Rigid medical packaging made from a clear recyclable shrink sleeve suitable for autoclave steam sterilization

Abstract

The present disclosure describes a multi-step process for purposely inducing stress and strain into a thermoplastic film or sheet to make a shrink film, configuring and fixing the film into a cylindrical or other-shaped, shrinkable sleeve shape, inserting package content (a device, liquid or liquid with solids), and heating the entire assembly to purposely shrink the sleeve around the content to be packaged without use of a mold. In instances where a crystalline or semi-crystalline resin for the shrinkable film or sheet has been utilized, a heat setting step can be employed wherein the resulting clear package can withstand steam sterilization without a significant degree of visual haze.

Description

RIGID MEDICAL PACKAGING MADE FROM A CLEAR RECYCLABLE SHRINK SLEEVE SUITABLE FOR AUTOCLAVE STEAM STERILIZATIONBACKGROUND OF THE INVENTION

[0001] Today, clear, rigid medical packaging is normally made from non-oriented PETG copolyester, or alternatively, from the less expensive, non-oriented polyesters PET / APET. While these package materials and methods to manufacture them are fit-for-use, there are multiple opportunities for improvements. One type of segmentation to apply involves categorization of the rigid medical packaging into two groups: clamshell type thermoformed designs with a hinged lid and bottom-only thermoformed trays utilizing opaque lid stock on the top surface as is common with form-fill-seal type processing. The improvement opportunities common to both package designs include poor rccvclability. expensive manufacturing tooling and processing, limited sterilization techniques and expensive resin sourcing. Improvement opportunities specific to packages with lid stock include opacity from the lidding film, dissimilar lid stock chemistry and adhesive application.

[0002] For example, of the many opportunities for improvement, one opportunity for improvement for rigid packaging involves its lack of recyclability. Another opportunity for improvement for rigid packaging involves the unnecessary expense of thermoforming tooling and processing. The next opportunity for improvement for rigid packaging concentrates on the form / fill / seal designs where an opaque upper lid stock is used. Y et another opportunity for improvement for rigid packaging focuses on avoidance of a single-sourced resin, often with its associated high resin cost. Further opportunities for improvement for the status quo rigid packaging pertain to the propensity for a package to warp. An additional opportunity for improvement for the status quo rigid packaging involves simplification of the validation process.SUMMARY OF THE INVENTION

[0003] In the present disclosure, either an amorphous or semi-crystalline thermoplastic film is extruded and oriented or stretched and subsequently provided as an intermediate shrinkable film or sheet to downstream customers for additional processing. Customers then process the intermediate shrinkable film into a desired shape, such as a cylindrical sleeve by cutting, rolling and sealing an edge to form a tube or with at least one open end. Alternative package shapes will be discussed elsewhere in the disclosure. A packageable item (such as medical or other device, solid or liquid food item, etc.) is then inserted into the sleeve, with optional elevating and impact-absorbing supports, when the ends are sealed. The sleeve with the packageable item inside is then subjected to an elevated temperature, usually above tire material’s glass transition temperature, where the sleeve shrinks to securely package the packageable item. In cases where a semi-crystalline resin is used instead of an amorphous version, this construct can then be optionally heat treated to heat set and complete cry stallization to enable high temperature package properties, including autoclave steam sterilization use. In some embodiments, the heat treatment that shrinks the fdm also heat sets the film. After shrinking, whether heat set or not, the package and packageable item are normally ready for sterilization via ethylene oxide, gamma, e-beam or chemically-activated processes (or steam sterilization in some embodiments). The packaging and packaging process of this disclosure is well suited for use with packageable items such as medical devices, solid food items and liquid food times based on the packaging’s suitability for sterilization, and based on tire packaging’s other properties as will be apparent from this disclosure.

[0004] In contrast to prior-art packaging, rigid packaging which employs the current disclosure addresses the above outlined issues while additionally providing benefits regarding light-weighting, negating the propensity toward warping, many physical property improvements and potentially optimizing the validation process for new packages. Specifically, with respect to the opportunities for improvement outlined above, the packaging of this disclosure has the following advantages.

[0005] Prior art rigid packaging lacked recyclability. For example, PETG copolyester is the dominant chemistry used for conventional clear medical packaging. Unfortunately for this chemistry, its relatively low heat-distortion temperature and amorphous morphology lead to troubles in the recycle industry. Recycled PETG involves grinding these packages into flakes which subsequently stick to form non-processable agglomerations when its concentration is above about 2 to 3 weight percent loading in PET flake during the recycle process. These findings led tire state of California to rc-classify PETG from a recycle identification code (RIC) # 1 to its current classification as RIC #7, or “other”, the catch-all category for all other plastics not adhering to RIC streams 1 through 6. While package recyclability issues are present when using PETG, some embodiments of this disclosure permit use of PETG in the current disclosure for customers who desire to continue using PETG.

[0006] Similar to PETG, there are also recyclability issues with conventional thennofonned packages made from PET or APET chemistries. Like trays made from PETG, PET or APET thermoformed trays typically possess amorphous morphology and can therefore stick and agglomerate in the recycle process for processors who don’t possess the proper equipment to overcome this issue. This is a known phenomenon in the recycle industry and is the basis for a special provision in the clumping test procedure where agglomerations are allowed to be broken up before continuing the test. One such test method is PET- S-08 issued by The Association of Plastic Recyclers. While the current disclosure does include use of PET or APET chemistries, the processing technique herein utilized to give the film its shrinkable characteristics leads to a strain-induced molecular architecture with small spherulite crystals which do not agglomerate in the recycle process and are therefore easily recycled and properly classed as RIC#1.

[0007] With respect to the expense of thermoforming tooling and processing, conventionally, when a new package design is under consideration, a thermoformed tray must be designed to accept both the rigid and flexible parts of a medical device. Many hours are spent on the design and multiple revisions to these designs with special attention paid to the radii of every edge or comer and polishing tire metal molds to a high mirror finish so that flat sections of tire package maintain optimal clarity. In addition to theexpensive design and tooling phase, the thermoforming process itself is expensive and utilizes expensive in-line equipment. The current disclosure bypasses all aspects of thennofonning by use of a one-size-fits- all tube or similar shape that shrinks around the packageable item (such as a medical device) and its optional, impact-absorbing supports. It has been discovered that utilizing the shrink sleeve concept tends to naturally avoid tight radii in package contours that otherwise can become notch-sensitive stress concentrators which can embrittle the package.

[0008] The next opportunity for improvement for the status quo rigid medical packaging concentrates on the form / fill / seal designs where an upper lid stock is used. In this design, the bottom tray still utilizes clear trays made from PETG or APET but opaque lid stock has been heat sealed to form the package’s top surface. This lid stock is often a different chemistry than tire bottom tray which leads to recyclability concerns. Hie lidding is believed to be made from a spunbond or otherwise manufactured polyolefin with special coating so that it is heat sealable to the clear bottom tray. An example of the type of lid stock often used is Tyvek available through DuPont. In addition to recyclability concerns, the lidding is also sub-optimal because it hides the package content, being opaque lidding. Being highly engineered, the lid stock is also expensive as a raw material and requires the expensive step of heat sealing, which itself can have processing issues called ‘'branching,” a type of heat-sealing defect, presumably from an electrical or static-based coronal discharge that can harm package and device sterility. The current disclosure bypasses all of these aforementioned issues since no lidding material is used and triboelectric or other sourced discharges from dissimilar material use is prevented.

[0009] Yet another opportunity for improvement for the status quo rigid medical packaging focuses on avoidance of a single-sourced resin, often with its associated high resin cost. In some embodiments and in some markets, the current disclosure utilizes lower cost and more readily available PET and APET resin (compared to PETG) that can be sourced from a myriad of suppliers globally. Further, packaging can optionally include partial or full utilization of PET or APET post-industrial or post-consumerpellet or flake resin forms for mechanically-recycled sources that are not readily available for the competitive PETG resin.

[0010] Further opportunities for improvement for tire status quo rigid packaging (in particular rigid medical packaging) pertain to the propensity' for a package to warp. Packages made from PETG or PET / APET can warp during ethylene oxide (EO) sterilization, as anon-limiting example. Hie temperature set point for this process is often maintained by injection of steam. In some EO chamber designs, poor chamber mixing can lead to localized hot spots, especially near the injection port. Packages located close to the injection port can experience a higher temperature than packages located in other parts of the chamber, which can lead to package or tray warping. This warping often manifests itself with flat trays being bowed from one end to the other or by twisting along its longest radial direction or by flange sections in clamshell designs separating from one another (top and bottom sections, when closed). In certain embodiments of this disclosure, because a thermal environment above the material’s glass transition is desired to purposely shrink the film around the medical device, intentional warpage is desired and is engineering into the package such that any additional warpage achieved during sterilization shrinks inward, toward the medical device, to further secure and hold the device in place and does not appear as aesthetically displeasing bowing and twisting as can be seen in thermoformed trays.

[0011] An additional opportunity for improvement for the status quo rigid packaging (particularly rigid medical packaging) involves the validation process. During validation, new package designs are rigorously tested to ensure the package meets all fitness for use requirements for tire new package. Even when existing materials are used, the validation process can highlight issues with the thermoformed radii, closure mechanisms and other package design elements. In certain embodiments of this disclosure, the validation process is optimized and perhaps shortened or completely omitted since the shrink sleeve design is closer to a one-size-fits-all set-up with no new design elements to validate.BRIEF DESCRIPTION OF THE DRAWINGS

[0012] The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate one or more implementations described herein and, together with the description, explain these implementations. The drawings are not intended to be drawn to scale, and certain features and certain views of tire figures may be shown exaggerated, to scale or in schematic in the interest of clarity and conciseness. Not every component may be labeled in every drawing. Like reference numerals in the figures may represent and refer to the same or similar elements or function. In the drawings:

[0013] FIG. 1 illustrates an article comprising a sleeve and packageable item in accordance with this disclosure. Tire sleeve is shown before heat shrinking and sterilization.

[0014] FIG. 2 illustrates the article illustrated in FIG. 1 but after heat shrinking.

[0015] FIG. 3 illustrates an article in accordance with this disclosure, wherein the article comprises a sleeve and packageable item, and tire packageable item is a food item.DETAILED DESCRIPTION

[0016] Tire present disclosure may be understood more readily by reference to this description as well as to the examples included herein. In addition, numerous specific details are set forth in order to provide a thorough understanding of the embodiments and examples described herein. However, those of ordinary skill in the art will understand the embodiments and examples described herein can be practiced without these specific details. In other instances, methods, procedures and components have not been described in detail so as not to obscure the related relevant feature being described. Also, the description is not to be considered as limiting the scope of the embodiments described herein. Tire drawings are not necessarily to scale, and the proportions of certain parts may have been exaggerated to better illustrate details and features of the present disclosure.

[0017] As used herein and in the appended claims, an element or component that “comprises” or“includes” one or more specified components or steps means that the element or component includes thespecified component(s) alone or includes the specified component(s) together with one or more additional components. An element or component that ‘"consists of’ one or more specified components means that the element or component includes only the specified component(s). An element or component that “consists essentially of’ one or more specified components means that the element or component consists of the specified component(s) alone, or consists of the specified component(s) together with one or more additional components that do not materially affect the basic properties of the clement or component. Whenever a range is disclosed herein, the range includes independently and separately every member of the range extending between any two numbers enumerated within the range. Furthermore, the lowest and highest numbers of any range shall be understood to be included within the range set forth.

[0018] The film or sheet (herein after “film” when used alone will refer to a film or sheet unless the context dictates otherwise) utilized in the disclosure can be produced by a variety of methods . One method is extrusion and includes traditional extrusion of a molten polymer extrudate through an optional coat hanger die with a three-roll cooling roll stack. Other suitable methods are film or sheet casting, also involving molten extrudate through a heated die, usually with a two-roll cooling stack where the film is optionally pinned to the cooling roll with an air knife, vacuum box or via electrical / static pinning methods. Tire film could alternatively be made via blown film extrusion where the molten extrudate is pushed through an annular die, often with cooling air forced through the center of the film tube, often without any cooling rolls being present. Some degree of pre -stretching can occur during the blow n film extrusion process.

