Thermoregulatory packaging materials

Abstract

Thermoresponsive packaging materials and packaging systems configured to regulate the temperature of heat-sensitive material and methods of making the same are disclosed. The thermoresponsive packaging materials and packing systems include a first phase change material, a second phase change material and a barrier layer between the phase change material. The packaging materials and packaging system are configured for packaging products such as medical devices.

Description

THERMOREGULATORY PACKAGING MATERIALSTECHNICAL FIELD

[0001] The present disclosure relates to packaging materials and packaging systems configured to contain products that require a desired temperature during storage and transportation and the methods of manufacturing the same.BACKGROUND

[0002] Various chemical, biochemical, medical, electrical and electronic materials and products are sensitive to thermal conditions such as extreme temperatures and temperature changes that may cause spoliation and / or degradation of such products and materials. It is desirable to limit the exposure of these materials to such thermal conditions. Medical, diagnostic and pharmaceutical products are generally sensitive to one or both high and low temperature conditions. High and low temperature conditions are often encountered during one or both of storage and shipment of products and materials, for example, storage in a container or warehouse and shipment in a vehicle such as a train car, a truck, plane or ship. To alleviate problems associated with exposure to such thermal conditions, products such as medical, diagnostic and pharmaceutical are shipped and stored in thermoregulated packages. This ensures that the product does not deteriorate or spoil during storage and shipment.

[0003] The medical industry utilizes a variety of thermoregulatory materials and systems to store and ship pharmaceuticals and medical devices. Some of these materials and systems take advantage of physicochemical properties of phase change materials that undergo phase transition in temperature ranges that are suitable for storage of specific products. Although some of these materials systems provide packaging materials with a desired heat capacity, they are expensive, have high carbon footprints, and are not capable of thermoregulating products for an extended period of time. For example, Styrofoam has a high carbon footprint, requires large amounts of space and is not recyclable.

[0004] There is a need for thermoregulatory packaging materials and systems that provide excellent temperature regulated shipment and storage capabilities inrecommended temperature ranges. In addition, it would be desirable to provide thermoregulatory packaging materials and systems that are inexpensive, reduce carbon footprint relative to existing materials and systems, and / or are configured to maintain a desired temperature range for packaged materials and products for an extended period of time.SUMMARY

[0005] A first aspect of the disclosure pertains to a packaging material comprising a first layer comprising a first thermoresponsive material; a second layer comprising a second thermoresponsive material that has a property that is different from a property of the first thermoresponsive material; and a barrier layer between the first layer and the second layer, wherein the packaging material is configured to regulate a first temperature in the first layer and a second temperature in the second layer, the second temperature different from the first temperature.

[0006] A second aspect of the disclosure pertains to a method of manufacturing a packaging material. The method comprises applying a barrier layer on a first surface of a first layer comprising a first thermoresponsive material; and applying a second layer comprising a second thermoresponsive material that has a property different from a property of the first thermoresponsive material on the barrier layer.BRIEF DESCRIPTION OF THE DRAWINGS

[0007] So that the manner in which the above recited features of the present disclosure can be understood in detail, a more particular description of the disclosure, briefly summarized above, may be made by reference to embodiments, some of which are illustrated in the appended drawings. It is to be noted, however, that the appended drawings illustrate only typical embodiments of this disclosure and are therefore not to be considered limiting of its scope, for the disclosure may admit to other equally effective embodiments.

[0008] FIG. 1A is schematic a side view of a packaging material in accordance with one or more embodiments;

[0009] FIG. 1B is a perspective view of a packaging material in accordance with one or more embodiments;

[0010] FIG. 2 is a cross-sectional view of a packaging material accordance with one or more embodiments;

[0011] FIG. 3 is perspective view of a container in accordance with one or more embodiments;

[0012] FIG. 4A is a schematic view of a packaging system including a container and packaging material in accordance with one or more embodiments;

[0013] FIG. 4B is an exploded view of the packaging material shown in FIG. 4A

[0014] FIG. 5 is a graph of temperature distribution vs. thickness for a packaging material in accordance with one or more embodiments;

[0015] FIGS. 6A-C respectively show temperature distribution in a packaging material at 1 day, 10 days and 40 days in accordance with one or more embodiments; and

[0016] FIG. 7 is a flow chart illustrating a method according to one or more embodiments of the disclosure.

