copolymer. As the mole percent of FDCA increases, the rate and extent of crystallization of the PET may decrease.

[0036] The repeat unit (M) may be based on terephthalic acid ("PTA" or "TPA"). In one embodiment, the repeat unit (M) is based on 10.0 mol% to 99.5 mol%, or to 99.0 mol%, or to 98.5 mol%, or to 98.0 mol%, or to 91.5 mol%, or to 97.0 mol%, or to 96.5 mol%, or to 96.0 mol%, or to 95.5 mol%, or to 95.0 mol%, or to 94.5 mol%, or to 94.0 mol%, or to 93.5 mol%, or to 93.0 mol% mol%, or to 92.5 mol%, or to 92.0 mol%, or to 91.5 mol%, or to is ~91.0 mol%, or ~90.5 mol%, or ~90.0 mol%, or ~85.0 mol%, or ~80.0 mol%, or ~75.0 mol%, or ~70.0 mol%, or ~65.0 mol%, or ~60.0 mol%, or ~55.0 mol%, or ~50.0 mol%, or ~45.0 mol%, or ~40.0 mol%, or ~35.0 mol%, or ~30.0 mol%, or ~25.0 mol%, or ~20.0 mol%, or ~15.0 mol%, or ~10.0 mol%; or 10. 0 mol%~, or 15.0 mol%~, or 20.0 mol%~, or 25.0 mol%~, or 30.0 mol%~, or 35.0 mol%~, or 40.0 mol%~, or 45.0 mol%~, or 50.0 mol%~, or 55.0 mol%~, or 60.0 mol%~, or 65.0 mol%~, or 70.0 mol%~, or 75.0 mol%~, or 80.0 mol%~, or 85.0 mol%~, or 90.0 mol%~, or 90.5 mol%~, or 91.0 mol%~, or 91.5 mol% It may be present in an amount of from 92.0 mol% to 92.5 mol% to 93.0 mol% to 93.5 mol% to 94.0 mol% to 94.5 mol% to 95.0 mol% to 95.5 mol% to 96.0 mol% to 96.5 mol% to 97.0 mol% to 97.5 mol% to 98.0 mol% to 98.5 mol% to 90.0 mol%, or any range consisting of any two of the aforesaid numbers (including any subranges therebetween).In certain embodiments, the repeat unit (M) may be present in an amount of 94 mol % to 99.5 mol %, including all subranges therebetween, while in other embodiments, the repeat unit (M) may be present in at least 10.0 mol % of the copolymer.

[0037] The repeat unit (N) is based on IPA and can be optional. In certain embodiments, the repeat unit (N) can be present in an amount of 0 mol % to 4 mol %, including all subranges therebetween.

[0038] In one embodiment, the FDCA modified PET copolymers described herein may function as a polymerization / melt processing aid and may provide several processing advantages including, for example, improving melt phase polymerization times and / or processing temperatures; allowing lower melt phase processing temperatures, which may reduce thermal decomposition by-products and improve the b* (yellow) color of the copolymer; as the FDCA concentration is increased, the process temperature is reduced, protecting the polymer from thermal decomposition by-products that may be associated with FDCA polymers made at typical unmodified PET processing temperatures; reducing the melt temperature of the copolymer, allowing for lower processing temperatures in closure formation; reducing the melt temperature without reducing the melt viscosity in closure formation; producing polymers with high intrinsic viscosity ("IV") at polymerization times and temperatures associated with unmodified PET; and / or producing high IV polymers with high IV at solid state polymerization times and temperatures associated with unmodified PET.

[0039] In one example, crystal nucleation in PETF containing FDCA in amounts less than 2 mol % can be promoted by nanoparticles capable of nucleating crystals in PET. In another example, the nucleation rate of PETF containing FDCA in amounts greater than 2 mol %, or even greater than 5 mol %, can be increased using crystallization additives such as graphene.

[0040] In one embodiment, the PEF component may have a lower entanglement density than PET.

[0041] In one embodiment, the PETF provided herein may have low PETF yellowing due to the low fraction of FDCA used.

[0042] In one embodiment, pellet blending for PETF concentration can be an alternative route to PET with low mole percent FDCA.

[0043] In one embodiment, PETF for use in the polyester resin closures described herein may be prepared by esterification of ethylene glycol ("EG") with PTA in the presence of FDCA and optionally IPA. In certain instances, FDCA may be present in a range of 0.05 mol % to 6 mol %, or 1.5 mol % to 2 mol %, including all ranges and subranges therebetween. In other embodiments of PETF that also incorporate IPA, IPA may be present in a range of 0.01 mol % to 2 mol %, including all subranges therebetween.

[0044] PTA-based melt polymer process In one example, the initial reaction of the PTA-based polymer process can involve reacting PTA with EG at 250-270°C under a pressure of 40-50 psig. Water can be evaporated and separated using a distillation column. The reaction can be carried out under pressure due to the low solubility of PTA in EG at EG's boiling point of 197°C. After most of the theoretical amount of water has been collected, the pressure can be reduced to atmospheric pressure as the remaining water dissipates. The resulting bis(2-hydroxyethyl) terephthalate ("BHET") can be heated in the presence of a suitable catalyst (such as antimony triglycolic acid) and two molecules of BHET can form a dimer while EG can be extracted as a sort of transesterification. Further reactions can be possible if the released EG is removed from the system by distillation. In certain examples, a dimer can react with another BHET molecule to form a trimer; two molecules of a dimer can form a tetramer. Such a stepwise growth process can produce high molecular weight polymers.

[0045] In certain embodiments, suitable catalysts used in PET polymerization may include Sb-based catalysts and Ti-based catalysts. In other embodiments, phosphoric acid and phosphate salts may be added to perform one or more of several roles, including, for example, acting as a catalyst or minimizing thermal oxidation. In yet other embodiments, impurities in the PTA may be one or more of Fe, Co, Mo, Ni, Ti, Cr, Ca, Al, Mg, Na, and K at less than 1 ppm. Higher amounts of impurities may be present in the PTA, where the impurities may act as chain terminators or cause discoloration.

[0046] For melt phase polymerization, high temperatures such as 265-300 °C may be required, and the pressure above the molten polymer must be reduced to about 1 Torr to promote the high molecular weight necessary for polymer performance. In production plants, pressures as low as about 1 Torr can be achieved using multi-stage steam or glycol ejectors.

[0047] PTA-based solid phase polymerization (“SSP”) Polyesters can be polymerized in either the solid or melt phase. In one example, to achieve solid-state polymerization, polymer chips produced in the melt polymer process can be heated to high temperatures, such as 200-210°C, under vacuum or in a flow of inert gas, such as nitrogen. The SSP process can allow for high molecular weights to be achieved without the problems associated with processing high temperature and highly viscous melts. Additionally, the reaction temperature of the SSP process is lower than melt polymerization, which can minimize thermal degradation of the polymer.

[0048] During melt polymerization, decomposition reactions can result in the formation of acetaldehyde ("AA") and carboxyl end groups. The SSP process acts as a "wash" process that can remove the dissolved phase decomposition products and reduce AA levels in the polymer chips to 1 ppm or less. Reducing AA levels can be important for polymers used to make food grade bottles that are meant to contain soda and water, since even trace amounts of AA can cause off-flavors.

[0049] The primary reaction in SSP is polyesterification, which is the result of a dehydration reaction between carboxyl and hydroxyl end groups on the polymer chain. As a result of the polyesterification process, SSP imparts the ability to increase viscosity and reduce carboxyl end group ("CEG") levels in the polymer, both of which can be desirable properties in downstream applications. Additionally, SSP also removes cyclic oligomers formed in the melt phase polymer that can cause precipitation problems in downstream polymer applications.

[0050] The rate of SSP may depend on the diffusion of water and glycol and / or the removal rate of AA from the polymer chip. The reaction rate may be highly dependent on the size of the polymer chip, and there may be a molecular weight gradient from the surface to the center of the polymer chip.

[0051] In one embodiment, formulations can be used to adjust the color of the resulting PETF.

[0052] In one embodiment, PETF for the closure can be produced by melt mixing or blending pellets containing a high concentration of FDCA with PET without FDCA. In a specific embodiment, 10 mole % PET containing 10% FDCA content is blended with 90 mole % PET without FDCA to yield PET with 1% FDCA.

[0053] Thermoformed PET closure with plug seal Referring to FIG. 1, a side view with partial diametric cross section of an example thermoformed polyester resin closure 100 is shown attached to an example finish 200 of a container typically used to store liquid contents, such as non-carbonated or carbonated beverages. The closure 100 may be made from any of the polyester resins described herein. The closure 100 includes internal threads 102 formed in an outer cylindrical wall 104 of the closure 100 for engaging with external threads 206 of the finish 200. The threads 206 may be continuous or groove threads. Other embodiments may be configured for snap-on engagement with the finish 200. The outer cylindrical wall 104 extends downwardly from an annular wall 112.