[0019] Besides extrusion, films suitable for use in this disclosure could also be made via a calendering process. This method is preferred for amorphous films but not preferred for crystalline or semicrystalline polymers w ithout the use of additives or modifiers to slow or prevent the crystallization induced during the process.

[0020] While a significant portion of the disclosure appears to assume a focus on orienting a monolithic film substrate (to ease readability), occasions arise where a coating or a thin co-extruded cap layer is needed to impart properties to the film’s exterior surfaces. This could include an aqueous silicone coating which can be sprayed, roll-applied, liquid bath or dip-applied, or passed through a doctor blade orsimilar methods to remove excess solution prior to drying. Alternatively, a co-extruded cap layer containing denest additives which alter intimate film to film surface contact, or alter the coefficient of friction and diminish film to film surface blocking, or ultra-violet inhibitors or absorbers to slow weathering in exterior environments, etc., can also be applied. While the residual silicone coating is much thinner, the co-extruded cap layers are typically 0.002 to 0.004 inches thick and are located on one or both exterior surfaces. This disclosure includes film or sheet configurations that arc cither monolithic or contain one, two or multiple cap layers or coatings.

[0021] Besides monolithic substrates, or those with thin, co-extruded cap layers, another alternative film suitable for the current disclosure is micro-layered film. This film usually contains 50 to over 1000 discrete but alternating layers of at least two different materials, often where at least one of the layers is made from a semi-crystalline resin. To better understand the referenced micro-layer film, one of its manufacturing methods are herein described. The microlayer film is made with a main extruder and a co-extruder to fonn an ’AB" molten polymer layer, each with layer thicknesses X and Y, respectively, where layers A and B contain different polymer chemistries or intrinsic viscosities. After encountering the first multiplier unit, tire initial AB layer becomes an AB AB layer with relative thicknesses of 0.5*X and 0.5*Y, respectively. Tire ABAB, four-layer molten stream then encounters another multiplier unit whereupon an eight-layer molten stream is formed. This procedure is repeated with multiple multiplier units placed in series until the desired film microlayer thickness is achieved. The multi-layered molten stream then traverses through an optional coat hanger die with a three-roll cooling roll stack, similar to the monolithic substrate previously described. For additional infonnation regarding the manufacture and use of a micro-layer film, refer to PCT App. No. PCT / US2024 / 032032.

[0022] Once the film is produced, it next needs to be oriented to impart the desired shrinking characteristics. The methods of orientation suitable for certain aspects of this disclosure include both in-line and off-line or secondary processes. In-line orientation methods include traditional machine -direction orientation (MDO), transverse-direction orientation (TDO), diagonal-direction orientation (DDO), combinations thereof being orientation in both directions (bi-axially oriented film). These same in-lineorientation methods can alternatively be used off-line, post-extrusion in a different time and place as extrusion. Other secondary processes involve batch-type stretching or tenter frames. In embodiments, the practitioner need not extrude the film himself but can alternatively purchase or otherwise acquire film and perform the stretching themselves.

[0023] While stretching tire film normally occurs at a temperature set point that is about 10 to 15 degrees Celsius higher than the material’s glass transition temperature (Tg), embodiments include stretching at temperatures beyond this traditional range (e.g., up to 100 degrees Celcius above the Tg). Higher temperatures are optionally needed for the thickest of film. This can be due to limited heat transfer to the center of the film (large temperature gradient from the surface to the center of the film) on thick substrates and also due to limitations with torque equipment or side grip / clamp limitations during stretching. As such, the film according to tire current disclosure can commonly have film thicknesses for clear, rigid packaging (post-stretching in some embodiments and post-stretching then post-shrinking in other embodiments) of 0.002 inches to 0.060 inches (about 0.05 mm to about 1.5 mm) but more typically 0.010 inches to 0.040 inches (about 0.25 mm to about 1.0 mm). Because tire stretching process thins the film, initial or pre-stretched sheet thicknesses in some embodiments are as high as 0.236 inches (about 6 mm), but average 0.015 to 0.118 inches (about 0.038 mm to about 3 mm). Past stretching processes, including those used for decorative labels for bottles, were applicable only to relatively thin films (starting — prestretched — thickness of less than 0.4 mm, and often less than 0.2 mm). Accordingly, such stretching processes could not both adequately stretch the sheet and achieve the desired thickness for packaging. For example, the starting thickness might be from 0.20 mm to 0.35 mm and have a final thickness of about 0.03 mm to 0.12 mm, which is thinner than desired for some medical packaging designs. Advantageously, the processes of this disclosure can be applied to pre-stretch sheets of 0.5 inches (about 12.7 mm) or less. For example, the sheets can be from 0.01 inches to 0.50 inches (about 0.25 mm to 12.7 mm). For example, the sheets can have a starting thickness (pre-stretch) of from 0.7 mm to 6.0 mm, or from 1.0 to 6.0 mm, or from 0.7 mm to 3.0 mm or from 1.0 to 3.0 mm. Tire post stretch thickness of such films under the current disclosure could be, for example, 0.2 mm to 2.0 mm. In embodiments, the preferred thickness range isabout 0.03 mm to 0.2 mm. Certain uncommon devices could need final package thicknesses post-stretch thicknesses above or below this range, but the range covers a maj ority of packages in common use . It should be noted that the stretching or orientation process is almost additive when comparing a film stretched in one direction versus two directional or bi-axial stretching. For example, a film stretched 1.65 times in one direction then stretched 1.65 times in a second, planar direction approximates some film properties of a uniaxial film stretched at 2.7 times its starting length. Concerning post-shrinkage processing, the film is expected to regain some portion of its initial or pre-stretched thickness, but the thickness recovery will not quite approach 100% due to hysteresis losses and extensions beyond the yield point in some embodiments.

[0024] In embodiments, a practitioner of film orientation will expect the film to become thinner as it is stretched. Similarly, as a film is stretched in one direction, using the MDO process as an example, the film will also neck down or become narrower versus its initial width. Lastly, oriented crystallization also has a densification effect upon the overall film density. Results have shown that orienting the film is approximately divided equally amongst these three mechanisms. Therefore, as an example, a film that is stretched 1.65 times on a MDO line with an initial starting thickness of 0.065 inches and 24 inches wide necks down to 19.5 inches wide and the film thickness becomes about 0.053 inches. Roughly a third of the initial film volume involves thinning, a third involves width narrowing and a third is lost due to crystallization and planar densification. While one might expect an initial starting thickness of 0.065 inches, stretched at 1.65 times, to become 0.039 inches thick from linear mathematical calculations, this is not always the case in embodiments.

[0025] In embodiments, it is a preferred practice to avoid heat setting the film immediately poststretching. Heat setting would relax the film, thereby reducing or eliminating the desired shrinking characteristics. In other embodiments, the film shrinking characteristics diminish overtime through natural physical aging or stress relaxation via molecular chain mobility. This mechanism often requires a stated shelflife for optimal film shrinkage performance. Physical aging can be directionally slowed by a plurality of methods: minimizing the ambient temperature, reducing the relative humidity and by starting with a polymer with directionally longer chain length (higher inherent or intrinsic viscosity). Similarly, inembodiments, semi-crystalline polymers are preferred over amorphous polymers since the small spherulites that are induced upon stretching tend to better lock in the shrinkage properties or slow physical aging at a measurably slower rate than their amorphous counterparts, a desirable feature in many applications.

[0026] After stretching, the film is then cut bent to form a circumferentially-closed shape often called a shrink tube or shrink sleeve. For example, the film can be rolled to fomi a cylindrical shape. Hie film could optionally be creased, longitudinally or otherwise, in one or more locations to form a shape other than cylindrical which still falls within the spirit and intent of the current disclosure. Similarly, it could be folded on itself with edge sealing to form a pouch. While not limiting, a partial list of other shapes includes ellipsoidal, rhombohedron, rhombic hexahedron, triangular prism or tetrahedron, conic, cuboidal, spheric, three-dimensional saddle points, hyperbolic paraboloids, elliptic hyperboloids, parallel piped, trapezoidal prism, etc. The cylindrical shape optionally has a slight overlap of the two adjoining film layers. When sealed, this slight overlap of tire two edges forms a lap seal. Proper sealing methods can include, but are not limited to. heat seals (heated bar seals, impulse seals, RF welding seals, dielectric seals, laser seals, vibrational seals, friction seals, induction seals, conduction-based seals, radiative seals, etc ), adhesive seals (heat activated, solvent activated, pressure sensitive, air cured, UV cured, visible light cured, IR cured, tw o- part or multicomponent cured, tapes, double-side tapes, VHB tapes, etc.) and solvent bonding seals (solvents containing dissolved polymers, plasticizers and sole solvent or solvent mixtures, especially where the Hansen or Hildebrand solubility parameter and / or vapor pressure is matched to the film being bonded within a range of about + / - 2). In embodiments, other sealing methods are also appropriate for temporarily or permanently joining the two surfaces.

[0027] In embodiments, a shrink sleeve is fonned w ith two open ends. In other embodiments, one sleeve end can be sealed concurrently with the lap seal previously described so the resulting sleeve possesses only one open end which is needed for insertion of the packageable item, similar to a toothpaste tube shape. In other embodiments, a semi -permeable membrane or layer can be inserted (or even coextruded or in-line laminated at extrusion) between one or more sealing surfaces to optimize selective permeability for more efficient sterilization processing w here ethylene oxide, as a single but non-restrictiveexample, is required to penetrate the package interior to achieve sterility of the packageable item. A suitable definition in this scenario for ‘"permeable” is a non-zero migratory test result for any gas. vapor or liquid. In embodiments, tire permeable layer is of the same chemistry’ as the shrink tube package, thus enhancing recyclability. As such, open or closed cell foamed, or micro-voided layers are appropriate. Note that foamed structures often result from either a physical blowing process during extrusion or a chemical blowing agent. In contrast, micro-voided layers often result from intentional polymeric mis-matchcd blends where the stretching process creates the desired micro-voided features, especially when the film is stretched beyond the yield point for one or more polymers in the film. Further, the micro-voided features could also be formed from a two or more poly meric blend where a water soluble (or other solvent based system) is used to dissolve and extract a portion of the film, causing voids.

[0028] The next step in the process is to insert the packageable item into the sleeve. This can be perfonned exactly as described, or an optional bag (or liner, typically clear) can be used between the packageable item and the shrink sleeve. Further, optional inserts may be used with the packageable item. The inserts can be cushioning supports, such as elastomeric inserts, optionally a thermoplastic polyurethane, and can be used in strategic locations, often where a sharp comer or protrusion on the packageable item touches the package, to further reduce rubbing between the packageable item and tire package which causes scratching. In other embodiments, the inserts are supporting stands. Thus, the packageable item is optionally? placed on a supporting stand which often contacts the packageable item in one, two or more locations. This stand separates the packageable item from the shrink sleeve sides or walls, somewhat elevating the packageable in the package, which transfers the force from undesirable impacts to the supporting stand, thereby enhancing protection of the packageable item. In embodiments, the supporting stand is of the same chemistry as the shrink sleeve to improve recyclability. In other embodiments, the supporting stand is made from a material which intentionally absorbs energy from undesirable impacts. Tire supporting stand can be made with foamed or micro-voided features, improving impact resistance, as previously described. The stand can also contain additives often called impact modifiers which optionally possess a glass transition temperature below common room or ambient temperatures. In otherembodiments, the package content can be liquids or liquids with solid content, instead of a rigid device or rigid item. The liquids or liquids with solid content can be injected, pumped or poured into the pouches.

[0029] In embodiments, one sealed edge can include methods of the quick-opening and optionally reclosable variety. Non-limiting examples include zippers, snaps, zip-lock, hook and loop, mushroom (of the “Velcro" type), taped, glued (adhesive), resealable opening, cap and closure sealing, and tear-opening mechanisms often with loop or tab starting mechanisms.