[0017] In the appended figures, similar components and / or features may have the same reference label. Further, various components of the same type may be distinguished by following the reference label by a dash and a second label that distinguishes among the similar components. If only the first reference label is used in the specification, the description is applicable to any one of the similar components having the same first reference label irrespective of the second reference label. The cross-hatched shading of the components in the figures are intended to aid in visualization of different parts and do not necessarily indicate different materials of construction.DETAILED DESCRIPTION

[0018] As used herein according to one or more embodiments, "thermoresponsive" materials (e.g., thermoresponsive polymers) refer to materials such as polymers that exhibit changes in their physical properties with temperature, sometimes discontinuous changes in properties. In one or more embodiments, a lower criticalsolution temperature (LOST) material or polymer is soluble below a critical temperature and insoluble above a critical temperature. In one or more embodiments, an upper critical solution temperature (UCST) material or polymer is insoluble below a critical temperature and soluble above UCST. LCST and UCST materials, in one or more embodiments, transition from a single phase into a two-phase system, and may exhibit coil-to-globule transition, and solid-solid phase transitions. As used herein according to one or more embodiments, the term "thermoregulatory" refers to a material, a package, a container or a packaging system that is configured to maintain and / or control temperature. In some embodiments, a thermoregulatory material is activated at selected temperature and undergoes an endothermic and or exothermic phase transition at a desired temperature. These transitions involve the absorption and or release of energy due to the thermoregulatory nature of material which help in maintaining the desired temperature inside of a container such as a shipping box. A packaging material according to one or more embodiments comprises, consists essentially of or consists of two or more layers alternately or in a prescribed order as described further in this disclosure. In an embodiment, a packaging material comprises a first layer comprising a first thermoresponsive material, a second layer comprising a second thermoresponsive material that has a property that is different from a property of the first thermoresponsive material, and a barrier layer between the first layer and the second layer, wherein the packaging material is configured to regulate a first temperature in the first layer and a second temperature in the second layer, the second temperature different from the first temperature. As used herein, “consisting essentially of' refers to the addition of layers that do not materially change the function of the packaging material, for example a paper or a polymer lining that can be positioned at any useful location with respect to the packaging material.

[0019] As used herein, "applying a barrier layer" refers to disposing a barrier layer to a surface of another material, for example, a first surface of a first layer of a first thermoresponsive material or a first surface of a second layer of a second thermoresponsive material. Applying according to one or more embodiments includes placing a barrier layer on another surface, for example, a pre-formed barrier material such as a porous sheet of material or a porous web such as a honeycomb, ontoanother layer. In other embodiments, applying a layer comprises forming a layer, for example by growing or depositing a layer on a first surface of a first layer comprising a first thermoresponsive material or a second surface of a second layer comprising a second thermoresponsive material. Depositing includes, but is not limited to chemical vapor deposition, cyclical deposition, atomic layer deposition, physical vapor deposition and spin-coating.

[0020] As used herein, void space includes spaces between two layers that include empty space such as pores, openings or gaps in a body of solid material or between the two layers, for example, pillars of material may have gaps or spaces between the pillars. A porous material comprises a solid material with gaps or openings between the solid material making up the porous material. Furthermore, a porous material may have open and closed pores. Void ratio is the ratio of the volume of voids to the volume of solids. In one or more embodiments, the void ratio of the void space is in a range of from 30-90%, 30-80%, 30-70%, 30-60%, 30-50%, 40-90%, 40-80%, 40-70%, 40-60%, 50-90%, 50-80%, and 50-70%.

[0021] Before describing several exemplary embodiments of the disclosure, it is to be understood that the disclosure is not limited to the details of construction or process steps set forth in the following description. The claimed packaging material, packaging system and methods described herein are capable of other embodiments and of being practiced or being carried out in various ways.