[0054] The closure 100 includes a plug seal 108 for sealing against an inner surface 204 of the finish 200. The plug seal 108 includes a cylindrical wall 110 extending downwardly from an annular wall 112 of the closure 100. The annular wall 112 may be configured to abut an upper surface 210 of a rim 208 of the finish 200. An outwardly facing radial surface 114 of the inner cylindrical wall 110 of the plug seal 108 may be dimensioned to provide an interference fit with a corresponding inwardly facing surface 204 of the rim 208 of the finish 200 for sealing. In a particular embodiment, the interference fit may be 0.05 millimeters for a wall thickness of 0.5 millimeters. When the closure 100 is threaded onto the finish 200, the plug seal 108 is forced into compression into the mouth of the finish 200, with the outward radial surface 114 of the plug seal 108 pressing against the inward surface 204 of the finish 200 to form a seal, the mouth being the open volume between the diametrically opposed inward surfaces 204 of the rim 208 of the finish 200. The inner cylindrical wall 110 extends downwardly from the annular wall 112 to the lower wall 120. The degree of interference fit and dimensions of the plug seal 108 and the finish 200 determine the sealing force, and therefore these parameters may be adjusted to adjust the degree of sealing force for a given application. The interference fit between the plug seal 108 and the finish 200 may function as a locking mechanism to lock the closure 100 to the finish 200. The plug seal 108 may include a chamfer 122 to guide the plug seal 108 over a lip 212 of the mouth of the finish 200 when the closure 200 is capped onto the container.

[0055] The plug seal 108 may be configured to have a relatively wide sealing interface with the finish 200, the sealing interface being the contact area between the outward radial surface 114 and the inward facing surface 204 of the finish 200, the sealing interface being designed to fill in imperfections (e.g., scratches) that may be present in the finish 200. An example of the width of the contact area between the outward radial surface 114 and the inward facing surface of the finish may be 0.7 millimeters for a finish 200 with an inner diameter of 26 millimeters and 1.5 millimeters for a finish 200 with an inner diameter of 48 millimeters.

[0056] To allow the closure 200 to elastically deform in the area of ​​the plug seal 108, the closure 200 may be designed to allow a clearance between the outer skirt 126 of the outer cylindrical wall 104 of the closure 100 and the outer surface 214 of the corresponding rim 208 of the finish 200. The amount of clearance may be at least as large as the amount of interference between the plug seal 108 and the finish 200. For example, for an interference of 0.05 millimeters, the amount of clearance may be 0.05 millimeters or more.

[0057] An interference fit 250 may be provided on the threads 102 to ensure that the closure 100 fits tightly into the finish 200. An exemplary interference fit is 0.05 millimeters. The interference fit 324 on the threads 102 may also function as a locking mechanism to lock the closure 100 into the finish 200. The interference may increase with decreasing stress in the closure 100 material.

[0058] The closure 100 includes a tamper evidence feature 116, shown in FIG. 1 in the form of a folding band 106 that engages a tamper evidence ledge 202 of the finish 200. When the closure 100 is threaded onto the finish 200, the folding band 106 straddles the top of the ledge 202 and, once the folding band 106 has cleared the ledge 202, snaps into place beneath the ledge 202, as shown in FIG. 1. The tamper evidence feature 116 may include a plurality of spaced bridges 128 that connect the folding band 106 to the body 124 of the closure 100. When the closure 100 is removed from the finish 200, the folding band 106 is held in place by the ledge 202. The upward force from removing the closure 100 will eventually create enough stress on the bridges 128 that they will break, providing evidence that the closure 100 has been tampered with.

[0059] Optionally, one or more of the bridges 128 may be sized such that its breaking stress is greater than the breaking stress of the remaining bridges 128, thereby providing a tether for the one or more bridges 128 to remain intact and keep the closure 100 attached to the bottle upon removal.

[0060] In certain embodiments of the closure 100, a pull tab may be included in place of the foldover band 106 as the tamper evidence feature 116. The pull tab may be configured such that at least partial removal of the pull tab is required to disengage the closure 100 from the finish 200.

[0061] Closure 100 may be thermoformed from a sheet of PET (or any of the materials described herein) having a thickness between 0.22 millimeters and 1.0 millimeters, preferably about 0.5 millimeters.

[0062] In other embodiments, the interface between the annular wall 112 of the finish 200 and the upper surface 210 of the rim 208 may function as a secondary seal. In yet other embodiments, the secondary seal may be formed and / or strengthened by welding the two surfaces together, for example, ultrasonically or by the application of direct heat.

[0063] In yet other embodiments, the portion of the closure 100 having the largest diameter is in the shape of a generally cylindrical shape with a pronounced outwardly protruding uninterrupted cylinder. For example, as shown in FIG. 1, the lower outer wall 120 of the outer cylindrical wall 104 of the body 124 at the largest diameter of the closure 100 may be vertical, which may allow for the use of conventional capping devices that are typically designed to grip cylindrical shapes.

[0064] The bottom wall 130 extends across the bottom of the inner cylindrical wall 110. In certain embodiments, the bottom wall 130 may have an upwardly concave shape, as shown in the example of FIG. 1, that becomes downwardly convex when pressure is applied upward against the bottom wall 130 from the pressurized contents of the container that the closure 100 closes. The change in shape may result in pressure being applied to the bottom wall 130 increasing the pressure on the sealing interface between the plug seal 108 and the finish 200. In other embodiments, the bottom wall 130 may include one or more ridges, such as cylindrical ridges, or other features that control the shape that the bottom wall 130 may form when under pressure.

[0065] The thermoformed polyester resin closure may be configured with an exterior seal instead of or in addition to a plug seal. The exterior seal may be easier to thermoform than a plug seal and may provide adequate sealing for at least some beverages. Optionally, a heat shrink step may be used to solidify the exterior seal of the closure.

[0066] 2, a diametrical cross-sectional view of another embodiment of a thermoformed resin closure 300 including an exterior seal 380 for sealing to a container finish 350 is shown. The closure 300 may be made from any of the polyester resins described herein. The exterior seal 380 may be provided by an interference fit between an inner surface 302 at the top end of the closure 300 and an outer surface 354 of the mouth 352 of the finish 350. An exemplary interference fit may be 0.05 milliliters.

[0067] 1, the closure 300 may be configured for threaded engagement with the finish 350 or may be configured for a snap-on pressure fit engagement with the finish 350. The closure 300 may also include tamper-evident features, such as a folding band 304, like the folding band 106 in the closure 100.

[0068] 3, a perspective view of yet another example of a closure 400 is shown. An outer wall 402 of the closure 400 includes a plurality of threaded portions 404 evenly distributed about the outer wall 402. Between each of the plurality of threaded portions is a respective one of a plurality of knurled portions 406. The plurality of knurled portions 406 are evenly distributed about the outer wall 402. The knurls (or "ridges") of the plurality of knurled portions 406 may be axial and may extend at least partially through a path between an annular wall 408 and a lower outer wall 410.

[0069] Referring to Figure 4A, a perspective view of yet another example of a closure 450 formed around a container finish but not completely disposed is shown. A bottom wall 452 includes a tamper evidence feature 456 and a folding band 454 that is not disposed to fold behind the tamper evidence feature 456 and below a ledge of the finish (not shown). Figure 4B shows a perspective view of yet another example of a folding band 454 that is disposed to fold behind the tamper evidence feature 456 and below a ledge of the finish (not shown).

[0070] Referring to FIG. 5, a diametrical cross-section of yet another example closure 500 including multiple internal knurling 504 around the periphery of the inner surface of the tamper evidence feature 502. The multiple internal knurling 504 may be evenly or non-uniformly distributed around the periphery of the inner surface of the tamper evidence feature 502. The multiple internal knurling 504 may provide non-conventional handling by contacting the surface of the folding band 506 as the closure 500 is processed in the container finish. The surface contact of the multiple internal knurling 504 may contrast with the conventional method of surface contact with knurling on the outer surface of the closure, specifically the outer surface that is not the surface of the tamper evidence band. While both internal and external knurling are possible in the closures described herein, the multiple internal knurling 504 may be more easily formed in the thermoformed closures described herein.

[0071] 6, a partial diametrical cross-sectional view of the example closure 500 shown in FIG. 5 processed into a container finish 600. As shown in FIG. 6, a face of a folding band 506 contacts a plurality of internal knurls 504 of a tamper evidence feature 502.

[0072] 7, a perspective view of yet another example of a closure 700 is shown. The closure 700 includes a tamper-evident feature that includes a band 702 that is folded outwardly around an outer wall 706 of the closure 700. The folded band 702 includes a plurality of slits 704 that are evenly distributed circumferentially around the folded band 702.