[0030] Tire next step in the process is to seal the end from which the packageable item was inserted, then shrink the sleeve around the packageable item, thereby securing it in place, preferably without the use of a mold in some embodiments. As illustrated in FIG. 1, a three-dimensional article 10 is shown having the sleeve, which is outer clear packaging 12. Sleeve 12 has been formed by folding a film on itself, thus it has heat sealed centerline 14. Three-dimensional article 10 has packageable item 16 already inserted into sleeve 12. In FIG. 1, packageable item 16 is a medical device which requires sterilization for use in operating rooms. Ends 18 and 20 are heat sealed so that packageable item 16 encased within sleeve 12. Additionally, inserts 22. which may be cushioning supports or stands as described above, are illustrated within sleeve 12 and around portions of packageable item 16.

[0031] Next the sleeve can be shrunk by heat shrinking or similar. While any sleeve will have a set maximum shrinking depending on the polymer used and its treatment, as are known in the art, The sleeve will not always be shrunk to the maximum shrinking but should be shrunk sufficiently to remove a majority of the shrinkage properties. As will be realized from this disclosure, once a shrink polymer has been shrunk, heating the material a second time will not typically cause it to shrink further. Thus, in accordance with tire below discussion, the sleeve should undergo sufficient heat shrinking conditions to prevent further shrinkage on reheating (that is “shrunk sufficiently to remove a majority of the shrinkage properties"). In some cases, such as medical device packaging, the sleeve can be shrunk sufficiently to firmly encase the medical device, as is illustrated in FIG. 2. For example, the sleeve may shrink from 10% to 50% of its original size. In other cases, such as illustrated in FIG. 3, a food item 24 may require very little shrinkage. For example, the sleeve may shrink from 1 to 5% of its original size. In FIG. 3, note thedrawing shows the clear package with some shading drawn to better highlight the three-dimensional character of the package. Despite the slight shading, the package is clear in some embodiments.

[0032] For commercial operations, the shrink sleeve’s skin temperature minus the shrink sleeve’s glass transition temperature must be about zero or a positive number for tire sleeve to shrink. However, there can be some shrinkage when the sleeve is at a temperature as low as about 8° C below tire glass transition temperature of the thermoplastic making up the sleeve. To explain the phenomenon, an unstressed or annealed pellet, film or plastic substrate usually begins molecular mobility at the glass transition temperature. However, internal stresses initiate molecular mobility below the glass transition temperature, allowing polymer chains to slide past one another. This is analogous to the heat distortion temperature (aka, the deflection temperature under load) for plastic where 66 psi (0.455 MPa) or 264 psi (1.82 MPa) external forces cause a pre -determined amount of flexural bending at temperature below the material’s glass transition temperature (see ASTM D648). In the present art, internal film stresses from the orientation process allows some shrinkage below Tg. More typically, there can be some shrinkage at temperatures of about 4° C below the glass transition temperature; however, shrinkage for the described thermoplastic will occur at the glass transition temperature or at higher than the glass transition temperature . This is most often accomplished by heating the shrink sleeve. While heated, “dry” tunnels, like enclosed, heated conveyors can be used to shrink the form-fitting sleeve, steam tunnels can also be used. Other heating methods, including but not all inclusive, could alternatively involve infrared heating, induction heating, radiative heating, conductive heating, dielectric heating, convective heating, etc., are all within the scope of the current disclosure. In embodiments, besides heating the shrink sleeve, an alternative method to shrink the sleeve is to expose the sleeve to a plasticizing chemical in vapor, aerosol, liquid, wiped, dipped, etc., form. While not being bound by theory, the plasticizing chemical temporarily depresses the shrink sleeve’s glass transition temperature below the shrink sleeve's skin temperature, allowing shrinkage to occur. In embodiments, the plasticizing chemical can be of a chemical composition that also sterilizes the packageable item and entire package. Note that the shrink sleeve process is much less expensive and faster than other forming processes wherein an expensive and time-consuming mold design is utilized.

[0033] In some embodiments, the next optional step in the process is to heat set tire package postshrinkage. This step is most commonly employed when the shrink sleeve has been made from a semicrystalline polymer. The stretching step previously mentioned forms high-temperature spherulites or small crystals which impart desirable properties beyond its amorphous morphology. The optional heat setting step completes the crystallization process and provides additional package stability in high temperature environments, including steam sterilization, while relieving part internal stresses. In other embodiments, it is preferred to sterilize or heat treat post-shrunk sleeves above the material’s glass transition temperature in order to reset the package age, preferably to zero age, thereby optimizing impact properties. Note that with amorphous shrink sleeves, the sterilization or heat treatment above it’s Tg cannot be sustained ’‘too long” or gravity could cause sleeve sections to excessively droop and warp. “Too long” cannot accurately be described without an equation since it is a function of sleeve thickness, the amount of heat treatment applied above the material’s Tg. the presence of moisture, and the residence time of heating. As general guidance, a 0.030-inch-thick sleeve, made from amorphous PETG, treated at 220 degrees Fahrenheit for 10 minutes would likely cause an excessive amount of sleeve drooping and warpage for some applications. Similarly, a 0.030-inch-thick sleeve, made from amorphous PETG, treated at 270 degrees Fahrenheit for 5 minutes would also likely cause an excessive amount of sleeve drooping and warpage. In contrast, a clear sleeve made from APET under either scenario would still retain its shape due to its crystallinity and now higher temperature resistance. In embodiments, heat setting of a semi-crystalline sleeve could occur simultaneously with a sterilization process at elevated temperatures, thereby improving process efficiency or providing additional security through additional, though unintended, sterilization. For additional information regarding the manufacture and use of semi-crystalline films for higher heat stability applications, refer to PCT App. No. PCT / US2024 / 032059.

[0034] The next step in the process is sterilization of the package and its contents which will be discussed in detail elsewhere in the disclosure.

[0035] In some embodiments, the completed article will comprise only the sleeve packaging and the packageable item. However, it will be understood that some items may be in a bag before being placedin the sleeve; thus, the bag is around the item, and both are inside the clear packaging formed from the sleeve. Further, in some embodiments the article may be placed inside a container, such as a cardboard box, and may be on a stand within the box to suspend the device between the inner surfaces of the box. For food, the food is in the clear package which might have a label affixed or the clear package might be put into a cardboard box or similar container with the container having labeling and instructions.

[0036] Tire next step involves methods to open the package. For example, a medical device package would typically be opened in the operating room. A plurality of methods are suitable to open the package, and some non-restrictive methods and embodiments include cutting the package open with scissors, shears, or other cutting blades or devices with optional heated blades. In other embodiments, a package seam can be opened by peeling apart the seam, especially when adhesive substances, heat or pressure activated, were used. In other cases, hook and loop or plastic zipper (“zip-lock”) closures are permitted, as are score-n-snap and tear strip methods, with or without full or partial perforations, threaded or push to seal mating or interlocking tabs and surfaces. A package can also be preferentially weakened in areas to more easily open the package by use of cold temperatures or chemical attack, or combinations of all of these methods.

[0037] Concerning materials suitable for the current disclosure, clear, rigid medical packaging is most often made from an amorphous polyester that has been modified in the polymerization reactor by the resin supplier such that it is no longer crystallizable. The most common version of this amorphous polyester is glycol-modified copolyester (PETG). PETG thermoforms well and has sufficient free volume engineered into its morphology such that it generally retains its strength and clarity after sterilization processes. These sterilization procedures include ethylene oxide and gamma radiation, amongst others, where the elevated temperature during sterilization must remain below the material’s glass transition point or package shrinkage and warpage, among other detrimental effects, result. While PETG is a suitable material for some embodiments, PETG cannot be steam sterilized since warping and subsequent package failure from a probable loss in sterility begins to occur near PETG’s glass transition temperature of approximately 80- degrees Celsius.

[0038] To keep the cost of rigid packaging to a minimum, or to tout improved recyclability, certain extrusion companies offer lower-cost alternatives to PETG, such as thermoformable film made from polyester (PET) or amorphous PET (APET), which are suitable for some embodiments of tire current disclosure. While the semantics for these materials can be confusing, PET and APET are chemically very close in composition to one another. While the acronym implies a homopolymer, PET often contains between approximately 1 to 2.5% modifier, where the modifier is most often isophthalic acid (IP A). APET historically contains slightly more modifier than PET at approximately 2.5 to 4.5% modifier content on a molar basis. Similarly, in an effort to better codify the chemistry of PET suitable for the stream 1 PET recycle industry (RIC#1, resin identification code for polyesters), the state of California limited the composition of PET or APET as a polyester containing a maximum of 10% ‘'other” modifier beyond the terephthalic acid and ethylene glycol base monomers used to make PET. The higher level of 1PA modifier, or other monomer modifiers, in APET slows the rate of crystallization. PET can be extruded up to approximately 0.075 inches thick and remain clear whereas APET can be extruded up to a maximum of about 0.150” where the cooling capacity of certain extrusion lines alter the final thickness available from these chemistries. Beyond this thickness, the residual heat from the extrusion process cannot be removed from the extrudate sheet quickly enough, leading to the generation of cry stallization. Thermally-induced crystallization usually contains relatively large-sized cr stals, which, when present in film, leads to the generation of haze. For practical purposes, an average cry stal size larger than the wavelength of visible light leads to haze. Fully crystallized sheet results in turning the sheet from clear (in its amorphous morphological state) to opaque white in the fully crystallized state. PET sheet extruded below 0.060 inches and quenched quickly is amorphous, clear, and begins to distort at approximately 80 degrees Celsius (the glass transition point for PET). In contrast, PET sheet that has been thermally cry stallized (which is hazy, even to the point of being opaque white) no longer softens or sags during shrinking at 80 degrees Celsius, but instead, generally retains its stiff shape up to a temperature as high as its melt point of about 245 degrees Celsius for “bottle grade” PET. These approximate values are easily obtained via testing with a PerkinElmer differential scanning calorimeter (DSC) at a scan rate of 20 degrees Celsius per minute and are well-known by those skilled in the art. Since PET and APET are so close in chemical composition and properties, the PET acronym will be used most often for simplicity but generally describes either or both materials to within a close approximation. The crystallization half times suitable for some aspects of the present disclosure are between 5 seconds and 30 minutes (via DSC or SALLS test methods). In contrast, PETG contains multiples of the aforementioned levels of polymer chain modification (comonomer modification, often between 28 to 33% on a molar standpoint on a diol basis) that renders it as being truly amorphous. PETG generally cannot be crystallized, evidenced by the fact that it has been extruded at 1 inch thick while remaining clear. The cry stallization halftime ofPETG is often measured as greater than 10,000 hours, when the test is often terminated. PETG therefore shows a glass transition temperature of about 80 degrees Celsius but no melt point during traditional DSC testing since it essentially amorphous and cannot be crystallized.

[0039] The preceding paragraph describes two morphological states of PET: amorphous and crystalline, where the crystallinity has been initiated or allowed to occur, by thermal means. Other routes, such as chemical or solvent means, can also lead to crystallization. Crystals in PET are often relatively large, leading to haze, opacity and brittleness in articles that have been crystallized. A third or quasi- morphological state can also be obtained. Mechanically stretched or oriented PET leads to small cry stallites, also called pseudo-cry stals or spherulites. These small pseudo-crystals have the effect of retaining clarity (because the pseudo-cry stal size is smaller than the wavelength of light) yet they increase the measured heat distortion temperature to values much above the glass transition temperature of about 80 degrees Celsius because small crystals are present. In addition, the orientation and small pseudo crystals have the added beneficial effect of improving toughness, often well beyond the levels tested with amorphous morphologies. In contrast to PET. when PETG film is oriented, it forms shrink film, generally without the formation of the small pseudo-crystals. Therefore, PETG, either in the oriented or amorphous state, still cannot generally be used in all applications requiring rigid stability above its glass transition temperature of 80 degrees Celsius. This definition of PETG assumes the optimal amount of modifier has been added such that no crystallization is formed during the DSC test. It should be noted that some casual use of the acronym PETGcan, in some instances, refer to modification levels that are not located at the crystallization curve apex and therefore can still be crystallized. This situation would also occur when mixing, for example, 70% PETG with 30% PET, as well as many other ratios, diluting tire modifying diol beyond those levels leading to the most amorphous target.