[0022] One or more embodiments of the present disclosure advantageously provide a packaging material that is in the form of a combination of two layers comprising different thermoresponsive materials with different physical and chemical properties and a barrier layer between the layers. Each of the first thermoresponsive material and the second thermoresponsive material may comprise, consist essentially of, or consist of phase change materials ("PCMs"). Consist essentially of refers to the addition of a material that does not change the thermoregulatory properties of the first thermoresponsive material or the second thermoresponsive material, for example, a liner. An advantage of the packaging material according to one or more embodiments of the present disclosure is that the packaging material is configured to regulate heat flux from one side of the packaging material to an opposite side of packaging materialfor an extended period of time. In some embodiments, the packaging material is configured to regulate temperature of the individual layers and between the individual layers for an extended period of time.

[0023] In one or more embodiments, the packaging material is in the form of a laminar composite to provide a laminar composite packaging material. A laminar composite packaging material according to one or more embodiments comprises a combination of two layers of thermoresponsive materials comprising PCMs having different physical and chemical properties. In one or more embodiments, the different layers of the laminar composite packaging material are bound together, by intramolecular bonds and / or intramolecular forces. Intramolecular bonds comprise one or more covalent bonds, ionic bonds or metal bonds. Intramolecular forces comprise one or more of electrostatic forces, van der Waals bonds, ion-dipole, hydrogen bonds or dipole-dipole forces.

[0024] In one or more embodiments, PCMs include LOST and UCST materials. A non-limiting list of exemplary UCST materials includes poly(methyl methacrylate) (PMMA) and poly(2-oxazoline)s in alcohol-water mixtures, PNAGA-poly(N-acryloyl glycinamide) and PEG-b-polyacrylamide-co-acryionitrile in hydrogel and poly(betaine)s in aqueous solutions. Two common poly(betaine)s with UCST behavior are poly(2-di methyl (methacryloxyethyl) ammoniumpropane sulfonate) (PDMAPS-MA) and poly(3-(N-(3-methacrylamidopropyl)-N,N-dimethyl) ammonium propane sulfonate (PDMAPS-MAM). A non-limiting list of exemplary LCST materials includes poly(N- isopropyl acrylamide), PEG-b-poly(acrylamide-co-acrylonitrile), polyethylene glycol)- poly(2-hydroxyethyl methacrylate), poly( / V, / V-diethyl acrylamide) and combinations thereof.

[0025] A poly(N-isopropyl acrylamide) (abbreviated PNIPAM) is a vinyl polymer with secondary amide pendant groups. The two lone pairs of the oxygen atom and the lone pair of the nitrogen atom of the amide bond are acceptors of hydrogen bonds, whereas the hydrogen covalently attached to the nitrogen atom is a donor of hydrogen bonds. LCST of PNIPAM based polymers can be tuned according to application by copolymerization with more hydrophilic or hydrophobic polymers. In some embodiments, a lower critical solution temperature material is tunable bycopolymerization with at ieast one of a hydrophilic polymer and a hydrophobic polymer and the upper critical solution temperature material is insoluble below a critical temperature and soluble above the critical temperature. The packaging material results in no change in the form factor the cardboard boxes, and thus the packaging material can be substituted and used in place of existing materials such as Styrofoam insulation. The packaging material comprises a uniquely designed material architecture which comprises a barrier layer that may include a vacuum in between the first layer 12 and the second layer 14 provided by small pillars such as nanopillars, which enhance the efficiency of phase change material.

[0026] According to one or more embodiments, the packaging materials used herein comprise a polymer insert which can utilized with conventional cardboard boxes, or any other type of common packages or containers used for the storage and shipping of food, pharmaceutical, medical and other products in which temperature needs to be regulated.

[0027] In one or more embodiments, the barrier layer comprises void space. In one or more specific embodiments, the void space further comprises a gas. According to some embodiments, the barrier layer 18 comprises a web or a plurality of pillars. The plurality of pillars, which may be in the form of a web, maintain the structural integrity of the packaging material and strengthens the packaging material. In one or more embodiments, the plurality of pillars comprises, consists essentially of or consists of a metal or metal oxides. In more specific embodiments, the plurality of pillars comprises, consists essentially of or consists of silicon oxide (SiOs), aluminum oxide (AI2O3) and combinations of aluminum oxide and silicon oxide.