[0073] 7, a side view of yet another example of a closure 700 is shown. Closure 700 includes a plurality of threads 702 evenly distributed around a sidewall of closure 700, with each separate thread of the plurality of threads 702 including one of a corresponding plurality of thread starts 704.

[0074] Referring to FIG. 8A, a perspective view of yet another example of a closure 800 is shown. The closure 800 includes a thread 802 with a thread start 804 at the beginning of the thread 802. The tamper evidence feature 806 includes a plurality of knurls distributed circumferentially around the closure 800. The plurality of knurls may be distributed circumferentially, evenly, or unevenly around the closure 800. FIG. 8B illustrates a side view of yet another example of a closure 850. The closure 850 includes a plurality of threads 852, such as, for example, three threads, distributed evenly around a sidewall of the closure 850. Each of the plurality of threads 852 includes one of a corresponding plurality of thread starts 854. In certain embodiments, the example closure 800 may conform to industry standard container finish PCO1881. In other embodiments, the example closure 850 may conform to industry standard container finish 26 / 22mm. 8A and 8B show that closures 800, 850 can be prepared from the polyester resins described herein for a variety of finish formats having a range of different thread starter numbers and sizes.

[0075] 9, a side view of yet another example of a closure 900 is shown. The closure 900 includes a plurality of threads 902, each thread including one of a corresponding plurality of thread starts 904. In certain embodiments, the plurality of threads 902 may include 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, or more separate threads each corresponding to a plurality of thread starts 904, and may include a number of 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, or more separate thread starts equal to the number of threads. The plurality of threads 902 may allow for snap-on and twist-off removal of the closure 900 from a finish of a container.

[0076] Referring to FIG. 10A, a perspective view of yet another example of a closure 1000 is shown. The closure 1000 includes two separate thermoformed layers that are subsequently assembled. The outer layer 1004 includes a plurality of knurls 1002 that are uniformly or non-uniformly distributed circumferentially around the outer surface of the outer layer outer cylindrical wall of the outer layer 1004, and the inner layer 1006 includes threads 1008 on the inner surface of the inner layer outer cylindrical wall. The outer layer 1004 and the inner layer 1006 may be bonded to each other by any convenient mechanism, such as chemical bonding, mechanical bonding, or thermal bonding. As shown in FIG. 10A, as in the perspective diametrical cross-section of FIG. 10B, the outer layer 1004 includes a first shaped lower recess 1020 in the outer layer lower wall, and the inner layer 1006 includes a second shaped lower recess 1018 in the inner layer lower wall. 10C, the lower surface 1014 of the downward recess 1020 of the first shape can be axially locked against the upper surface 1016 of the downward recess 1018 of the second shape. The outer layer 1004 includes an outer layer folded band 1010 disposed radially outwardly along a bottom periphery of the outer layer outer cylindrical wall that can be locked against a groove in the inner layer folded band 1012. The outer layer 1004 and inner layer 1006 can be rotationally and axially locked together when combined, but may also be thermoformed separately, whereby the plurality of knurls 1002 and the internal threads 1008 can both be defined by direct contact with a mold surface.

[0077] 11A, a perspective view of yet another example of a closure 1100 is shown. The closure 1100 may be used with a container finish that includes a wide mouth. The closure 1100 includes threads 1104 and a top wall 1102. The closure 1100 may be configured to close over a seal 1110. The seal 1110 may be attached to a top surface 1132 of the container finish 1130 around a perimeter 1112 of the seal 1110. The seal 1110 may be a foil seal or a foam seal. The seal 1110 may be configured as a tamper evidence feature that indicates if the container has been opened by blocking contact between the perimeter 1112 and the top surface 1132. The seal 1110 may include a brand logo on a surface of the seal 1110 that faces the top wall 1102 of the closure 1100. The closure 1100 may be transparent so that a brand logo on the face of the seal 1110 is visible through the closure 1100, providing a marketing opportunity. FIG. 11B shows the closure-seal combination 1120 of the closure 1100 with the seal 1110 when it is inside the closure 1100 and visible through the top wall 1102. FIG. 11C shows a perspective view of the closure-seal combination 1120 on the finish 1130. The threads 1104 of the closure contact the threads 1134 of the finish 1130, thereby causing the closure 1100 to cover the seal 1110. Under the closure 1100, the periphery 1112 of the seal 1110 is attached to the top surface 1132.

[0078] 12, a perspective diametrical cross-section of yet another example of a closure 1200 on an end 1250 of a container is shown. The finish 1250 may have a wide diameter to accommodate a container having a wide mouth. The top wall 1202 of the closure 1200 includes a perimeter 1204 that is ultrasonically or thermally bonded to the top surface 1252 of the finish 1250.

[0079] Referring to FIG. 13, a perspective view of yet another example of a closure 1300 is shown. The closure 1300 includes a branding feature 1302 on the top wall of the closure 1300, which may be selectively colored. The geometry of the closure 1300 may enhance the surface rigidity of the closure 1300. As shown in FIG. 13, the arms of the star branding feature 1302 may be formed as ribs or reinforcing elements to minimize deformation of the closure 1300. A typical deformation may be doming or curvature caused by internal pressure from carbonation of a liquid within a container closed with the closure 1300.

[0080] The present disclosure further provides methods of making the closures described herein.

[0081] In one embodiment, a method of making a closure as described herein can include thermoforming a sheet of polyester resin into the closure. In a particular embodiment, the thermoforming can include applying a sheet of polyester resin to a male mold.

[0082] In another example, the method of making the closures described herein can include injection or compression molding a polyester resin into the closure.

[0083] The present disclosure further provides methods of sterilizing the closures and containers described herein.

[0084] In one embodiment, the method of sterilizing the closures and containers described herein can include exposing the closure to an electromagnetic radiation source capable of inactivating pathogens. Exposure of the closure to the electromagnetic radiation source can be enhanced by the transparency of the closure. The closure can be exposed to the electromagnetic radiation source before or after the closure is attached to the container. The electromagnetic radiation may be capable of inactivating pathogens. For example, the electromagnetic radiation can be of a wavelength of 200-300 nanometers. In certain embodiments, the exposure can be for a period of from 1 minute, or from 2 minutes, or from 5 minutes, or from 10 minutes, or from 15 minutes, or from 20 minutes, or from 25 minutes to 30 minutes or more, or from 2 minutes to 5 minutes, or from 10 minutes, or from 15 minutes, or from 20 minutes, or from 25 minutes, or from 30 minutes or more, or any range consisting of any two of the foregoing numbers (including any subranges therebetween). In other embodiments, the electromagnetic radiation source can be of a wavelength of 253 nanometers to 254 nanometers. In yet another embodiment, the electromagnetic radiation source can be at a wavelength between 255 nanometers and 280 nanometers. In yet another embodiment, the electromagnetic radiation source can be at a wavelength of about 230 nanometers. In yet another embodiment, the electromagnetic radiation source can be at a wavelength of about 10 -7 In yet another embodiment, the electromagnetic radiation source may be of wavelength less than 10 meters. -11 In yet another embodiment, the electromagnetic radiation source may be of wavelength less than 10 -6 The electromagnetic radiation source may be of a wavelength in the range formed by any two of the aforementioned wavelengths, including any subrange therebetween. In yet other examples, the exposure may be to successive bursts of electromagnetic radiation of the same or different wavelengths. Examples of electromagnetic radiation sources may include low pressure mercury lamps, ultraviolet light emitting diodes, and pulsed xenon lamps. In yet other examples, the closure may include an antimicrobial coating on the exterior or interior surface.

[0085] In one embodiment, the present disclosure provides a thermoformed polyester resin closure for closing a container, the closure including an annular wall that lies against an upper surface of a rim of a finish of the container, an outer cylindrical wall extending downwardly from the annular wall, the outer cylindrical wall including an outer skirt configured to be spaced outwardly from an outer surface of the rim of the finish and providing clearance between the closure and the outer surface of the finish, an inner cylindrical wall extending downwardly from the annular wall, the inner cylindrical wall configured such that an outward facing surface of the inner cylindrical wall has an interference fit with an inward facing surface of the finish of the container for sealing against the inward facing surface of the finish, and a bottom wall extending across a bottom of the inner cylindrical wall.

[0086] In certain examples, the polyester resin may include polyethylene terephthalate (PET).

[0087] In another example, the polyester resin may include polyethylene furan dicarboxylate (PEF).

[0088] In yet another embodiment, the polyester resin may be a copolymer including PET and PEF.

[0089] In yet other embodiments, the bottom wall may include a sloped portion for centering the inner cylindrical wall while the closure portion is engaged with the finish portion.

[0090] In yet another embodiment, the lower wall has an upwardly concave shape in an unpressurized state and a downwardly concave shape when the closure closes a pressurized container, whereby pressure is applied to increase the sealing force of the inner cylindrical wall against the finish.

[0091] In yet other embodiments, the closure may be colored with removable dyes and / or inks.