[0040] Using methods common to those skilled in the art, rigid medical packaging thennofonned today utilize PETG, PET or APET film that all contain amorphous morphology and therefore process similarly with similar characteristics. Specifically, thermoformed trays made today using PETG, PET and APET film are all clear and amorphous and are heated to a surface temperature of about 280 to about 340 degrees Fahrenheit prior to thermoforming into a rigid medical package. Similarly, in embodiments, all of these materials can also be used in shrink packaging. All of these packages made from any of these three substrates would also be clear and retain their shape during sterilization as long as the temperature doesn’t exceed about 80 degrees Celsius. Certain protocols for steam sterilization often specify 121 degrees Celsius as the target temperature. Clear, rigid medical packages made according to today’s methods would not survive this level of steam sterilization. One with limited experience in the art might try to alleviate the aforementioned low heat distortion temperature of PET or APET by thermally crystallizing the packaging after thermoforming. A PET package can therefore be heated while still on the thermoforming mold to crystallize said article. While thermally induced crystallization can occur at a range of times and temperatures, for PET the maximum rate of cry stallization would occur at about 175 to 185 degrees Celsius. After several minutes of heating and subsequent cooling, the resulting article can withstand steam sterilization at 121 degrees Celsius without deformation, but the thermoformed article would no longer be fit-for-use as rigid packaging because it would have become opaque white (no longer visually clear, which is typically a necessary feature for medical packaging) and it would become brittle. For applications such as medical packaging, opaque, brittle packages cannot withstand the various transportation steps between the sterilization facility and tire operating room and would break and lose device sterility. Note that this package construction is analogous to opaque CPET (crystallized PET) food trays.

[0041] Concerning the mechanically stretched or oriented state of PET, when stretched beyond about 2.65 times its original dimensions (for 0.065-inch-thick sheet), an effect, herein called strain hardening, can occur. When strain hardening occurs in PET or other semi-crystalline materials, it becomes more difficult to stretch it farther. Attempts to stretch it slightly farther yield multiple physical property enhancements but significant stretch lengths beyond the strain hardening point often leads to part failure. In embodiments, the present disclosure therefore involves partially stretching the film via mechanical means (in its two-dimensional or flat form) but leaving the capability of the film to be stretched farther. The point of strain hardening is therefore recognized as almost (i.e., ~85% of total elongation) at the approximate upper limit for this novel process. In some embodiments, the upper limit for stretching the crystalline or semi-crystalline substrate is up to the point wherein strain hardening is initiated. In other embodiments, the upper limit for stretching the crystalline or semi-crystalline substrate is beyond the strain hardening initiation region, right up to the elongation at break (right before the full tensile strength is reached). In other embodiments, certain thermoplastic chemistries begin to lose their maximum shrinkage percentage at elongation near or beyond the strain hardening region and must be stretched well below its initiation. In other embodiments, for film thicknesses highlighted in this disclosure, an upper limit for the stretch ratio would be 2.75 or 3.0 times its original length in one or more directions.

[0042] Similar to an upper stretching limit, a lower stretch limit is also involved with embodiments of the present disclosure. As an extreme example, in embodiments, some simple package configurations would only require as little as about 1 to 5% shrinkage to properly package the article, whereas more complex designs might require up to perhaps 70% shrinkage or more. In other embodiments, especially where the formation of small spherulites is required for higher heat applications, the lower limit for stretching is the point where a certain minimum percentage of crystallinity is achieved, as quantified by DSC. This percentage of crystallinity of 8%, or 15%, or 25%, or 35% are required in various embodiments. In embodiments, a stretch ratio as low as about 2.0 is required.

[0043] A film substrate naturally possesses the three dimensions of length, width and height (or thickness). However, for the purpose of the current disclosure, these substrates will be referred to as havingtwo dimensions where the height or thickness of said film has not been altered as made (extruded, calendered, blown, etc.). The planar direction of the film can be expressed herein as the x- and y-directions in Cartesian or Gaussian coordinates and the height or thickness as tire z-direction. The two-dimensional film remains flat as made. In contrast, a three-dimensional film, sheet or article is defined as a two- dimensional film that has been manipulated such that the height of the planar film has been altered in the z- dircction, different from which it was originally made. Manipulation means fomration of and subsequent shrinking of a sleeve where these steps add contours in the z-direction that are at least 10% out-of-plane versus the flat film as initially made.

[0044] In some embodiments of the present disclosure, molten polymeric film and sheet comprise and contain linear or branched polymeric strands that are generally deposited in random orientations when deposited under low to no stress-environments, leading to isotropic properties. These molten films or sheets are quickly quenched to freeze the molecular orientation in tire random state, leading to high clarity in film. Herein the term “quickly quenched"’ refers to cooling the molten polymer to or below its glass transition temperature in a time period that is a small fraction of its crystallization half-time for cry stalline or semicrystalline polymer types. In certain conditions where the film is not quickly quenched, cry stals can fomr from this thermally-activated mechanism which grow to a relatively large size. When the large-sized crystal is larger than the wavelength of visible light (400 to 700 nanometers), visible light is scattered in nonrandomized directions which leads to haze and eventually opacity when the size and quantity of large crystals exist. It is the intention of embodiments of the present disclosure to avoid large crystals leading to haze and possible opacity from crystal sizes larger than about 2000 nanometers, or 1500 nanometers, or 1000 nanometers, or more preferably 700 nanometers or most preferably the crystal sizes are below 400 nanometers. Clarity is best maintained when the size of crystals, crystallites, pseudo-crystals or spherulites are below 400 nanometers. For the purposes of the present art, a crystal is herein defined as non-random polymeric strands with initially high free volume or interstitial pocket void space between the polymer strands which subsequently become more ordered or stacked into smaller areas which have densified to possess less than tire maximum amount of free volume and which now, post crystallization, contain a higherfraction of both dipole and van der Waals force interactions between the adjacent polymer strands, leading to non-linear measurements during DSC testing at constant energy input. These crystals also have a true melt temperature that ishigherthan the glass transition temperature of the randomized, non-oriented sections of the polymer, measurable and quantifiable during DSC testing. In some embodiments, crystallites, pseudo-crystals or spherulites are herein defined as small crystals, less than 700 nanometers in size, that also manifest themselves during DSC testing by affecting non-lincar measurements during DSC testing at constant energy input whereas a completely amorphous or randomized arrangement of polymeric strands do not show a melt point but only a glass transition temperature during the first DSC scan.

[0045] In one embodiment, the crystal size is measured as the radius of the calculated hydrodynamic volume. In other embodiments, since the film can be intentionally stretched where some degree of orientation in the film is generated during film neck-down as the extrudate exits the die. the crystal size is measured as the length of the longest direction according to the crystal’s aspect ratio. In other embodiments, the crystal size is measured as the length of the shortest direction according to the crystal’s aspect ratio. In other embodiments, the crystal size is measured as the average of the dimensions for tire cry stal’s aspect ratio. In other embodiments, the crystal size is limited to a maximum based on tire physical properties of the film. More specifically, physics dictates that a cry stal size is below 400 nanometers when an article remains clear, yet crystals are knoyvn to be present based on the measured heat distortion temperature or testing by differential scanning calorimetry (DSC) and calculating the percentage crystallinity as is a yvell-known procedure by DSC practitioners. In embodiments, the crystallization mechanism mentioned above can also occur due to mechanical forces being induced in a film under certain environmental conditions. These pseudo-crystals, induced by mechanical means tend to be smaller and their size and rate of fomration are more easily controlled via mechanical means than thermal means. When the mechanical force or stretching occurs in one direction, whether that be in-line yvith the extrusion direction, herein defined as machine direction orientation, or across the film web, herein defined as transverse direction orientation, usually leads to anisotropic properties. Tire force to tear the film, for example, will be different when tom in tire general direction of the orientation versus a tear force measured perpendicularto the direction of orientation. Similarly, anisotropic sheet properties often lead to undesirable preferential, directional shrinkage during processing. It is therefore a preferred embodiment of the present disclosure to stretch or orient the film in both the x and y directions in a bi-axial manner to better maintain isotropic properties, of which the tear force and uniform shrinkage during thermoforming previously mentioned are two of many properties thusly affected. In other embodiments, anisotropic sheet properties are preferred to take advantage of directional shrinkage during tire shrinking process.

[0046] It should be noted that steam sterilization is not an obligatory end point for the current disclosure. Articles made from pre-stretched sheet, then shrunk, then heat set leads to an overall tougher product than packages made from amorphous PET or PETG film. Similarly, heat setting is also an optional element for this art. Articles made from pre-stretched sheet, then shrunk, without heat setting also yields to an overall tougher product than packages made from amorphous PET or PETG film. In other words, PET that has been partially or fully oriented generally has higher instrumented impact values than PET or PETG that has not been oriented when tested according to ASTM D3763. Further, the final article in the present art need not be intended exclusively for rigid medical packaging. Any thermofomied article with three- dimensional character focused on any market using pre-stretched sheet is applicable in the current disclosure.

[0047] In embodiments of the current disclosure, the performance of packages exposed to sterilization methods at elevated thermal conditions is improved. This is true for packages exposed to not only steam sterilization but also for sterilization methods not utilizing steam. For example, in ethylene oxide sterilization (EO or ETO), an elevated thermal climate is used with amorphous packages, but the temperature must remain below the material's glass transition temperature to prevent warping. In embodiments of the current disclosure, the presence of the small spherulites enables increased temperatures during ETO sterilization (ie, more severe sterilization protocols) and other sterilization methods which can result in faster sterilization cycle times, higher efficacy post sterilization (fewer sterilization cycles or repeated processing from undesirable biological indicator results) and a tougher part since sterilization above the material’s glass transition temperature leads to reduced or essentially no aging in the amorphousregions between the spherulites. The preceding description focused on PET packages because medicalgrade PET resin tends to be less expensive than medical-grade PETG resin, yet packages made with PET according to the process described herein often result in a package with superior properties when compared to PETG, which has heretofore been recognized as the preferred material for use in clear, thermoformed rigid medical packaging. Oriented film from other semi-crystalline polymers also yields similar or better properties as oriented film from PET but perhaps at a higher raw material price point. Concerning other sterilization methods, the phrase “chemically-activated” sterilization is used and includes, but is not limited to, chlorine dioxide, peroxide, peracetic acid, formaldehyde, glutaraldehyde, ozone, performic, alcohol, supercritical carbon dioxide and nitrogen dioxide, etc. In this context, it is recognized that ethylene oxide is also a “chemically-activated” sterilization method. It has been previously highlighted due to its prevalence in the sterilization industry.

[0048] In embodiments of the current disclosure, packages made from amorphous substrates, such as PETG, polycarbonate, acrylic or polyvinyl chloride, have already experienced intentional shrinkage to secure an item or device. Upon sterilization, it is a preferred embodiment to expose the package to a temperature greater than the glass transition temperature of the amorphous substrate to preferentially erase the physical aging, or polymeric densification, thereby preventing embrittlement from excessive aging. While it is true that some package shrinking and warping can occur, the resulting shape is not undesirable since a mold or otherwise pre -determined shape is not required.

[0049] In embodiments of the present disclosure, the suitable crystalline or semi-crystalline polyesters can be either aromatic or aliphatic in nature and comprise, but are not limited to, polyethylene terephthalate (PET), amorphous polyethylene terephthalate (APET). glycol-modified polyethylene terephthalate (PETG). acid-modified polyethylene terephthalate (PETA), polycyclohexylenedimethylene terephthalate (PCT), glycol-modified polycyclohexylenedimethylene terephthalate (PCTG), acid- modified polycyclohexylenedimethylene terephthalate (PCTA). polyethylene naphthalate (PEN), polypentamethylene naphthalate (PPN), polyethylene furanoate (PEF), polytrimethylenc terephthalate (PTT), polybutylene terephthalate (PBT), polybutylene naphthalate (PBN), polybutylene adipate-co-terephthalate (PBAT), polytrctramcthylcnccyclobutylcnc terephthalate (PCTM), polycyclohexanedimethyl cyclohexanedicarboxylate (PCCD). polycyclohexylene dimethylene cyclohexanedicarboxylate (PCCE, copolyester ether elastomer), polycyclohexanedimethylene-co-isosorbide terephthalate, polylactic acid (PLA), polyhydroxyalkanoates (PHA), polybutylene succinate (PBS), poly (3-hydroxybutylrate-co-3- hydroxyvalerate) (PHBH) and copolymers, isomers and blends thereof.