[0028] According to one or more embodiments, configuring layers of thermoresponsive materials and a barrier layer in the packaging material regulates the temperature across the packaging material and of a product contained in a package including the packaging material. The packaging materials described herein provide for the ability to manufacture packaging systems that are capable of regulating the temperature of a product when there is a considerable difference between the temperature of the product and the immediate outer environment for an extended period of time.

[0029] One or more embodiments of the present disclosure provide a packaging system comprising a container having an interior and an interior surface including at least one layer of the packaging material and / or the laminar composite packaging material in accordance with one or more embodiments, in specific embodiments, the interior surface includes a layer of the packaging material according to one or more embodiments of the present disclosure. In one or more embodiments the interior surface includes laminar composite packaging material.

[0030] In one or more embodiments, the interior surface includes a plurality of the packaging material according to one or more embodiments of the present disclosure and additional layers of an insulator(s) positioned alternately or in any prescribed order between the plurality of packaging material. In one or more embodiments, conventional packaging material may be used as additional layers positioned alternately or in any prescribed order between the plurality of the packaging material.

[0031] In one or more embodiments, the packaging material included in the interior surface of the container absorbs heat when the temperature of the immediate outer environment is higher than a desired storing temperature and releases heat when the temperature of the immediate outer environment is lower than a desired storing temperature. In one or more embodiments the LCST material of the packaging system absorbs heat in a range of 5 to 200 J / g and the UCST material of the packaging system releases heat in a range of 50 to 200 J / g.

[0032] An advantage of the packaging materials and packaging systems in accordance to one or more embodiments of the present disclosure packaging materials and systems are configured to regulates the temperature of a product in a wide variety of temperature ranges. For example, in one or more embodiments, the packaging materials and packaging systems described herein are configured to regulate the temperature of a product in a range of about 0-45 °C, 0-40 °C, 0-37 °C, 0-27 °C, 0-17 °C, 0-8 °C, 1-45 °C, 1-40 °C, 1-37 °C, 1-27 °C, 1-17 °C, 1-8 °C, 2-45 °C, 2-40 °C, 2-37 °C, 2-27 °C, 2-17 °C, 2-8 °C, 3-45 °C, 3-40 °C, 3-37 °C, 3-27 °C, 3-17 °C, 3-8 °C, 4-45 °C, 4-40 °C, 4-37 °C, 4-27 °C, 4-17 °C, 4-8 °C, 5-45 °C, 5-40 °C, 5-37 °C, 5-27 °C, 5-17 °C, 5-8 °C, 6-45 °C, 6-40 °C, 6-37 °C, 6-27 °C, 6-17 °C, 6- 8 °C, 7-45 °C, 7-40 °C, 7-37 °C, 7-27 °C, 7-17 °C, 7-8 °C, 8-45 °C, 8-40 °C, 8-37 °C,8-27 °C, 8-17 °C, 9-45 °C, 9-40 °C, 9-37 °C, 9-27 °C, 9-17 °C, 10-45 °C, 10-40 °C, 10-37 °C, 10-27 °C, 10-17 °C, 11-45 °C, 11-40 °C, 11-37 °C, 11-27 °C, 11-17 °C, 12- 45 °C, 12-40 °C, 12-37 °C, 12-27 °C, 12-17 °C, 13-45 °C, 13-40 °C, 13-37 °C, 13-27 °C, 13-17 °C, 14-45 °C, 14-40 °C, 14-37 °C, 14-27 °C, and 14-17 °C for an extended period of time. An extended period of time according to one or more embodiments ranges from 0 days to 1 day, 0 days to 5 days, 0 days to 7 days, 0 days to 14 days, 0 days to 21 days, 0 days to 28 days, 0 days to 56 days or 0 days to 84 days. According to one or more embodiments, the iaminar packaging materiai comprising an upper critical solution temperature material and a lower critical solution temperature material having a barrier material therebetween provides an unlimited number of thermoregulatory packaging configurations in terms of temperature ranges and periods of time to regulate the interior of a package within a desired temperature range. The laminar composite packaging material allows the storage of temperaturesensitive materials without requiring active air conditioning, which consumes energy, providing a packaging system that reduces the carbon footprint and a more environmentally beneficial solution.