[0092] In yet another embodiment, a nanocoating may be deposited on the surface of the closure.

[0093] In yet other embodiments, the closure may include a tamper-evident band around a bottom periphery of the outer cylindrical wall.

[0094] In yet other embodiments, the tamper evidence band may include a plurality of knurls distributed around an exterior or interior surface of the tamper evidence band.

[0095] In yet other embodiments, the tamper evidence band may be configured to form a tether for attaching the closure to the container when the closure is removed from the finish.

[0096] In yet other embodiments, the outwardly facing surface of the inner cylindrical wall may be smooth.

[0097] In yet another embodiment, the outwardly facing surface of the inner cylindrical wall may include a roughness of 0.2 microns.

[0098] In yet other embodiments, the closure may further include threads on the outer cylindrical wall for engaging the threads on the finish.

[0099] In yet other examples, the closure may include a plurality of threads on the outer cylindrical wall, each of the plurality of threads beginning at a corresponding thread beginning.

[0100] In yet other examples, the outer cylindrical wall may include a plurality of knurls or a plurality of knurled portions distributed around at least a portion of the exterior or interior surface of the outer cylindrical wall.

[0101] In yet other embodiments, the closure may further include a seal attached to the rim of the finish to close the finish of the container, the seal contacting the bottom wall of the closure when the closure is attached to the finish of the container.

[0102] In yet another embodiment, the container may comprise PET.

[0103] In yet another embodiment, the container may comprise PET.

[0104] In yet another embodiment, the container may include a copolymer including PET and PEE.

[0105] In yet another embodiment, a method of sterilizing the closure may include exposing the closure to a source of electromagnetic radiation capable of inactivating pathogens.

[0106] In yet other embodiments, the method may further include applying a closure to the container prior to the exposing.

[0107] In yet other embodiments, the method may further include applying a closure to the container after exposing.

[0108] In yet another embodiment, the electromagnetic radiation source may be of wavelength between 200 and 300 nanometers.

[0109] In yet other embodiments, the closure may include an antimicrobial coating on the exterior and / or interior surface.

[0110] In yet another embodiment, a method of manufacturing a closure may include thermoforming a sheet of polyester resin into the closure.

[0111] In yet another embodiment, thermoforming may involve applying a sheet of polyester resin to a male mold.

[0112] In another embodiment, the present disclosure provides a thermoformed polyester resin closure for closing a container comprising polyester, the closure including a top wall that rests against an upper surface of a rim of a finish of the container, and a cylindrical wall extending downwardly from the top wall, the inwardly facing surface of the cylindrical wall configured to have an interference fit with the outwardly facing surface of the rim for sealing against the outwardly facing surface of the rim.

[0113] In certain examples, the polyester resin may include polyethylene terephthalate (PET).

[0114] In another example, the polyester resin may include polyethylene furan dicarboxylate (PEF).

[0115] In yet another embodiment, the polyester resin may be a copolymer including PET and PEF.

[0116] In yet other embodiments, the closure may be colored with removable dyes and / or inks.

[0117] In yet another embodiment, a nanocoating may be deposited on the surface of the closure.

[0118] In yet other embodiments, the closure may include a tamper-evident band around the bottom periphery of the cylindrical wall.

[0119] In yet other embodiments, the tamper evidence band may include a plurality of knurls distributed around an exterior or interior surface of the tamper evidence band.

[0120] In yet other embodiments, the tamper evidence band may be configured to form a tether for attaching the closure to the container when the closure is removed from the finish.

[0121] In yet other embodiments, the closure may further include threads on the cylindrical wall for engaging the threads on the finish.

[0122] In yet other examples, the closure may include a plurality of threads on the cylindrical wall, each of the plurality of threads beginning at a corresponding thread beginning.

[0123] In yet other embodiments, the cylindrical wall may include a plurality of knurls or a plurality of knurled portions distributed around at least a portion of the exterior or inwardly facing surface of the outer cylindrical wall.

[0124] In yet other embodiments, the closure may include a seal attached to the rim of the finish to close the finish of the container, the seal contacting the underside of the upper wall of the closure when the closure is attached to the finish of the container.

[0125] In yet another embodiment, the container may comprise PET.

[0126] In yet another embodiment, the container may contain a PEF.

[0127] In yet another embodiment, the container may include a copolymer including PET and PEF.

[0128] In yet other embodiments, the closure portion may be reduced over the finish portion.

[0129] In yet another embodiment, the closure may be heat shrunk onto the finish.

[0130] In yet other embodiments, the closure may be bonded to the finish by thermal or ultrasonic bonding.

[0131] In yet another embodiment, the closure may be bonded to the top surface of the rim of the finish.

[0132] In yet other embodiments, the bond of the closure to the finish may be configured to provide tamper evidence.

[0133] In yet another embodiment, a method of sterilizing the closure may include exposing the closure to a source of electromagnetic radiation capable of inactivating pathogens.

[0134] In yet other embodiments, the method may further include applying a closure to the container prior to the exposing.

[0135] In yet other embodiments, the method may further include applying a closure to the container after exposing.

[0136] In yet another embodiment, the electromagnetic radiation source may be of wavelength between 200 and 300 nanometers.

[0137] In yet other embodiments, the closure may include an antimicrobial coating on the exterior and / or interior surface.

[0138] In yet another embodiment, a method of manufacturing a closure may include thermoforming a sheet of polyester resin into the closure.

[0139] In yet another embodiment, thermoforming may involve applying a sheet of polyester resin to a male mold.

[0140] In yet another embodiment, the present disclosure provides an injection molded polyester resin closure for closing a container comprising a polyester, the polyester resin comprising polyethylene furan dicarboxylate ("PEF").

[0141] In certain examples, the polyester resin can include up to 90 mole percent PEF, which can be derived from the reaction of furandicarboxylic acid (FDCA) with polyethylene glycol (PEG) and / or diethylene glycol (DEG).

[0142] In other examples, the method of manufacturing the closure may include injection or compression molding a polyester resin into the closure.

[0143] In yet another embodiment, the present disclosure provides a thermoformed polyester resin closure for closing a polyester-containing container, the closure including an outer layer including an outer layer annular wall, an outer layer outer cylindrical wall extending downwardly from the outer layer annular wall, an outer layer inner concave wall extending downwardly from the outer layer annular wall, and an outer layer lower wall extending across a bottom of the outer layer inner concave wall, the outer layer lower wall including a lower recess of a first shape, and an inner layer including an inner layer annular wall, an inner layer outer cylindrical wall extending downwardly from the inner layer annular wall, and an inner layer inner concave wall extending downwardly from the inner layer annular wall. the inner layer inner concave wall extending downwardly from the inner layer annular wall, the inner layer inner concave wall configured such that an outwardly facing surface of the inner layer inner concave wall has an interference fit with the outwardly facing surface of the finish portion for sealing against the outwardly facing surface of the finish portion; and the inner layer lower wall extending across a bottom of the inner layer inner concave wall, the inner layer lower wall including a lower recess of a second shape that receives the lower recess of the first shape, the lower surface of the lower recess of the first shape configured to face and lock with an upper surface of the lower recess of the second shape.

[0144] In certain embodiments, the outer layer outer cylindrical wall may include an outer layer folded band disposed radially outwardly along a bottom periphery of the outer layer outer cylindrical wall.

[0145] In other embodiments, the outer layer outer cylindrical wall may include a plurality of knurls circumferentially distributed about an outer surface of the outer layer outer cylindrical wall.

[0146] In yet another embodiment, the inner surface of the inner layer outer cylindrical wall may include threads for engaging threads on a finish of the container.

[0147] In yet another embodiment, the inner layer outer cylindrical wall may include an inner layer folded band disposed radially outwardly along a bottom periphery of the inner layer outer cylindrical wall.

[0148] In yet other embodiments, the outer layer folding band can be configured to fit snugly within a groove between the outer surface of the inner layer outer cylindrical wall and the inner layer folding band.

[0149] In certain examples, the polyester resin may include polyethylene terephthalate (PET).

[0150] In another example, the polyester resin may include polyethylene furan dicarboxylate (PEF).

[0151] In yet another embodiment, the polyester resin may be a copolymer including PET and PEF.

[0152] In yet another embodiment, the inner layer lower wall may include a sloped portion for centering the inner layer inner cylindrical wall during engagement of the closure portion with the finish portion.

[0153] In yet another embodiment, the inner layer lower wall may have an upwardly concave shape in an unpressurized state and a downwardly concave shape when the closure closes a pressurized container, whereby pressure is applied to increase the sealing force of the inner layer inner cylindrical wall against the finish.

[0154] In yet other embodiments, the outer layer and / or the inner layer may be colored with removable dyes and / or inks.

[0155] In yet other embodiments, a nanocoating may be deposited on the surface of the outer layer and / or the inner layer.