[0050] In embodiments of the present disclosure, the polymeric composition contains both primary and secondary diol or diacid modifying monomers and additional comonomers, including multi-functional branching monomers, either aromatic or aliphatic in nature, and comprise cyclohexane dimethanol, butanediol, propanediol, neopentyl glycol, spiroglycol, isosorbide, 2,2,4,4-tetramethyl-l,3- cyclobutanediol, diethylene glycol, ethylene glycol, bisphenol A (BPA), branchers (TMA), pentaerythritol or polyethylene glycol (PEG).

[0051] In embodiments of the present disclosure, the diol component of the polyesters in the blends of the disclosure may contain up to 10 mole percent of tire residues of a modifying diol. Examples of modifying diols include propylene glycol, 1,3 -propanediol, 2.4-dimethyl-2-ethylhexane-l,3-diol, 2,2- dimethyl-l,3-propanediol, diethylene glycol, 2-ethyl-2-butyl-l,3-propanediol, 2-ethyl-2-isobutyl-l,3- propanediol, 1,3 -butanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 1,8- octanediol, 2, 2, 4-trimethyl- 1,6-hexanediol, thiodiethanol, 1,2-cyclohexanedimethanol, 1,3- cyclohexanedimethanol, 1,4-cyclohexanedimethanol, p-xylylene glycol, polyethylene glycol, diethylene glycol, polytetramethylene glycol, 2,2,4,4-tetramethyl-l,3-cyclobutanediol, and combinations thereof.

[0052] In embodiments of the present disclosure, one, two, three, or more dicarboxylic acids which may be used with terephthalic acid include phthalic acid, isophthalic acid, furandicarboxylic acid, (FDCA), 1,4-. 1,5-, 2.6-, and 2,7-naphthalenedicarboxylic acid. 1,3-, 1.4-cyclohexanedicarboxylic acid (which maybe cis, trans or a mixture thereof), cyclohexanediacetic acid, trans-4.4'-stilbenedicarboxylic acid, 4,4'- oxydibenzoic acid, 3,3'- and 4,4'-biphenyldicarboxylic acids, malonic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, suberic acid, pimelic acid, nonane, decane, dodecanedicarboxylic acids. The copolyester may be prepared from one or more of the above dicarboxylic acids. It should beunderstood that use of the corresponding acid anhydrides, esters, and acid chlorides of these acids is included in the term "dicarboxylic acid". The "residue" of the dicarboxylic acids described herein is that portion of the diacid which constitutes a portion of a diester of the diacid. The diacid residues may be derived from the dicarboxylic acid, dialkyl esters thereof, e.g., dimethyl terephthalate and bis(2-hydroxyethyl) terephthalate, acid chlorides thereof and. in some cases, anhydrides thereof.

[0053] In embodiments of the present disclosure, rigid medical packaging is desired to have optimal clarity and brightness as measured by the Hunter Lab, ASTM E308, or CIELAB L* value as high as possible. The highest L* values are obtained when utilizing PET resin that contains no reheat aids. Without reheat aids, favorable L* brightness values on 1 mm thick sheet are preferred to measure at least 65, or more preferred at least 75, or most preferred above 85. The reheat aids often used in bottle processing, herein preferably to be avoided, include FesCL, carbon black, reduced antimony, etc. Typically, embodiments of the this disclosure result in articles that have a haze value of less than 10% (or less than 8%) as measured by ASTM D1003 and / or a measured light transmission of greater than 70% (or greater than 75%) as measured by ASTM D1003, and the article retains one or both of these properties even after heating to a temperature above the glass transition temperature but less than tire melt temperature of the thermoplastic polymer from which the article is formed.

[0054] In embodiments of the present disclosure, packaging might also preferably utilize PET with catalyst systems that avoid elements of concern, including heavy metals as listed by CONEG (Coalition of Northeastern Governors), Toxics in Packaging Clearinghouse (TPCH) and elsewhere. Since antimony- based catalysts are most often used in the manufacture of PET resin, instances can be cited where antimony- free PET residues are preferred.

[0055] In embodiments of the present disclosure, the polyamide composition can contain both primary and secondary diamines or diacid modifying monomers and additional comonomers, including multi-functional branching monomers, either aromatic or aliphatic in nature.

[0056] Tire polymer blends of the disclosure may further comprise one or more additives in amounts that do not adversely affect the resulting blend properties. Examples of additives includeantioxidants, melt strength enhancers, chain extenders, flame retardants, fillers, acid scavengers, dyes, colorants, pigments, anti-blocking agents, flow enhancers, impact modifiers, antistatic agents, processing aids, mold-release additives, plasticizers, slip agents, stabilizers, waxes, UV absorbers, optical brighteners, lubricants, pinning additives, foaming agents, nucleators, glass beads, metal spheres, ceramic beads, carbon black, cross-linked polystyrene or acrylic beads, and the like . Colorants, sometimes referred to as toners, may be added to impart a desired neutral hue and / or brightness to the polyester blends. Representative examples of fillers include calcium carbonate, talc, clay, mica, zeolites, nepheline syenite, wollastonite, kaolin, diatomaceous earth, T1O2. NH4CI, silica, calcium oxide, sodium sulfate, calcium sulfate, zinc oxide, and calcium phosphate. Titanium dioxide and other pigments or dyes, may be included. In another embodiment, crystallization seeding is employed utilizing various additives including linear low-density polyethylene or polypropylene additives.

[0057] In embodiments of the present disclosure, the amorphous, crystalline or semi-crystalline polyesters can have an inherent viscosity (IV) ranging from about 0.5 to about 1.3 dL / g. when measured at 25 degrees Celsius using 0.50 grams of polymer per 100 mL of a solvent consisting of 60 weight percent phenol and 40 weight percent tetrachloroethane as generally described in ASTM Method D2857-95.

[0058] The glass transition temperature can be measured by conventional methods. For example, the glass transition temperature of the amorphous, crystalline or semi-crystalline polyesters can be measured according to ASTM D 3418.

[0059] In one aspect of the present disclosure, the branching agent comprises a multifunctional acid or multifunctional alcohol having at least three acid or alcohol groups or a combination of acid and alcohol groups including, but not limited to, trimesic acid, trimellitic acid, trimellitic anhydride, pyromellitic dianhydride, trimethylolpropane, glycerol, pentaerythritol, citric acid, tartaric acid, 3- hydroxyglutaric acid or mixtures thereof. In another aspect the branching agent comprises an epoxide, including, but not limited to, glycidyl methacrylate. In another aspect tire branching agent comprises a dendritic polymer having at least three reactive functional groups such as carboxylic acids, esters, hydroxyl or combinations thereof.

[0060] It has also been found that other clear, thermoplastic polymers can be mechanically oriented and yet are shrinkable when processed according to the methods described in the present disclosure. In addition to polyesters, other suitable polymers include polyamides, polyurethanes, polystyrene, polyvinyl chloride, polycarbonate, polyacrylates (acrylic and block polymers utilizing polyacrylates), polypropylene, polyethylene, cyclic olefin polymers and copolymers (COP / COC), polyarylatcs, polycaprolactonc, polylactic acid (PLA), and copolymers, combinations and blends thereof.

[0061] While the use of recycled material may contain a small percentage of contamination, this contamination has been shown to be of a low amount (less or equal to 2%) such that the required orientation level for packages made according to the current disclosure is often unaffected. Therefore, film and sheet utilizing either virgin-sourced resin or recycled content, or blends thereof, are suitable for the current disclosure.

[0062] In another aspect of the present disclosure, the multi-step process of orienting the package enhances the toughness. Articles made according to the prescribed procedure have higher energy at maximum load values than the amorphous, non-oriented packages when tested according to ASTM D3763 or the Bruceton staircase method. Similarly, up to three times the impact energy has been measured via Gamder Impact testing versus amorphous, non-oriented APET and PETG films of comparable thicknesses.

[0063] In another aspect of the present disclosure, the multi-step process of orienting the package enhances the strength. Articles made according to the prescribed procedure have higher tear force than the amorphous, non-oriented packages when tested according to Elmendorf Tear Resistance testing, ASTM D1922 or Trouser Tear Resistance @ 200 mm / min, ISO 6383-1). Similarly, testing of non-oriented APET sheet exhibited a tensile strength at the yield point of about 8.200 psi whereas oriented APET tested at approximately 25,000 psi, over a 200% improvement.

[0064] In another aspect of the present disclosure, the multi-step process of orienting the package increases the tensile and flexural moduli according to ASTM D638 and ASTM D790, respectively. Specifically, testing of non-oriented APET sheet exhibited a tensile modulus of about 320,000 psi whereas oriented APET tested at approximately 720,000 psi, an improvement of over two times. This feature, whencoupled with the increased toughness, leads to the ability to downgauge the product without sacrificing toughness and package sterility. Downgauging, when utilized, can lead to several improvements such as lower package weight (material and shipping advantages) and faster thermoforming cycle times (lower energy per part produced), all factors enhancing sustainability.

[0065] In another aspect of the present disclosure, the multi-step process of orienting the package slows the vapor transmission rate of various chemical species, vapors and gases, which is often desired. Testing of non-oriented APET sheet exhibited a moisture vapor transmission rate of about 4.0 (g / 100in2»24h) versus 2.0 for tire oriented APET sample. Oxygen Permeability was likewise 13 and 5 (cm3»mil / 100in2»24h»atm), respectively.

[0066] In another aspect of the present disclosure, the multi-step process of orienting the package improves the chemical resistance. While not wishing to be bound by theory, this feature is believed to occur from tire reduced chemical permeability from oriented polymer chains (lower free volume) and an increase in the fraction of impermeable pseudo crystals or spherulites. Such spherulites represent impermeable barriers for which chemical migration, through random diffusion mechanisms, must move around for deeper penetration into said article, often possessing lower free volume with fewer interstitial areas for said chemical molecules to reside (for one method of improvement). Traditional packaging made from amorphous PET or PETG both can experience situations where a damp ethanol cloth, for example, is used to clean the package. In certain situations, this ethanol exposure can cause chemical attack and crazing which may manifest itself as microcracks in the package. These microcracks weaken the package and cause concern for sterility retention. A second method of improvement to chemical resistance is that the maximum percentage of crystallinity has already been attained, some through the orientation process and the remainder through the heat setting process. The chemical attack of crystallizable polyesters often leads to large sized crystals in amorphous sheet, leading to embrittlement. In the present disclosure, the full extent of crystallinity has already been attained so embrittlement from chemical attack is averted. A two-pronged improvement to chemical resistance is therefore the result.

[0067] In another aspect of the present disclosure, the multi-step process of orienting the package improves the Q 10 factor where the package physically ages during sterilization at a slower rate versus nonoriented, amorphous morphologies. Traditional packaging made from amorphous PET or PETG both undergo physical polymeric aging where toughness decreases as densification increases from molecular rearrangement, leading to a decrease in total free volume. One skilled in the art would understand that the propensity for crack propagation, leading to package failure, increases as total free volume decreases. The multi-step stretching process in the current disclosure, leading to pseudo crystals or spherulites, acts similarly to a low-density cross-link, slowing polymer chain rearrangement and thus improved physical aging as measured by ASTM F1980-02 and similar methods. Additionally, it should be noted that densification or physical aging increases as the delta or difference between the “room” temperature and the material's glass transition decreases. The room temperature is herein defined as the environment at which the article or package is maintained. However, physical aging is reset where a package or article’s effective age becomes essentially zero when the room temperature exceeds the material’s glass transition temperature. For those skilled in the art, it would therefore be an optional goal to have a package intentionally exceed its glass transition temperature so that an effective zero age, and therefore the highest attainable toughness, is maintained. However, since amorphous articles also warp and sag under this condition, this process cannot be completed on amorphous PET or PETG since the package would be distorted and ruined. In contrast, under the present art, the oriented and heat set package can experience a temperature above the material’s glass transition temperature because the pseudo crystals or spherulites essentially hold the package shape together with minimal or non-existent warpage. In summary, in one embodiment of the current disclosure, the room temperature is preferred to exceed the material’s glass transition temperature because the amorphous sections of the article or package, surrounding and between the pseudo crystals or spherulites, have an effective age that's reset to zero. Packages made according to the current disclosure have improved Q10 factors and age slower versus their amorphous counterparts because of both the restricted molecular rearrangement and due to the resetting of the effective ago to zero ofthe amorphous sections around the pseudo cr stals or spherulites. Tire Q10 factor for amorphous PET andAPET thermoformed trays for rigid medical packaging has historically been measured at approximately 10. When manufactured according to the methods discussed in the current disclosure, the Q 10 aging factor for these configurations were measurably improved, estimated to be between circa 6 to 8.5 with limited data and mathematical extrapolation.