[0033] In one or one or more embodiments, the product disposed in the container comprises, consists essentially of or consists of a chemical, medical, electrical, biochemical, cosmetic or biological materials. In more particular embodiment, the product is a pre-filled syringe, a flush syringe, coated catheters, diagnostic reagents or diagnostic dyes.

[0034] In one or more embodiments, the container may have any desired shape or geometry (e.g., spherical, rectangular, cylindrical, etc.). The shape of the container can be symmetric or asymmetric. The packaging material may be shaped to conform to the shape of the container so that an entire interior surface and / or exterior surface of the container includes the packaging material. In one or more embodiments, the container may be made of cardboard, paper, polymer, ceramics, glass metal or composite.

[0035] Referring now to the drawings, FIG. 1A illustrates a schematic side view of a packaging material according to one or more embodiments. The packaging material 10 includes a first layer 12 comprising a first thermoresponsive material 13 and asecond layer 14 comprising a second thermoresponsive material 15. A barrier layer 18 is disposed between the first layer 12 and the second layer 14. In one or more embodiments, the first layer 12 comprises an LOST or an UCST material. In one or more embodiments, the second thermoresponsive material 15 comprises an LCST material or an UCST material. In more particular embodiments, both the first thermoresponsive material 13 and the second thermoresponsive material 15 comprise an UCST or an LCST material. It will be appreciated that the first layer 12 and the second layer 14 may be disposed on either side of the barrier layer 15 in a prescribed order. For example, while the first layer 12 may be disposed adjacent to an outer surface of a container, and the second layer 14 may be adjacent to an interior of a container, the packaging material 10 may be arranged so that the second layer is adjacent the other surface of a container and the second layer is adjacent to an interior surface of the container.

[0036] FIG. 1 B is a partially sectioned perspective view of a packaging material in the form of a laminar composite packaging material including a plurality of pillars. In reference to FIG. 1A, the laminar composite packaging material 10 includes the barrier layer 15 which is formed or applied between the first layer 10 and the second layer 20. In one or more embodiments, the barrier layer 18 in the form of a plurality of pillars 25. In other embodiments, the barrier layer 18 may be deposited with a preferred geometry such as honeycomb. The plurality of pillars 25 are configured to form a void space 26 within the barrier layer 18. Depending on the density of the barrier layer 18, the void space 26 may have a porosity in a range of 5-95 percent by volume, or a narrower range. The void space may comprise, consist essentially of or consist of vacuum or the void space may comprise a gas such as an inert gas. In some embodiments, the plurality of pillars 25 are nanometer-sized pillars (e.g., having height and diameter dimensions in a range of 1-100 nanometers). Thus, in some embodiments, nanopillars are formed on the first layer 12 and / or the second layer 12. As an example, the nanopillars may be formed via an ultraviolet lithography process by depositing an array of nanopillars on the first layer 12 and / or the second layer 14. The first layer or the second layer may be any of the materials described herein and may be in the form of a polymer film substrate. After formation of the plurality of pillars25 between the first layer 12 and the second layer 14, the first layer 12 and the second layer 14 are sealed, for example by heat sealing or an adhesive such as an epoxy to create a vacuum in the barrier layer 18. The barrier layer 18 comprises a thickness "b" and is superimposed by the second layer 14. In one or more embodiments, the laminar composite packaging material is configured so that the barrier layer 18 is sealed, thus keeping the gas inside the void space 26 or maintaining vacuum in the void space. According to one or more embodiments, the overall thickness T of the packaging material 10 may be in a range of 1 to 20 mm, for example 1 to 15 mm, 1 to 10 mm, 1 to 8 mm, 1 to 5 mm, 1 to 4 mm or 1 to 3 mm. According to one or more embodiments, the thickness of each of the first layer 12, the second layer 12 and the barrier layer 18 are in a range of 0.1 to 5 mm, 0.1 to 4 mm, 0.1 to 3 mm, 0.1 to 2 mm, 0.1 to 1 mm, 0.2 to 5 mm, 0.2 to 4 mm, 0.2 to 3 mm 0.2 to 2 mm, 0.2 to 1 mm, 0.5 to 5 mm, 0.5 to 4 mm, 0.5 to 3 mm, 0.5 to 2 mm or 0.5 to 1 mm.