[0156] In yet other embodiments, the closure may include a tamper-evident band around a bottom periphery of the inner layer.

[0157] In yet another embodiment, the inner surface of the outer cylindrical wall may include a plurality of threads, each of the plurality of threads beginning at a corresponding thread beginning.

[0158] In yet another embodiment, the container may comprise PET.

[0159] In yet another embodiment, the container may contain a PEF.

[0160] In yet another embodiment, the container can be a copolymer including PET and PEF.

[0161] In yet another embodiment, a method of sterilizing the closure may include exposing the closure to a source of electromagnetic radiation capable of inactivating pathogens.

[0162] In yet other embodiments, the method may further include applying a closure to the container prior to the exposing.

[0163] In yet other embodiments, the method may further include applying a closure to the container after exposing.

[0164] In yet another embodiment, the electromagnetic radiation source may be of wavelength between 200 and 300 nanometers.

[0165] In yet other embodiments, the closure may include an antimicrobial coating on the exterior and / or interior surface.

[0166] In yet another embodiment, a method of making a closure includes thermoforming a sheet of polyester resin into an outer layer, separately thermoforming a second sheet of polyester resin into an inner layer, and combining the outer layer and the inner layer.

[0167] In yet another embodiment, the transforming may include applying a sheet of polyester resin to the male mold.

[0168] In yet another embodiment, the separately transforming may include applying a sheet of a second polyester resin to the second male mold. EXAMPLES

[0169] The present disclosure may be better understood in connection with the following examples. Furthermore, the non-limiting examples are illustrative. Those skilled in the art will understand that for any given example of the present disclosure, it may be necessary to modify the procedure, for example, to change the order or steps and / or chemical reagents used.

[0170] Example 1 Thermoformed PET closure Described herein is the development of replacing injection molded HDPE / PP based PCO1881 plastic bottle caps with PET closures thermoformed from PET sheet. Among the challenges during development was developing a mold and process to solve the problems associated with plug seals and tamper-evident capabilities.

[0171] The use of a benchtop style JT-018 Denial Thermoformer ("JT-018") was investigated. The primary objective was to create a prototype mold geometry to model a PET closure and then manufacture it. The goal was to create a thermoformed plug seal that would meet or exceed industry standards for closures while also developing a TE band.

[0172] The use of JT-018 allowed for the production of various iterations of a single closure that could be tested for product seal, closing and opening torque, and functionality against industry standards for tamper evident closures. Considerations in producing the prototype also included mass production capabilities and closure processes used by the bottling industry and equipment manufacturers.

[0173] Off-the-shelf equipment was modified to provide better process control, for example adding controls to the heating elements of JT-018.

[0174] We developed specialized tools for testing and process intensification: for example, the pressure test skid allowed us to pressure test the finished mold; the cap punch allowed us to efficiently cut off the finished closure; the pressure bell allowed us to increase the external pressure on the thermoformer to obtain finer details.

[0175] A design for the mold to thermoform the closure was developed to allow for different shapes of release without jamming. A CAD program, Solid Works, was utilized to develop a mold that could be printed 3-dimensionally and communicated to stakeholders. 3-D printing an early prototype mold allowed for economical trial of several concepts with quick turnaround of mold modifications. Rough surfaces reflected in the finished thermoformed closure and causing seal integrity issues were polished using a multi-step polishing process starting with 800 grit and ending with 80,000 grit orthotic polishing compound. A die was utilized to cut the final thermoformed product and tested for performance against industry standards.

[0176] Technical considerations included temperature control, aluminum molds, external pressure devices, and hermetic testing.

[0177] A. Temperature Control: PET is a crystalline plastic that has its own properties while it is being heated. PET enters its glass transition range and becomes malleable and transparent at 67-80°C (153-76°F). Over time, PET crystallizes at 80-260°C (176-500°F), turns white, and becomes brittle. PET melts at 260°C (500°F). Therefore, PET is versatile in its applications, but can have limitations. Molding machines have a maximum temperature of 457°C (855°F) and can heat the plastic too quickly. Therefore, variable resistors were inserted into the molding machines to manage the temperature control, allowing them to have a more precise temperature and more easily control the molding of PET.

[0178] B. Aluminum Mold: High thermal conductivity, or rapid heat transfer, allows the heat to be removed very quickly from the PET during molding, resulting in fast cooling of the PET closure and fast cooling of the mold.

[0179] C. External Pressure Unit: A vacuum within the machine was needed to draw the hot plastic into the mold crevice. The maximum vacuum achievable is 1 bar (14 psi). Working in the glass areas of the PET, more pressure was needed to form the sharp angles seen in the mold. The external pressure unit allows for several ranges of external pressure, and diminishing returns in forming the plastic around the mold occurred after reaching 4.1 bar (60 psi). With an external pressure of 4.1 bar (60 psi) added to an internal pressure of 1 bar (14 psi), the plastic could easily form around the mold. Higher external pressures could further improve the definition of the part features.

[0180] D. Seal Testing: Testing for leaks on a seal requires a way to create pressure in the cap. A pressure test apparatus was created to apply pressure to the cap and then use water to find any air bubbles escaping from the cap.

[0181] Testing performed on the closures included torque testing, weight and measurement (e.g., based on thread depth and weight of the cap), and seal testing. Tests were performed to determine the crystallization point of the material. Excessive heat created a rapid crystallization transition phase that was difficult to control. A resistance control to JT-018 was added to control the heat for the replicate trials.

[0182] Table 1 provides the crystallization data (cycle times for PET plastic molding). The heater temperature was about 875° F. for all runs, which was the maximum heater temperature. The level from the heater was midway between the mold and the heater. [Table 1]

[0183] Preliminary testing was done on the completed mold with marginal results. The laboratory scale vacuum forming process had limitations and was unable to produce a fully developed thread. As a result, torque above 0.5Nm was not achieved and the cap was unable to sustain measurable pressure. Trials were repeated with additional equipment added to induce external pressure and improved control.

[0184] The apparatus was constructed to allow the application of external pressure during the forming process. The vacuum treatment was limited to a differential pressure of 1 atm (1.01 bar) under completely sealed conditions. With a modified system it was possible to apply an additional differential pressure of up to 10 bar to force the forming of finer details. Tests showed that 4 bar was sufficient. The data are summarized in Table 2. [Table 2]

[0185] A correlation has been observed between closure torque and seal pressure: as the closure torque increases or decreases, the ability to hold a seal is proportional.

[0186] Improvements in thread detail were seen in sealing when external pressure was applied during the thermoforming process. A correlation was found between increased sealing pressure and generated thread torque.

[0187] The finished thermoformed cap was examined under a polarizing film to reveal stress lines and material deformation from the thermoforming process.

[0188] Other films were analyzed to validate the thermoforming process. These materials were unable to develop the ability to hold torque or pressure, but the analysis showed nearly fully developed thread detail. Therefore, modifications to increase pressure on the thermoformer may result in improved performance with thicker, stiffer PET materials.

[0189] Example 2 Injection molded PET closure In one embodiment, the closure can be an injection molded polyester resin, such as a polyester resin with FDCA and / or DEG content that increases the compliance of the polyester resin material relative to PET sufficiently so that the material can be injection molded. In certain embodiments, the closure is of standard injection molded configuration (in other words, the closure has a shape similar to injection molded HOPE and PP closures), as shown, for example, in Figures 16A and 16B. Figure 16A shows a partial cross-sectional view of the top of an injection molded polyester resin closure 1400. Figure 16B shows a partial cross-sectional view of the closure 1400 attached to a finish 1402. The closure 1400 includes a conventionally injection molded plug seal 1404. The FDCA modified and / or DEG modified polyester resin can have sufficiently low stress that the plug seal 1404 can achieve a relatively high melt deformation, as is evident by comparing the deflection of the plug seal 1404 in Figure 16B to Figure 16A.

[0190] In certain examples, the injection molded closures are constructed similarly to standard injection molded HOPE or PP closures, but with thinner wall thickness to reduce the relative stiffness of the closure. In addition to wall thickness, interference fits can be reduced, as described for the ranges used for thermoformed PET closures, to accommodate the relatively high stiffness of PET or comonomer modified polyesters.

[0191] Experimental Example 3 Copolymer for closure produced via synthesis of 2% FDCA in PET In one example, a copolymer suitable for closure was produced via polymerization of 2% FDCA in PET and SSP. The process of synthesizing the copolymer of PET and EG with 2% FDCA from PTA (or TPA) was divided into two stages. The transesterification stage was continued until the temperature at the top of the distillation was below 90°C and the mixture was clear. Polycondensation was carried out after esterification. During the course of the synthesis, the reaction was monitored based on the amount of water produced and the amount of water collected in the buffer tank. About 369 milliliters of water were collected. The material was extracted from the reactor when the intrinsic viscosity reached approximately 0.55 dL / g based on torque calibration. The intrinsic viscosity can be increased using solid state polymerization, which further improves the performance of the prepared material for injection molding applications. Tables 3 and 4 below provide the reaction conditions in the esterification reactor and polycondensation reactor, respectively. [Table 3] [Table 4]

[0192] Example 4 Effect of FDCA fraction on crystallization The effect of the amount of FDCA present in the copolymer on crystallization in a polyester resin copolymer suitable for closures was demonstrated. Specifically, it was observed that as the FDCA fraction increased, the rate and extent of crystallization in PET decreased.