[0068] In one aspect of the present disclosure, the properties of the resulting article are improved and decay or change overtime more slowly versus articles made in the traditional, non-oriented, amorphous methods. Such properties include the relaxation modulus, the creep modulus, storage modulus, tire reduced storage modulus, creep compliance, reduced creep compliance, loss modulus and complex modulus. One applicable testing equipment is DMA for another embodiment.

[0069] In one aspect of the present disclosure, the properties of the resulting article are improved and decay or change overtime more slowly versus articles made in the traditional, non-oriented, amorphous methods. Such properties include the tensile modulus, tensile force, tensile elongation, tensile stress, and tensile strain.

[0070] In embodiments, the surface hardness (such as Shore A and Shore D durometer measurements) of the resulting article is improved by the elongation then shrinkage aspects of the targeted package.

[0071] In embodiments, the scratch resistance of the resulting article is improved by tire elongation then shrinkage aspects of the targeted package as measured by Taber testing at 25 to 200 cycles with a 500 gram weight and type F wheel. The change in haze is measured by ASTM D 1003.

[0072] In embodiments, the coefficient of friction and propensity to block or denest of the resulting article is improved by the elongation then shrinkage aspects of the targeted package, often negating the need for denest (slip plus antiblock) additives.

[0073] In another aspect of the present disclosure, the multi-step process of orienting the package leads to differences in the degree of polymer chain alignment in different directions. This birefringence is quantifiable by evaluating tire ratio or difference of the refractive index when measured in the film planar vs thickness directions. The significance is that this method might be used by one skilled in the art tocharacterize the properly oriented film or article, wherein a difference of 0.005 of the refractive index as measured in the planar versus thickness direction is determined to be an important threshold.

[0074] In another aspect of the present disclosure, the multi-step process of orienting the package raises the article or package’s temperature stability. Partially orienting or partially stretching the substrate to form tire package can mechanically induce small pseudo-crystals. These small crystallites increase the package’s temperature stability such that the material’s use temperature can and preferably docs exceed the material’s glass transition temperature. Part shrinkage is avoided or reduced when an optional heat setting step is involved. One applicable method for measuring a higher temperature stability is the heat distortion test (ASTM D648). Another applicable test method is the continuous use temperature (or RTI, relative thermal index) that’s often part of the UL yellow card designation using ASTM 746B.

[0075] In one aspect of the current disclosure, traditionally manufactured PET, APET and PETG trays, all of which maintain an amorphous morphology, have been found to fail certain PET recycle flake clumping test methods due to a high degree of agglomeration. When manufactured according to the methods discussed in the current disclosure, the PET and APET packages with small spherulites pass these test methods without agglomerations which otherwise are detrimental to the PET flake recycling process. One such test method is PET-S-08 issued by Tire Association of Plastic Recyclers, when the optional crystallization protocol is not performed.

[0076] Tire above method, its steps, and systems incorporating the method can be better understood by the following prophetic examples, which illustrates the process. Physical experiments have been performed to demonstrate this novel technology. However, such testing has not been completed, and thus, there are gaps in the data sets actually run. Further experiments are still progressing at the time of the filing of this application. To better avoid confusion, all experiments will be described as prophetic whereas partial work has been performed. Where necessary, the prophetic examples are extrapolated from actual experiments carried out; though, the inventors do not assert that the following prophetic examples themselves were caried out in their entirety. The prophetic examples are offered by way of illustration of the process and are not meant to be limiting; rather, the scope is defined by the claims.

[0077] PROPHETIC EXAMPLES

[0078] Example 1 :

[0079] APET recycle flake dries overnight (approximately 24 hours) in a Conair D400 desiccant dryer with -30 degree Celsius dew point at about 62.8 degrees Celsius (145 degrees Fahrenheit). This amorphous flake is from ground sheet of APET clamshell themioformed trays using resin 992 IM by Alpek, so it dries at this low temperature. This dried flake is then extruded into sheet on a 4.5-inch single screw, non-vented, 24: 1 Crown extrusion line at an average film thickness of about 0.065 inches. A straight temperature profile of 276.7 degrees Celsius (530 degrees Fahrenheit) is used with a production rate averaging 380 pounds per hour. The extrudate is deposited onto a three-roll, water-cooled calender stack with downward orientation using chrome rolls with a polished surface finish of about zero microinches Ra when new. Roll temperatures are 18.3 degrees Celsius (65 degrees Fahrenheit). 65.6 degrees Celsius (150 degrees Fahrenheit) and 71.1 degrees Celsius (160 degrees Fahrenheit) from the top to bottom rolls. The cooled film is trimmed to 24 inches wide and continuously rolled onto 6- inch paper / cardboard cores to make a roll with a final diameter of about 22 inches weighing approximately 300 pounds, designated as Sample A. This rolled film is then fed into a bi-axial, two direction stretching machine, available from Parkinson Technologies at a rate of 8 linear feet per minute. The film stretches in the machine direction by various percentages (see Table A) of its original length between rolls of differential speed at a film temperature of approximately 195 degrees Fahrenheit (MDO or machine direction orientation equipment) and is then pulled in the cross or transverse direction in a TDO machine (transverse direction orientation stretching) also by various percentages (see Table A) of its original length at 180, 215 and 225 degrees Fahrenheit in 3 progressive heating zones, respectively, and is trimmed and winds to produce stretched roll stock film. Tire bi-axial stretching thins the film as shown in the table. This film now has shrinkable properties since it was not heat set in tire stretching processes (the relaxation zone on the TDO was turned off).

[0080] Tire various films are then cut, rolled lengthwise and heat sealed along one edge to form a cylindrical shape with open ends. A 12-inch-long medical device is placed on supports about 3 inches fromeach end, being suspended in the middle, to elevate it above its supporting surface by about 1 inch. This device with supports is then placed in the cylindrical sleeve where the supports barely fit inside the sleeve. The entire package is placed in an oven at 400 degrees Fahrenheit for 20 minutes, a process used to simultaneously shrink, heat set, and sterilize the package. Upon removal from the oven and cooling, the collapsed but open ends are heat sealed.Table A

[0081] Concerning the results, after heat treating Sample B, the sample did shrink but it became excessively hazy. While it might be acceptable for some applications, it is generally not suitable for medical packaging where the highest clarity and lowest haze is most desired. Samples C through I all shrank properly and are considered fit for use in medical packaging. In general, Sample G with the highest stretch ratio in both MDO and TDO and the thinnest of all samples had generally the lowest haze value and made a very tough package. For customers who desire a package wall thickness that is thicker than Sample G, they can either choose a different stretch ratio (Samples C through I) or repeat this example but extrude Sample roll A thicker than the initial 0.065-inch thickness. Samples J through K broke in the TDO machine, thereby showing that this gauge, chemistry and stretch ratio combination exceeded the material’s tensile strength at full elongation. To summarize the results of Samples C through I, and specifically targeting SampleG, the resulting package shrinks around the medical device, being separated from the device at the supports, and it remains clear with less than 5% haze despite the high temperature and long exposure time. After shrinking, the film is now thicker than its starting point of 0.009 inches, being 0.011 inches in some areas near the supports versus 0.015 inches in other areas that were allowed to shrink more, getting closer to the device.

[0082] Example 2:

[0083] PETG resin dries for approximately 8 hours in a Conair D400 desiccant dryer with -30 degree Celsius dew point at about 62.8 degrees Celsius (145 degrees Fahrenheit). This resin is then extruded into sheet on a 4.5-inch single screw, non-vented, 24: 1 Crown extrusion line at an average film thickness of about 0.065 inches. A straight temperature profile of 248.8 degrees Celsius (480 degrees Fahrenheit) is used with a production rate averaging 380 pounds per hour. The extrudate is deposited onto a three-roll, water-cooled calender stack with downward orientation using chrome rolls with a polished surface finish of about zero microinches Ra when new. Roll temperatures are 18.3 degrees Celsius (65 degrees Fahrenheit), 65.6 degrees Celsius (150 degrees F ahrenheit) and 71.1 degrees C el sius ( 160 degrees F ahrenheit) from the top to bottom rolls. The cooled film is trimmed to 24 inches wide and continuously rolled onto 6-inch paper / cardboard cores to make a roll with a final diameter of about 22 inches weighing approximately 300 pounds, designated as Sample M. This rolled film is then fed into a bi-axial, two direction stretching machine, available from Parkinson Technologies at a rate of 8 linear feet per minute. The film stretches in the machine direction by 2.5 times its original length between rolls of differential speed at a film temperature of approximately 195 degrees Fahrenheit (MDO or machine direction orientation equipment) and is then pulled in the cross or transverse direction in a TDO machine (transverse direction orientation stretching) also by 2.5 times its original length at180, 215 and 225 degrees Fahrenheit in 3 progressive heating zones, respectively, and is trimmed to about 40 inches wide and winds to produce stretched roll stock film Sample N. The 2.5 by 2.5 bi-axial stretch thins the film down to approximately 0.013 inches thick. This film now has shrinkable properties since it was not heat set in the TDO process (the relaxation zone on tire TDO was turned off).

[0084] The film at 0.013 inches thick is then cut, rolled lengthwise and heat sealed along one edge to form a cylindrical shape with open ends. A 12-inch-long medical device is placed on supports about 3 inches from each end, being suspended in the middle, to elevate it above its supporting surface by about 1 inch. This device with supports is then placed in the cylindrical sleeve where the supports barely fit inside the sleeve. Tire entire package is placed in an oven at 200 degrees Fahrenheit for 1.5 minutes, becoming Sample O. Upon removal from the oven and cooling, the collapsed but open ends are heat sealed. The resulting package shrinks around the medical device, being separated from the device at the supports, and it remains clear with less than 2% haze. After shrinking, the film is now thicker than its starting point of 0.013 inches, being 0.016 inches in some areas near the supports versus 0.020 inches in other areas that were allowed to shrink more, getting closer to the device. Note that the PETG used in this sample is not crystallizable and therefore is not suitable for high temperature thermal climates, unlike Example 1 wherein the APET properly survives 20 minutes at 400 degrees Fahrenheit and remains generally clear.

[0085] Example 3:

[0086] APET resin 992 IM from Alpek dries for approximately 8 hours in a Conair D400 desiccant dryer with -30 degree Celsius dew point at about 148.9 degrees Celsius (300 degrees Fahrenheit). This resin is then extruded into sheet on a 4.5 -inch single screw, non-vented, 24: 1 Crown extrusion line at an average film thickness of about 0.065 inches. A straight temperature profile of 276.7 degrees Celsius (530 degrees Fahrenheit) is used with a production rate averaging 380 pounds per hour. The extrudate is deposited onto a three-roll, water-cooled calender stack with downward orientation using chrome rolls with a polished surface finish of about zero microinches Ra when new. Roll temperatures are 18.3 degrees Celsius (65degrees Fahrenheit), 65.6 degrees Celsius (150 degrees Fahrenheit) and 71.1 degrees Celsius (160 degrees Fahrenheit) from the top to bottom rolls. The cooled film is trimmed to 24 inches wide and continuously rolled onto 6-inch paper / cardboard cores to make a roll with a final diameter of about 22 inches weighing approximately 300 pounds, designated as Sample P. This rolled film is then fed into a machine direction orientation (MDO), single direction stretching machine, available from Parkinson Technologies at a rate of 8 linear feet per minute. The film stretches in the machine direction by 3 times its original length between rolls of differential speed at a film temperature of approximately 195 degrees Fahrenheit. It is then trimmed to about 16 inches wide and winds to produce stretched roll stock film becoming Sample Q. This film now has shrinkable properties, generally in one direction, since it was not heat set in the MDO process.