[0037] FIG. 2 illustrates a schematic view of the packaging material exposed to different temperatures. The first layer 12 is directly exposed to a high temperature 30, and the second layer 14 is exposed to a low temperature 35. The high temperature 30 can be the temperature of the ambient atmosphere surrounding a package, for example, the temperature in a warehouse, on a loading dock, or the temperature in a vehicle such as the cargo compartment of a delivery vehicle such as a courier truck, an airplane, a ship, or a train. The low temperature 35 may be a region of an interior of a container such as a cardboard box that includes a cooling medium such as an ice pack comprised of frozen water or dry ice. It will be understood that the ambient temperature may be a relatively high or relatively low temperature. Therefore, for example, in a cold atmosphere, the low temperature 35 may be the outside of the container or package and the high temperature 30 may be the interior of the package or container. In one or more embodiments, the first layer 12 may be a UCST material exposed to a high temperature 30. The high temperature 30 may be atmospheric temperature, for example, the interior of a shipping vehicle such as a courier truck, a train car or storage space within a larger shipping container. The second layer 14 may be an LCST material exposed to the low temperature 35. The low temperature 35 may be a desired storage temperature for a product. The temperature gradient betweenthe low temperature 35 and the high temperature 30 causes a heat flux as represented arrow 42 from the first layer 12 to the second layer 14. The heat flux 42 may be in the form of conduction, for example through the pillars 25, conduction through void space filled with gas, and radiation 49 between layers. In one or more embodiments, the first layer 12, upon exposure to the high temperature 30 absorbs heat and change phases, thus storing heat. In one or more embodiments the heat flux 42 exceeds the heat capacity of the first layer 12 and the heat flows through the barrier layer 18 and toward the second layer 14. In one or more embodiments, the barrier layer 18 is configured to function as an insulator, which reduces or prevents the flow of heat between the first layer 12 and the second layer 14. It will be appreciated that the direction of heat flux 42 will be reversed once the second layer 14 is exposed to the high temperature 30 and the first layer 12 is exposed to the low temperature 35. The packaging material 10 can be configured so that the flux of the heat flux 42 can be adjusted based on specific needs and the range of the temperature to be regulated. It is understood by one having ordinary skill in the art that the physical (e.g., geometry, thickness) and chemical (heat capacity, conductivity, etc.) properties of the layers of the packaging material determine the heat flux.

[0038] FIG. 3 is a perspective view of a container 50 according to one or more embodiments. The container 50 includes an interior 44, a lid 41 , a bottom 43, an interior surface 46, at least one sidewall 47, and an exterior 48. The interior 44 is configured to receive a product 56. In some embodiments, the wall 47 of the container 50 is corrugated, for example, corrugated cardboard or other board material such as corrugated plastic. The product 56 is any item that is intended to be thermoregulated to a desired temperature range. In one or more embodiments, the product 56 comprises a medical device, a diagnostic device or a dye material, and the interior surface46, the lid 41 , the bottom 43, and the wall 47 may have anti-static properties.

[0039] Referring now to FIGS. 4A-B, multiple sections of packaging material 10 in the form of a laminar composite packaging material as shown and discussed with respect to FIGS 1A-B and 2 are shown as placed in the interior 44 of the container 50 in a stacked relationship. FIGS. 4A-B illustrate the container 50 having a product 56contained therein. FIG. 4A illustrates a packaging system 60 that includes packaging material 10 in the form of a laminar composite packaging material placed in the interior 44 of the container 50. The packaging material system 60 includes at least two layers of the packaging material 10 disposed within the container 50 with at least one second packaging material 55 placed between the two layers of packaging material 10. FIG. 5B is an exploded perspective view of the layers of the packaging material 10 and the at least one second packaging material 55. In one or more embodiments, the at least one second packaging material 55 may be positioned alternately or in any prescribed order between multiple layers of packaging material 10. In one or more embodiments, the at least one second packaging material comprises an insulator or different types of insulators, a conventional packaging material or different types of conventional packaging material, or a combination thereof. The embodiment shown in FIGS. 4A-B is exemplary. It will be understood that a packaging system 60 according to one or more embodiments will comprise the container 50 and the packaging material 10 as shown and described with respect to FIGS. 1A-B and 2. The addition of more layers of the packaging material 10 and the at least one second packaging material 55 provides additional degrees of freedom in tailoring the packaging system to a particular product need that may be exposed to a variety of ambient conditions ranging from extreme cold (e.g., subzero (°C temperature) to extreme heat (e.g., exceeding 50 °C).