[0193] Table 5 provides DSC results demonstrating: (1) an increase in Tg with the FDCA fraction; (2) an increase in Tm; and (3) a decrease in % crystallinity. [Table 5]

[0194] Varying the amount of FDCA also varied other physical and chemical properties of the resulting copolymers, including, for example, modulus and gas diffusion (barrier) properties. Both the % crystallinity of the copolymer and the mobility of the furan dicarboxylic acid component of the copolymer affected the modulus and gas diffusion properties, such that the same % crystallinity in PET without FDCA had lower diffusion or mechanical properties than PET with FDCA.

[0195] Example 5 Thread depth and pressure retention Thread depth is a function of both the mold design and the molding process. With a given mold, thread depth can be adjusted through process control, which leads to changes in the performance of the closure. When the thread is fully formed, the interaction between the finish and the closure is maximized by a particular mold design, which results in an increase in the torque required to strip the closure by jumping the closure thread on the finish thread. Thread depth can also be a function of thickness and material stiffness, resulting for example from increased crystallinity, which can allow multiple ways to increase strip torque with one design. Once fully formed thread performance is understood, it can be useful to make modifications to the mold to deepen the possible forming limits of the thread. Another reason for adjusting thread depth and contact surface can be to avoid increasing installation or removal torque beyond the limit that is comfortable for the consumer.

[0196] Using a standard laboratory size torque tester, the preform was placed in a clamp and zeroed. The closure was installed by applying a consistent torque in a clockwise direction until it engaged or approximately 580 degrees. A positive value is the installation torque. Once the closure was installed, the closure was removed by applying a force in a counterclockwise direction. A negative value is the removal torque. The closure was installed by applying a consistent torque in a clockwise direction until it engaged or approximately 580 degrees beyond failure. A positive value is the strip torque. The closure will deform after the strip torque test. After several tests, the preform is replaced with a new unused preform because repeating the test may damage the neck finish and skew the data. Torque may also be tested with a blow bottle filled with water.

[0197] The pressure retention test uses a standard battery bike / ball air pump to generate the air pressure used to blow out the closure. The pump is connected to an additional pressure gauge to provide two readings for the pressure being applied. Pressurized air is passed through the 1881 neck. The 1881 closure is placed into the neck finish and secured using standard installation procedures. The 1881 neck finish may be replaced with another neck finish and additional 1881 necks. The air pressure is increased until the 1881 closure reaches failure. Failure may be a slow leak with a consistent drop in air pressure inside the neck finish or a dramatic failure with a rapid loss of pressure. [Table 6]

[0198] Figure 14 shows a plot of the average thread depth and pressure retention of the 25 sample closures, as well as the relationship between the average thread depth and pressure retention of the closure. Figure 15 shows a plot of the ability of the 25 sample closures to hold pressure when applied to a container finish. The higher performing examples of the 25 sample closures may be examples of minimum performance when the manufacturing process is optimized.

[0199] The use of the terms "a" and "an" and "the" and similar referents in the context of describing this disclosure (particularly in the context of the claims below) should be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. The use of the term "plurality of" is defined by the applicant in its broadest sense, and any other implied definition or limitation above or below refers to a plural quantity, unless expressly asserted by the applicant. All methods described herein may be performed in any suitable order, unless otherwise indicated herein.

[0200] It will be appreciated by those of skill in the art that, for any and all purposes, all ranges recited herein encompass any and all possible subranges and combinations of subranges, as well as the individual values, particularly integer values, making up the range. Thus, it is understood that each unit between two specific units is also disclosed. For example, if "10 to 15" is disclosed, 11, 12, 13, and 14 are also disclosed individually and as part of a range. A recited range (e.g., weight percentage or carbon group) includes each specific value, integer, decimal, or identity within the range. Any recited range can be easily recognized as breaking down the same range into at least one half, one third, one quarter, one fifth, or one tenth, making it fully descriptive and enabling. Also, as will be appreciated by those of skill in the art, terms such as "up to," "at least," "greater than," "less than," "greater than," "or greater than," etc., are inclusive of the recited numbers, and such terms refer to ranges that can then be broken down into subranges. Similarly, all ratios recited herein include all subratios that fall within the broader ratio. Thus, the specific values ​​recited for radicals, substituents, and ranges are for illustrative purposes only and do not exclude other defined values ​​of radicals and substituents, or other values ​​within defined ranges, It is further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint.

[0201] Those skilled in the art will also readily recognize that when members are grouped together in a common manner, such as in a Markush group, the invention encompasses not only the entire group as described as a whole, but also each member of the group individually, and all possible subgroups of the main group. Moreover, for all purposes, the invention encompasses not only the main group, but also main groups lacking one or more of the group members. Thus, the invention contemplates the explicit exclusion of any one or more of the recited group members. Thus, provisos may be applied to any of the disclosed categories or examples, whereby any one or more of the recited elements, species, or examples may be excluded from such categories or examples, for example, as used in an explicit negative limitation.

[0202] As used herein, the terms "comprise," "include," "having," "has," "can," "contain," and variations thereof are intended to be open-ended transitional phrases, terms, or phrases that do not exclude the possibility of additional acts or structures. The description also contemplates other embodiments that "comprising," "consisting of," and "consisting essentially of" embodiments or elements present herein, whether or not explicitly stated.

[0203] In describing elements of the disclosure, the term "first st )," "Second (2 nd "(a)", "first", "primary", "A", "B", "(a)", "(b)", etc. may be used. These terms are used only to distinguish one element from another and do not limit the corresponding elements without regard to the nature or order of the corresponding elements.

[0204] Unless otherwise defined, all terms, including technical and scientific terms, used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. Terms as defined in commonly used dictionaries should be interpreted as having the same meaning as the contextual meaning in the relevant technical field.

[0205] As used herein, the term "about" when used in the context of a stated numerical value or range means a variation of ±15%, ±14%, +10%, or ±5%, among others, and meets the definition of "about" unless more narrowly defined in a specific instance.

[0206] Although the present disclosure has been described with reference to examples and accompanying drawings, the present disclosure is not limited thereto, and may be modified and altered in various ways by those skilled in the art to which the present disclosure pertains without departing from the spirit and scope of the present disclosure.

[0207] The subject matter of the present disclosure may also relate to, inter alia, the following aspects:

[0208] A first aspect relates to a thermoformed polyester resin closure for closing a container, the closure including an annular wall that lies against an upper surface of a rim of a finish of a container, an outer cylindrical wall extending downwardly from the annular wall, the outer cylindrical wall including an outer skirt configured to be spaced outwardly from an outer surface of the rim of the finish and providing clearance between the closure and the outer surface of the rim of the finish, an inner cylindrical wall extending downwardly from the annular wall, the inner cylindrical wall configured such that an outward facing surface of the inner cylindrical wall has an interference fit with the inward facing surface of the finish of the container for sealing against the inward facing surface of the finish, and a lower wall extending across a bottom of the inner cylindrical wall.

[0209] A second embodiment relates to the closure of embodiment 1, wherein the polyester resin comprises polyethylene terephthalate ("PET").

[0210] A third embodiment relates to the closure of embodiment 1, wherein the polyester resin comprises polyethylene furan dicarboxylate ("PEF").

[0211] A fourth embodiment relates to the closure of any of the preceding embodiments, wherein the polyester resin is a copolymer comprising PET and PEF.

[0212] A fifth aspect relates to a closure according to any of the preceding aspects, wherein the bottom wall includes a sloped portion for centering the inner cylindrical wall during engagement of the closure with the finish.

[0213] A sixth aspect relates to a closure according to any one of aspects 1 to 4, wherein the lower wall has an upwardly concave shape in an unpressurized state and a downwardly concave shape when the closure closes a pressurized container, whereby pressure acts to increase the sealing force of the inner cylindrical wall against the finish.

[0214] A seventh aspect relates to a closure according to any of the preceding aspects, wherein the closure is colored with a removable dye and / or ink.

[0215] An eighth aspect relates to the closure according to any one of the first to sixth aspects, wherein a nanocoating is deposited on a surface of the closure.

[0216] A ninth aspect relates to a closure according to any of the preceding aspects, wherein the closure includes a tamper-evident band around a bottom periphery of the outer cylindrical wall.

[0217] A tenth aspect relates to the closure of aspect 9, wherein the tamper evidence band includes a plurality of knurls distributed around an outer or inner surface of the tamper evidence band.