[0087] The film is then cut, rolled lengthwise and heat sealed along one edge to form a cylindrical shape with open ends. A 12-inch-long medical device is placed on supports about 3 inches from each end, being suspended in the middle, to elevate it above its supporting surface by about 1 inch. This device with supports is then placed in the cylindrical sleeve where the supports barely fit inside the sleeve. The entire package is placed in an oven at 400 degrees Fahrenheit for 20 minutes becoming Sample R. Upon removal from the oven and cooling, the collapsed but open ends are heat sealed. Tire resulting package shrinks around the medical device, being separated from the device at the supports, and it remains clear with less than 5% haze. Note that a shrink film with one-directional stretching generally shrinks in one direction, thereby showing a directional preference when wrapped around devices of differing shapes.

[0088] Example 4:

[0089] APET resin 992 IM from Alpek dries for approximately 8 hours in a Conair D400 desiccant dryer with -30 degree Celsius dew point at about 148.9 degrees Celsius (300 degrees Fahrenheit). This resin is then extruded into sheet on a 4.5 -inch single screw, non-vented, 24: 1 Crown extrusion line at an average film thickness of about 0.065 inches. A straight temperature profile of 276.7 degrees Celsius (530 degrees Fahrenheit) is used with a production rate averaging 380 pounds per hour. The extrudate is deposited onto a three-roll, water-cooled calender stack with downward orientation using chrome rolls with a polished surface finish of about zero microinches Ra when new. Roll temperatures are 18.3 degrees Celsius (65degrees Fahrenheit), 65.6 degrees Celsius (150 degrees Fahrenheit) and 71.1 degrees Celsius (160 degrees Fahrenheit) from the top to bottom rolls. The cooled film is trimmed to 24 inches wide and continuously rolled onto 6-inch paper / cardboard cores to make a roll with a final diameter of about 22 inches weighing approximately 300 pounds, designated as Sample S. This rolled film is then fed into a transverse direction orientation (TDO), single direction stretching machine, available from Parkinson Technologies at a rate of 8 linear feet per minute. The film stretches in the cross or transverse direction by 3 times its original length by 3 times its original length at 180, 215 and 225 degrees Fahrenheit in 3 progressive heating zones, respectively, and is trimmed to about 40 inches wide and winds to produce stretched roll stock film Sample T. The 3X single direction stretch thins the film. This film now has shrinkable properties since it was not heat set in the TDO process (the relaxation zone on the TDO was turned off).

[0090] The film is then cut. rolled lengthwise and heat sealed along one edge to form a cylindrical shape with open ends. A 12-inch-long medical device is placed on supports about 3 inches from each end, being suspended in the middle, to elevate it above its supporting surface by about 1 inch. This device with supports is then placed in the cylindrical sleeve where the supports barely fit inside the sleeve. The entire package is placed in an oven at 400 degrees Fahrenheit for 20 minutes becoming Sample U. Upon removal from the oven and cooling, the collapsed but open ends are heat sealed. Tire resulting package shrinks around the medical device, being separated from the device at the supports, and it remains clear with less than 5% haze. Note that a shrink film with one-directional stretching generally shrinks in one direction, thereby showing a directional preference when wrapped around devices of differing shapes.

[0091] Example 5 (comparative):

[0092] PETG Sample N from Example 2 is used. The film at 0.013 inches thick is then cut. rolled lengthwise and heat sealed along one edge to fonn a cylindrical shape with open ends. A 12-inch-long medical device is placed on supports about 3 inches from each end, being suspended in the middle, to elevate it above its supporting surface by about 1 inch. Uris device with supports is then placed in the cylindrical sleeve where the supports barely fit inside the sleeve. The entire package is placed in an oven at 400 degrees Fahrenheit for 20 minutes, becoming Sample V. Upon removal from the oven and cooling,the sample is considered a failure because the 400 degree Fahrenheit for 20 minutes conditions were too excessive for PETG resin, causing the film to warp too badly to be considered fit-for-use. Note that the PETG used in this sample is not crystallizable and therefore is not suitable for high temperature thermal climates, unlike Example 1 wherein the APET properly survives 20 minutes at 400 degrees Fahrenheit and remains generally clear.

[0093] The processes and articles of this disclosure can be further understood from the following numbered cases.

[0094] Case 1 : A process for producing a three-dimensional article having an outer clear packaging, said process comprising:(a) heating a thermoplastic film comprising a thermoplastic having an average thickness of at least 0.005 inches but not more than 0.500 inches:(b) stretching the thermoplastic film from 1.5 to 7 times its original dimension in at least one direction without heat setting to generate and maintain the desired film shrinkage properties;(c) bending then sealing the thus resulting stretched film to form a circumferentially-closed shape with overlapping edges forming a first open end and a second open end, optionally the circumferentially-closed shape is a cylindrical shape;(d) sealing the first open end to form a shrinkable sleeve with the second open end;(e) inserting a packageable item into the circumferentially -closed shape to form a package, optionally resting on a supporting stand, optionally, the packageable item is a medical device, a solid food item, a liquid food item or a liquid food item with solids;(f) sealing the second open end to form a closed package;(g) heating the package to a temperature that is 8° C below the glass transition temperature of the thermoplastic or higher to shrink the film around tire packageable item, and optionally the supporting stand, to thus secure the packageable item in a tight mannerand form said three-dimensional article; and(i) optionally sterilizing the three-dimensional article or applying an elevated thermal climate for heat-setting and / or sterilizing said three-dimensional article wherein the three-dimensional article can withstand long-term exposure to tire elevated thermal climate, which is at least equal to the glass transition temperature of the thennoplastic, up to the melt temperature of the thennoplastic, wherein the three-dimensional article, post applying the elevated thermal climate, maintains an average haze of less than 10% (as measured by ASTM D1003) or an average light transmission of greater than 70% (as measured by ASTM DI 003).

[0095] Case 2: The process of case 1, wherein the thermoplastic film is made from an amorphous polymer.

[0096] Case 3: The process of case 1, wherein the thermoplastic film is made from a crystalline or semi-crystalline polymer.

[0097] Case 4: The process of any of cases 1, 2 or 3, wherein the thermoplastic film is made from a many layered film wherein at least one layer is made from a crystalline or semicrystalline polymer.

[0098] Case 5: The process of any proceeding case, wherein the stretching in step(b) is performed in a bi-axial manner;

[0099] Case 6: The process of any proceeding case, wherein the stretching occurs at the glass transition temperature of the thermoplastic plus 5 degrees Celsius up to, but not to exceed, the glass transition temperature plus 100 degrees Celsius.Case 7: The process of any preceding case, wherein the packageable item rests on a stand which suspends the packageable item between surfaces of the clear packaging.Case 8: The process of case 7, wherein the stand is made of a material that absorbsenergy, further protecting the device from undesirable impacts.

[0100] Case 9: The process of any proceeding case, wherein the device with stand is placed in a thin bag or liner prior to being placed in the circumferentially closed shape.

[0101] Case 10: The process of any proceeding case, wherein strategic locations on the packageable item have a pre-positioned thermoplastic elastomeric film, optionally polyurethane film, insert to prevent the device from rubbing and scratching the packaging.

[0102] Case 11 : The process of any proceeding case, wherein the heating which causes film shrinkage is due to a “dry” heated tunnel.

[0103] Case 12: The process of any of cases 1 to 11, wherein the heating which causes film shrinkage is due to steam.

[0104] Case 13: The process of any proceeding case, wherein the heating which causes film shrinkage omits use of a mold.

[0105] Case 14: The process of any proceeding case, wherein the elevated thermal climate is achieved via steam sterilization that occurs from 101 to 221 degrees Celsius (215 to 430 degrees Fahrenheit) for at least 5 seconds.

[0106] Case 15: The process of any proceeding case, wherein the elevated thermal climate is achieved via sterilization.

[0107] Case 16: The process of any of cases 1 to 13, wherein the sterilization is ethylene oxide, gamma, e-beam or chemically-activated sterilization.

[0108] Case 17: A three-dimensional article having an outer clear packaging, the clear packaging comprising a thermoplastic shrink film with a crystallization half time of at least one minute that has been shrunk around a packageable item, removing a majority of the shrinkage properties, optionally including an impact-absorbing stand, and optionally including a linerpositioned between the device and the thermoplastic shrink film.

[0109] Case 18: The article of claim 17, wherein the clear packaging is produced from a thermoplastic that can withstand long-term exposure to an elevated thermal climate that is at least equal to the glass transition temperature of the thermoplastic up to the melt temperature of the thermoplastic, and wherein the clear packaging, post thermal climate exposure, maintains an average haze of less than 10% (as measured by ASTM D1003) or an average light transmission of greater than 70% (as measured by ASTM DI 003).

[0110] Case 19: The article of case 18, wherein crystallization is present in the thermoplastic shrink fdm with a spherulite size of less than 700 nanometers.[OHl] Case 20: The article of either case 18 or 19, wherein the crystallinity of the thermoplastic shrink fdm is at least 8% as measured by DSC, SALLS or XRD.

[0112] Case 21 : The article of any of cases 18, 19 or 20, wherein the crystallinity percentage of the thermoplastic shrink fdm does not exceed 30%.

[0113] Case 22: The article of any of cases 17 to 21, wherein the clear packaging of the three-dimensional article has a birefringence or refractive index difference of greater than 0.005 when measured along the plane of the fdm in the stretched direction versus the non-stretched direction.

[0114] Case 23: The article of cases 17 to 21, wherein the clear packaging of the three-dimensional article has a birefringence or refractive index difference of greater than 0.005 when measured along the plane of the fdm in the stretched direction versus the measurement taken through the fdm thickness direction.

[0115] Case 24: The article of any of cases 17 to 23, wherein the thermoplastic shrink fdm comprises a thermoplastic selected from the group consisting of aromatic or aliphatic versionsof polyesters, polyamides, polyurethanes, polystyrene, polypropylene, polyethylene, polyvinyl chloride, polycarbonate, polyacrylates (acrylic and block polymers utilizing polyacrylates), cyclic olefin polymers and copolymers (COP / COC), polyarylates (PAR), Polycaprolactone (PCL), Polylactic acid (PLA), and copolymers, combinations and blends thereof.

[0116] Case 25: The article of case 24, wherein the thermoplastic shrink film consist essentially of a polyester and the polyester can be either aromatic or aliphatic in nature and is selected from the group consisting of polyethylene terephthalate (PET), amorphous polyethylene terephthalate (APET), glycol-modified polyethylene terephthalate (PETG), acid-modified polyethylene terephthalate (PETA), Polycyclohexylenedimethylene terephthalate (PCT), glycol- modified Polycyclohexylenedimethylene terephthalate (PCTG), acid-modified Polycyclohexylenedimethylene terephthalate (PCTA), polyethylene naphthalate (PEN), polypentamethylene naphthalate (PPN). polyethylene furanoate (PEF), Polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT), Polybutylene Naphthalate (PBN), Polybutylene adipate-co-terephthalate (PBAT, Polytretramethylenecyclobutylene terephthalate (PCTM), Polycyclohexanedimethyl cyclohexanedicarboxylate (PCCD), Polycyclohexylene dimethylene cyclohexanedicarboxylate copolymer (PCCE, copolyester ether elastomer), Polycyclohexanedimethylene-co-isosorbide terephthalate, polyhydroxyalkanoates (PHA), polybutylene succinate (PBS), poly (3-hydroxybutylrate-co-3-hydroxyvalerate) (PHBH) and copolymers, isomers and blends thereof.