[0218] An eleventh aspect relates to the closure of aspect 9, wherein the tamper-evidence band is configured to form a tether for attaching the closure to the container when the closure is removed from the finish.

[0219] A twelfth aspect relates to a closure according to any of the preceding aspects, wherein the outwardly facing surface of the inner cylindrical wall is smooth.

[0220] A thirteenth aspect relates to the closure of any one of aspects 1-12, wherein the outwardly facing surface of the inner cylindrical wall comprises a roughness of 0.2 microns.

[0221] A fourteenth aspect relates to a closure according to any of the preceding aspects, further comprising threads on the outer cylindrical portion for engaging threads on the finish.

[0222] A fifteenth aspect relates to the closure of aspect fourteen, including a plurality of threads on the outer cylindrical wall, each of the plurality of threads beginning at a corresponding thread beginning.

[0223] A sixteenth aspect relates to a closure according to any of the preceding aspects, wherein the outer cylindrical wall includes a plurality of knurls or a plurality of knurled portions distributed around at least a portion of an outer or inner surface of the outer cylindrical wall.

[0224] A seventeenth aspect relates to a closure according to any of the preceding aspects, which may further include a seal attached to the rim of the finish to close the finish of the container, the seal contacting the bottom wall of the closure when the closure is attached to the finish of the container.

[0225] An eighteenth embodiment relates to a container of any of the preceding embodiments, comprising PET.

[0226] A nineteenth embodiment relates to a container according to any one of the first to seventeenth embodiments, comprising a PEF.

[0227] A twentieth aspect relates to a container of any of the preceding aspects, comprising a copolymer comprising PET and PEF.

[0228] A twenty-first aspect relates to a method of sterilizing a closure according to any one of aspects 1 to 17, comprising exposing the closure and the container to a source of electromagnetic radiation capable of inactivating pathogens.

[0229] A twenty-second embodiment relates to the method of embodiment 21, further comprising attaching the closure to the container prior to the exposing.

[0230] A twenty-third embodiment relates to the method of embodiment 21, further comprising attaching the closure to the container after the exposing.

[0231] A twenty-fourth aspect relates to the method according to any one of aspects twenty-first to twenty-third, wherein the electromagnetic radiation source is of a wavelength between 200 and 300 nanometers.

[0232] A twenty-fifth aspect relates to the method of any one of aspects 21 to 24, wherein the closure comprises an antimicrobial coating on an exterior and / or interior surface.

[0233] A twenty-sixth aspect relates to a method of making the closure of any one of aspects 1-17, the method comprising thermoforming a sheet of polyester resin into the closure.

[0234] A twenty-seventh embodiment relates to the method of embodiment 26, wherein the thermoforming comprises applying a sheet of the polyester resin to a male mold.

[0235] A twenty-eighth embodiment relates to a thermoformed polyester resin closure for closing a container comprising polyester, the closure including a top wall that rests against an upper surface of a rim of a finish of the container, and a cylindrical wall extending downwardly from the top wall, the inwardly facing surface of the cylindrical wall configured to have an interference fit with the outwardly facing surface of the rim for sealing against the outwardly facing surface of the rim.

[0236] A twenty-ninth embodiment relates to the closure of embodiment twenty-eight, wherein the polyester resin comprises polyethylene terephthalate ("PET").

[0237] A thirtieth embodiment relates to the closure of embodiment 28, wherein the polyester resin comprises polyethylene furan dicarboxylate ("PEF").

[0238] A thirty-first aspect relates to the closure of any one of aspects 28-30, wherein the polyester resin is a copolymer comprising PET and PEF.

[0239] A thirty-second aspect relates to the closure of any one of aspects twenty-eight to thirty-first, wherein the closure is colored with a removable dye and / or ink.

[0240] A thirty-third aspect relates to the closure of any one of aspects twenty-eight to thirty-first, wherein a nanocoating is deposited on a surface of the closure.

[0241] A thirty-fourth aspect relates to the closure of any one of twenty-eight to thirty-three, wherein the closure includes a tamper-evident band around a bottom periphery of the cylindrical wall.

[0242] A thirty-fifth aspect relates to the closure of aspect 34, wherein the tamper evidence band includes a plurality of knurls distributed around an outer or inner surface of the tamper evidence band.

[0243] A thirty-sixth aspect relates to the closure described in aspect 34, wherein the tamper-evidence band is configured to form a tether for attaching the closure to the container when the closure is removed from the finish.

[0244] A thirty-seventh aspect relates to the closure of any one of aspects twenty-eight to thirty-six, further comprising threads on the cylindrical wall for engaging threads on the finish.

[0245] A thirty-eighth aspect relates to the closure of aspect thirty-seven, further comprising a plurality of threads on the cylindrical wall, each of the plurality of threads beginning at a corresponding thread beginning.

[0246] A thirty-ninth aspect relates to the closure portion of any one of aspects twenty-eight to thirty-eight, wherein the cylindrical wall includes a plurality of knurls, or a plurality of knurled portions, distributed around at least a portion of an outer surface or an inwardly facing surface of the cylindrical wall.

[0247] A 40th aspect relates to a closure portion described in any one of aspects 28 to 39, and may further include a seal attached to the rim of the finish portion to close the finish portion of the container, the seal contacting the underside of the upper wall of the closure portion when the closure portion is attached to the finish portion of the container.

[0248] A forty-first embodiment relates to the container according to any one of embodiments 28 to 40, which comprises PET.

[0249] A forty-second embodiment relates to a container according to any one of embodiments 28 to 40, comprising a PEF.

[0250] A forty-third embodiment relates to the container of any one of embodiments 28 to 42, comprising a copolymer comprising PET and PEF.

[0251] A forty-fourth aspect relates to the closure section according to any one of aspects forty-first to forty-third, wherein the closure section is shrunk onto the finish.

[0252] A forty-fifth aspect relates to the closure section of aspect 44, wherein the closure section is heat shrunk onto the finish.

[0253] A forty-sixth aspect relates to the closure section according to any one of aspects forty-first to forty-third, wherein the closure section is bonded to the finish section by thermal or ultrasonic bonding.

[0254] A forty-seventh aspect relates to the closure portion of aspect 46, wherein the closure portion is bonded to the top surface of the rim of the finish.

[0255] A forty-eighth aspect relates to the closure of any one of aspects forty-six or fourteen, wherein a bond between the closure and the finish is configured to provide tamper evidence.

[0256] A forty-ninth aspect relates to a method of sterilizing a closure according to any one of aspects 28 to 40, comprising exposing the closure to a source of electromagnetic radiation capable of inactivating pathogens.

[0257] A 50th embodiment relates to the method of embodiment 49, further comprising attaching the closure to the container prior to the exposing.

[0258] A fifty-first embodiment relates to the method of embodiment 49, further comprising attaching the closure to the container after the exposing.

[0259] A fifty-second aspect relates to the method of any one of aspects forty-nine to fifty-first, wherein the electromagnetic radiation source is of a wavelength between 200 and 300 nanometers.

[0260] A fifty-third embodiment relates to the method of any one of embodiments 49 to 52, wherein the closure comprises an antimicrobial coating on an exterior and / or interior surface.

[0261] A fifty-fourth aspect relates to a method of making the closure of any one of aspects twenty-eight to forty, the method comprising thermoforming a sheet of polyester resin into the closure.

[0262] A fifty-fifth embodiment relates to the method of embodiment fifty-four, wherein the thermoforming comprises applying a sheet of the polyester resin to a male mold.

[0263] A fifty-sixth embodiment relates to an injection molded polyester resin closure for closing a container comprising polyester, the polyester resin comprising polyethylene furan dicarboxylate ("PEF").

[0264] A fifty-seventh embodiment relates to the closure of embodiment fifty-six, wherein the polyester resin comprises up to 90 mole percent PEF, the PEF being derived from the reaction ion of furandicarboxylic acid ("FDCA") with polyethylene glycol ("TEG") and / or diethylene glycol ("DEG").

[0265] A fifty-eighth embodiment relates to a method of making the closure of embodiment fifty-six or fifty-seven, the method comprising injection or compression molding a polyester resin into the closure.

[0266] A fifty-ninth embodiment relates to a thermoformed polyester resin closure for closing a polyester-containing container, the closure comprising an outer layer including an outer layer annular wall, an outer layer outer cylindrical wall extending downwardly from the outer layer annular wall, an outer layer inner concave wall extending downwardly from the outer layer annular wall, and an outer layer lower wall extending across a bottom of the outer layer inner concave wall, the outer layer lower wall including a lower recess of a first shape, and an inner layer including an inner layer annular wall, an inner layer outer cylindrical wall extending downwardly from the inner layer annular wall, and an inner layer outer cylindrical wall extending downwardly from the inner layer annular wall. the inner layer including an inner concave wall, the inner layer inner concave wall configured such that an outwardly facing surface of the inner layer inner concave wall has an interference fit with the outwardly facing surface of the finish portion for sealing against the outwardly facing surface of the finish portion, and an inner layer lower wall extending across a bottom of the inner layer inner concave wall, the inner layer lower wall including a lower recess of a second shape that receives the lower recess of the first shape, the lower surface of the lower recess of the first shape being configured to face and lock into an upper surface of the lower recess of the second shape.