[0117] The article of case 25, wherein the polyester is formed from monomers selected from the group consisting of propylene glycol, 1,3 -propanediol, 2,4-dimethyl-2-ethylhexane-l,3- diol, 2, 2-dimethyl- 1,3 -propanediol, diethylene glycol, 2-ethyl-2-butyl-l,3-propanediol, 2-ethyl-2- isobutyl-l,3-propanediol, 1,3 -butanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 1 ,8-octanediol, 2,2,4-trimethyl-l,6-hexanediol, thiodi ethanol, 1 ,2- cyclohexanedimethanol, 1,3 -cyclohexanedimethanol, 1,4-cyclohexanedimethanol, p-xylylene glycol, polyethylene glycol, diethylene glycol, polytetramethylene glycol, 2,2,4,4-tetramethyl-l,3- cyclobutanediol, phthalic acid, isophthalic acid, furandicarboxylic acid, 1,4-, 1,5-, 2,6-, and 2,7- naphthalenedicarboxylic acid, 1,3-, 1,4-cyclohexanedicarboxylic acid (which may be cis, trans or a mixture thereof), cyclohexanediacetic acid, trans-4,4'-stilbenedicarboxylic acid, 4,4'- oxydibenzoic acid, 3,3'- and 4,4'-biphenyldicarboxylic acids, malonic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, suberic acid, pimelic acid, nonane, decane, dodecanedicarboxylic acids, cyclohexane dimethanol, butanediol, propanediol, neopentyl glycol, spiroglycol, isosorbide, 2, 2, 4, 4 - tetramethyl-l,3-cyclobutanediol, diethylene glycol, ethylene glycol, bisphenol A (BP A), pentaerythritol and polyethylene glycol (PEG), and combinations thereof.

[0118] Case 27: The article of any of cases 17 to 26, wherein the clear packaging is made from a hygroscopic polymeric material with a minimum moisture regain of at least 0.05%.

[0119] In this disclosure, the word “set point” has been used to signify a targeted range of specific conditions to properly process the substrate. For example, PET is often properly stretched at about 10 to 15 degrees Celsius above its glass transition temperature. The word “set point” therefore is used to designate the approximate target temperature at which this function should be performed. Using the same example, in one aspect “properly stretched” can refer to a stretch ratio of 1.75. The word “set point” can be used to designate the approximate range of sheet length and / or width extension to achieve a stretch ratio of 1.75. The word “set point” is used with other targeted conditions as well to facilitate targeted sheet properties.

[0120] Therefore, the present compositions and methods are well adapted to attain the ends and advantages mentioned, as well as those inherent therein. The particular examples disclosed above are illustrative only, as the present methods may be modified and practiced in different but equivalent manners apparent to those skilled in the art having the benefit of the teachings herein. Furthermore, no limitations are intended to the details of construction or design herein shown, other than as described in the claims below. It is therefore evident that the particular illustrative examples disclosed above may be altered or modified, and all such variations are considered within the scope and spirit of the present treatment additives and methods. While compositions and methods are described in terms of “comprising,” “containing,” “having,” or “including” various components or steps, the compositions and methods can also, in some examples, “consist essentially of’ or “consist of’ the various components and steps. Whenever a numerical range with a lower limit and an upper limit is disclosed, any number and any included range falling within the range are specifically disclosed. Every range of values (of the form, “from about a to about b,” or, equivalently, “from approximately a to b,” or, equivalently, “from approximately a-b”) disclosed herein is to be understood to set forth every number and range encompassed within the broaderrange of values. Also, the terms in the claims have their plain, ordinary meaning unless otherwise explicitly and clearly defined by the patentee.

Claims

What is claimed is:

1. A process for producing a three-dimensional article having an outer clear packaging, said process comprising:(a) heating a thermoplastic film comprising a thermoplastic having an average thickness of at least 0.005 inches but not more than 0.500 inches;(b) stretching the thermoplastic film or sheet from 1.5 to 7 times its original dimension in at least one direction without heat setting to generate and maintain the desired film shrinkage properties;(c) bending then sealing the thus resulting stretched film to form a circumferentially-closed shape with overlapping edges forming a first open end and a second open end;(d) sealing the first open end to form a shrinkable sleeve with the second open end;(e) inserting a packageable item into the circumferentially-closed shape to form a package;(f) sealing the second open end of the package; and(g) heating the package to a temperature that is 8° C below the glass transition temperature of tire thermoplastic or higher to shrink the film around the device to thus secure the packageable item in a tight manner to fomi said three-dimensional article.

2. The process of claim 1, wherein the thermoplastic film is made from an amorphous polymer.

3. The process of claim 1, wherein the thermoplastic film is made from a crystalline or semi-crystalline polymer.

4. The process of claim 1, wherein the thermoplastic film is made from a many layered film wherein at least one layer is made from a crystalline or semi-crystalline polymer.

5. The process of claim 1, wherein the stretching in step (b) is performed in a bi-axial manner.

6. The process of claim 1, wherein the stretching occurs at the glass transition temperature of the thermoplastic plus 5 degrees Celsius up to, but not to exceed, the glass transition temperature plus 100 degrees Celsius.

7. The process of claim 1, wherein the packageable item rests on a stand which suspends the packageable item between surfaces of the clear packaging.

8. The process of claim 7, wherein the stand is made of a material that absorbs energy, further protecting the device from undesirable impacts.

9. The process of claim 7, further comprising placing the packageable item and stand in a liner prior to step (e) of inserting the packageable item.

10. The process of claim 1, wherein strategic locations on the packageable item have a pre-positioned thermoplastic elastomeric film insert to prevent the device from rubbing and scratching the packaging.

11. The process of claim 1, wherein the heating which causes film shrinkage is due to a “dry” heated tunnel.

12. The process of claim 1, wherein the heating which causes film shrinkage is due to steam.

13. The process of claim 1, wherein the heating which causes film shrinkage omits use of a mold.14 Tire process of any of claims 1 to 13, further comprising applying an elevated thermalclimate for heat-setting and / or sterilizing said three-dimensional article wherein the three-dimensional article can withstand long-term exposure to the elevated thermal climate, which is at least equal to the glass transition temperature of the thermoplastic, up to the melt temperature of the thermoplastic, wherein the three-dimensional article, post applying tire elevated thennal climate, maintains an average haze of less than 10% (as measured by ASTM DI 003) or an average light transmission of greater than 70% (as measured by ASTM DI 003).

15. The process of claim 14, wherein the elevated thermal climate is achieved via steam sterilization that occurs from 101 to 221 degrees Celsius (215 to 430 degrees Fahrenheit) for at least 5 seconds.

16. The process of claim 1, further comprising sterilizing the three-dimensional article by ethylene oxide, gamma, e-beam or chemically-activated sterilization.

17. A three-dimensional article having an outer clear packaging, the clear packaging comprising a thermoplastic shrink fdm with a crystallization half time of at least one minute that has been shrunk around a packageable item, removing a majority of the shrinkage properties.

18. The article of claim 17, wherein the clear packaging is produced from a thermoplastic that can withstand long-term exposure to an elevated thermal climate that is at least equal to the glass transition temperature of the thermoplastic up to the melt temperature of the thermoplastic, wherein the clear packaging, post thermal climate exposure, maintains an average haze of less than 10% (as measured by ASTM DI 003) or an average light transmission of greater than 70% (as measured by ASTM DI 003).

19. The article of claim 18, wherein crystallization is present in the thermoplastic shrink fdm with a spherulite size of less than 700 nanometers.

20. The article of claim 18, wherein crystallinity of the thermoplastic shrink film is at least 8% as measured by DSC, SALLS or XRD.

21. The article of claim 18, wherein crystallinity percentage of the thermoplastic shrink film does not exceed 30%.

22. The article of claim 17, wherein the clear packaging of the clear, three-dimensional article has a birefringence or refractive index difference of greater than 0.005 when measured along the plane of the film or sheet in the stretched direction versus the non-stretched direction.

23. The article of claim 17, wherein the clear packaging of the clear, three-dimensional article has a birefringence or refractive index difference of greater than 0.005 when measured along the plane of the film or sheet in the stretched direction versus the measurement taken through the film or sheet thickness direction.

24. The article of any of claims 17 to 23, wherein the clear, thermoplastic shrink film comprises a thermoplastic selected from the group consisting of aromatic or aliphatic versions of polyesters, polyamides, polyurethanes, polystyrene, polypropylene, polyethylene, polyvinyl chloride, polycarbonate, polyacrylates (acrylic and block polymers utilizing polyacrylates), cyclic olefin polymers and copolymers (COP / COC), polyarylates (PAR), Polycaprolactone (PCL), Polylactic acid (PLA), and copolymers, combinations and blends thereof.

25. The article of claim 24, wherein the thermoplastic shrink film consist essentially of a polyester and the polyester can be either aromatic or aliphatic in nature and is selected from the group consisting of polyethylene terephthalate (PET), amorphous polyethylene terephthalate (APET), glycol-modified polyethylene terephthalate (PETG), acid-modified polyethyleneterephthalate (PETA), Polycyclohexylenedimethylene terephthalate (PCT), glycol-modified Polycyclohexylenedimethylene terephthalate (PCTG), acid-modifiedPolycyclohexylenedimethylene terephthalate (PCTA), polyethylene naphthalate (PEN), polypentamethylene naphthalate (PPN). polyethylene furanoate (PEF), Polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT), Polybutylene Naphthalate (PBN), Polybutylene adipate-co-terephthalate (PBAT), , Polytretramethylenecyclobutylene terephthalate (PCTM), Polycyclohexanedimethyl cyclohexanedicarboxylate (PCCD), Polycyclohexylene dimethylene cyclohexanedicarboxylate copolymer (PCCE, copolyester ether elastomer), Polycyclohexanedimethylene-co-isosorbide terephthalate, polyhydroxyalkanoates (PHA), polybutylene succinate (PBS), poly (3-hydroxybutylrate-co-3-hydroxyvalerate) (PHBH) and copolymers, isomers and blends thereof.

26. The article of claim 25, wherein the polyester is formed from monomers selected from the group consisting of propylene glycol, 1,3-propanediol, 2,4-dimethyl-2-ethylhexane-l,3- diol, 2, 2-dimethyl- 1,3 -propanediol, diethylene glycol, 2-ethyl-2-butyl-l,3-propanediol, 2-ethyl-2- isobutyl-l,3-propanediol, 1,3 -butanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6- hexanediol, 1,8-octanediol, 2,2,4-trimethyl-l,6-hexanediol, thiodi ethanol, 1,2- cyclohexanedimethanol, 1,3 -cyclohexanedimethanol, 1,4-cyclohexanedimethanol, p-xylylene glycol, polyethylene glycol, diethylene glycol, polytetram ethylene glycol, 2,2,4,4-tetramethyl-l,3- cyclobutanediol, phthalic acid, isophthalic acid, furandicarboxylic acid, 1,4-, 1,5-, 2,6-, and 2,7- naphthalenedicarboxylic acid, 1,3-, 1,4-cyclohexanedicarboxylic acid (which may be cis, trans or a mixture thereof), cyclohexanediacetic acid, trans-4,4'-stilbenedicarboxylic acid, 4,4'- oxy dibenzoic acid, 3,3'- and 4,4'-biphenyldicarboxylic acids, malonic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, suberic acid, pimelic acid, nonane, decane,dodecanedicarboxylic acids, cyclohexane dimethanol, butanediol, propanediol, neopentyl glycol, spiroglycol, isosorbide, 2, 2, 4, 4 - tetramethyl-l,3-cyclobutanediol, diethylene glycol, ethylene glycol, bisphenol A (BP A), pentaerythritol and polyethylene glycol (PEG), and combinations thereof.

27. The article of any of claims 17 to 23, wherein the thermoplastic shrink fdm of the three-dimensional article is made from a hygroscopic polymeric material with a minimum moisture regain of at least 0.05%.

28. The article of claim 17 wherein the clear outer package has been shaped and sealed to form a cylindrical, ellipsoidal, rhombohedron, rhombic hexahedron, triangular prism or tetrahedron, conic, cuboidal, spheric, three-dimensional saddle points, hyperbolic paraboloids, elliptic hyperboloids, parallel piped or trapezoidal prism form.

Images