[0267] A sixtieth aspect relates to the closure of aspect fifty-nine, wherein the outer layer outer cylindrical wall includes an outer layer folded band disposed radially outward along a bottom periphery of the outer layer outer cylindrical wall.

[0268] A sixty-first aspect relates to the closure of aspect 59 or 60, wherein the outer layer outer cylindrical wall includes a plurality of knurls distributed circumferentially around an outer surface of the outer layer outer cylindrical wall.

[0269] A sixty-second aspect relates to the closure of any one of aspects 59 to 61, wherein an inner surface of the inner layer outer cylindrical wall includes threads for engaging with threads of a finish of the container.

[0270] A 63rd aspect relates to a closure portion described in any one of aspects 59 to 62, wherein the inner layer outer cylindrical wall includes an inner layer folded band disposed radially outward along a bottom periphery of the inner layer outer cylindrical wall.

[0271] A 64th aspect relates to the closure portion of aspect 63, wherein the outer layer folding band is configured to fit securely within a groove between an outer surface of the inner layer outer cylindrical wall and the inner layer folding band.

[0272] A sixty-fifth aspect relates to the closure of any one of aspects fifty-nine to sixty-four, wherein the polyester resin comprises polyethylene terephthalate ("PET").

[0273] A sixty-sixth aspect relates to the closure of any one of aspects 59 to 65, wherein the polyester resin comprises polyethylene furan dicarboxylate ("PEF").

[0274] A sixty-seventh aspect relates to the closure of any one of aspects fifty-nine to sixty-six, wherein the polyester resin is a copolymer comprising PET and PEF.

[0275] A 68th aspect relates to a closure portion described in any one of aspects 59 to 67, wherein the inner layer lower wall includes a sloped portion for centering the inner layer cylindrical wall during engagement of the closure portion with the finish portion.

[0276] A 69th aspect relates to a closure portion according to any one of aspects 59 to 68, wherein the inner layer lower wall has an upwardly concave shape in an unpressurized state and has a downwardly concave shape when the closure portion closes a pressurized container, whereby pressure acts to increase the sealing force of the inner layer inner cylindrical wall against the finish portion.

[0277] A seventieth aspect relates to the closure of any one of aspects 59 to 69, wherein the outer layer and / or the inner layer are colored with a removable dye and / or ink.

[0278] A seventy-first aspect relates to the closure of any one of aspects 59 to 69, wherein a nanocoating is deposited on a surface of the outer layer and / or the inner layer.

[0279] A seventy-second aspect relates to the closure of any one of aspects 59-71, wherein the closure includes a tamper-evident band around a bottom periphery of the inner layer.

[0280] A 73rd aspect relates to a closure portion described in any one of aspects 59 to 72, wherein the inner surface of the inner layer outer cylindrical wall includes a plurality of threads, each of the plurality of threads starting at a corresponding thread start portion.

[0281] A seventy-fourth embodiment relates to the container of any one of embodiments 59 to 73, comprising PET.

[0282] A seventy-fifth embodiment relates to a container according to any one of embodiments 59 to 73, comprising a PEF.

[0283] A seventy-sixth embodiment relates to the container of any one of embodiments 59 to 75, comprising a copolymer comprising PET and PEF.

[0284] A seventy-seventh aspect relates to a method of sterilizing a closure according to any one of aspects 59 to 73, comprising exposing the closure to an electromagnetic source capable of inactivating pathogens.

[0285] A seventy-eighth embodiment relates to the method of embodiment seventy-seven, further comprising attaching the closure to the container prior to the exposing.

[0286] A seventy-ninth embodiment relates to the method of embodiment seventy-eight, further comprising attaching the closure to the container after the exposing.

[0287] An eightieth aspect relates to the method of any one of aspects 77 to 79, wherein the electromagnetic radiation source is of a wavelength between 200 and 300 nanometers.

[0288] An eighty-first aspect relates to the method of any one of aspects 77 to 80, wherein the closure comprises an antimicrobial coating on an exterior and / or interior surface.

[0289] An 82nd embodiment relates to a method of making a closure portion of any one of embodiments 59 to 73, comprising thermoforming a sheet of polyester resin to the outer layer, separately thermoforming a second sheet of polyester resin to the inner layer, and combining the outer layer and the inner layer.

[0290] An eighty-third embodiment relates to the method of embodiment 82, wherein the transforming includes applying a sheet of the polyester resin to a male mold.

[0291] An 84th embodiment relates to the method of embodiment 82 or 83, wherein the separately transforming includes applying a second sheet of the polyester resin to a second male mold.

[0292] In addition to the features mentioned in each of the independent aspects listed above, some examples may exhibit optional features mentioned in dependent aspects and / or disclosed in the above description and illustrated in the figures, either alone or in combination.

Claims

1. A polyester resin closure part attached to the finish portion of a container, wherein the polyester resin closure part is (a) A plug seal configured to seal against the inner surface of the finish portion and 、 (b) An annular wall configured to be positioned relative to the upper surface of the rim of the finish portion of the container, (c) An outer cylindrical wall extending downward from the annular wall, the outer cylindrical wall including an internal thread configured to engage with the finish portion, (d) A tamper evidence function configured to engage with the tamper evidence ledge of the finish portion, Includes, A polyester resin closure portion comprising polyethylene terephthalate, polyethylene flanger carboxylate, or a copolymer of polyethylene terephthalate and polyethylene flanger carboxylate.

2. The polyester resin closure according to claim 1, wherein the outer cylindrical wall includes an outer skirt having clearance with the corresponding outer surface of the rim to allow the polyester resin closure to deform in the area of ​​the plug seal.

3. The polyester resin closure portion according to claim 1, wherein the plug seal includes a chamfered portion for guiding the plug seal to pass over the inner lip of the finish portion when the polyester resin closure portion is capped onto the container.

4. The polyester resin closure portion according to claim 1, wherein the plug seal includes an inner cylindrical wall extending downward from the annular wall.

5. The inner cylindrical wall includes a radical surface sized to interlock with the corresponding inward-facing surface of the rim of the finish portion for sealing purposes. The aforementioned interlocking mechanism is configured to lock the polyester resin closing portion into the finishing portion. The polyester resin closure part according to claim 4, wherein the amount of the interference fit is optionally 0.02 mm to 0.2 mm.

6. The lower wall extends across the bottom of the inner cylindrical wall, Optionally, the lower wall is configured to change shape in response to the pressurized contents between the plug seal and the finish portion inside the container. The polyester resin closure portion according to claim 4, optionally having an upwardly concave shape that becomes convex upward when pressure is applied by the pressurized contents inside the container.

7. The plug seal is configured to establish a sealing interface with the finish portion, The polyester resin closure portion according to claim 4, wherein the width of the sealing interface is optionally configured to fill defects present in the finish portion.

8. The tamper-evident function includes a folding band, Optionally, the tamper-evidence function includes a plurality of spaced bridges connecting the folding band to the outer cylindrical wall of the polyester resin closure, Optionally, the multiple spaced bridges are configured to break when the polyester resin closure is removed from the finish portion. The polyester resin closure according to claim 1, wherein the folding band is optionally configured to be held in a predetermined position by the tamper-evident ledge when the polyester resin closure is removed from the finish portion.

9. The outer cylindrical wall is (i) Each of the multiple threaded portions that begin at the corresponding thread start, (ii) Multiple knurled portions arranged around the outer cylindrical wall, A polyester resin closure part according to claim 1, including the above.

10. A method for manufacturing a polyester resin closure part to be attached to the finish portion of a container, wherein the polyester resin closure part is (a) at least one layer, (i) an annular wall configured to be positioned relative to the upper surface of the rim of the finish portion, (ii) An outer cylindrical wall extending downward from the annular wall, wherein the outer layer outer cylindrical wall includes a plurality of knurled outer cylindrical walls, A layer including at least one layer, (b) A tamper evidence function configured to engage with the tamper evidence ledge of the finish portion, Equipped with, The aforementioned method, A method comprising thermoforming, injection molding, or compression molding a polyester resin onto the polyester resin closure portion.

11. The method according to claim 10, further comprising, before the thermoforming, injection molding, or compression molding, mixing polyethylene terephthalate with a certain amount of flanging carboxylic acid (FDCA), diethylene glycol (DEG), or a combination thereof to reduce the modulus of elasticity of the polyester resin so that the polyester resin closure can be discharged from the mold cavity.

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