[0040] FIG. 5 is a graph according to an exemplary embodiment illustrating a temperature profile across the thickness (T) of the packaging material 10 according to one or more embodiments. The first layer 12 is exposed to a high temperature of 45 °C. This temperature may be an ambient temperature or a storage temperature. The interior of the package is at 15. The packaging material 10 may regulate the low temperature to 15 °C. As shown in FIG. 5, the temperature across the thickness of the material, with 0.0 representing the outer surface of the packaging material exposed to the ambient environment, the temperature is 45 °C, while the temperature closer to the interior of the package is closer to 15 °C.

[0041] FIGS. 6A-C schematically illustrates a simulated time lapse temperature gradient across a thickness (T) of a laminar composite packaging material packagingmaterial 10 as shown in FIGS. 1A-B and 2 according to one or more embodiments over a time period of 40 days. The high temperature 30 is about 30 °C and the low temperature 35 is shown as regulated in a range of about 0-8 °C over a period of 40 days. FIG. 6A shows the packaging material at 0 days when the package has been sealed and the low temperature is 0 °C at the interior of the package where the product is located and a cooling medium such as a water ice pack or dry ice pack has been placed. The ambient temperature and the high temperature 30 of the packaging material 10 is at 30 °C. FIG. 6B shows a change in the low temperature 35 to about 5 °C, while the ambient temperature and the high temperature remains at 30 °C. FIG. 6C shows the ambient temperature and the high temperature of the packaging material 30 at 30 °C, while the low temperature has increased to about 8 °C. The diagonal pattern in FIGS. 6A-C represents the high temperature 30, and the white (no pattern) represents the low temperature 35, while the heavier stippled pattern represents a slightly lower temperature than the warm temperature (e.g., 12-22 °C), the lighter stippled pattern representing a still lower temperature (e.g., 6-10 °C) and the white (not pattern) representing about 8 °C.

[0042] The simulated time lapse temperature gradient shown in FIGS. 6A-C is exemplary and provided to show just one embodiment of how the packaging materials 10 described herein can be used to thermoregulate the interior of a package and how a packaging system can be utilized to maintain a product within a desired temperature range. In this particular example, the interior of the package was shown to be regulated between 0-8 °C over a period of 40 days. The packaging material according to one or more embodiments of the disclosure provides excellent for the storage of a variety of medical, pharmaceutical and diagnostic products in a range of from 0-8 °C over longer periods of time compared to conventional phase change materials used in packaging.

[0043] One or more embodiments of the present disclosure provide a method for manufacturing a packaging material that when included in a container thermoregulates a product in the container. Referring to FIG. 7, a method 100 according to one or more embodiments comprises at 110 applying a barrier layer on a first surface of a first layer comprising a first thermoresponsive material. At 120, themethod further comprises applying a second layer comprising a second thermoresponsive material that has a property different from a property of the first thermoresponsive material on the barrier layer. In some embodiments, the method further comprises patterning the barrier layer.

[0044] In some embodiments, applying the barrier layer comprises depositing the barrier layer on the first surface of the first layer comprises a method selected from the group consisting of chemical vapor deposition, cyclical deposition, atomic layer deposition, physical vapor deposition, spin-coating and physical vapor deposition.

[0045] According to one or more embodiments of the method, the first layer, the second layer and the barrier layer form a laminar composite. Patterning the barrier layer includes an ultraviolet lithography process according to some embodiments.

[0046] The first thermoresponsive material and the second thermoresponsive material each comprises a phase change material as described further herein. In some method embodiments, the lower critical solution temperature material is tunable by copolymerization with at least one of a hydrophilic polymer and a hydrophobic polymer and the upper critical solution temperature material is insoluble below a critical temperature and soluble above the critical temperature.

[0047] The method may further comprise forming a stack of multiple laminar composites, for example, two or more laminar composites as described herein.

[0048] In one or more embodiments, the barrier layer is a solid web of material that is imposed between the first and the second layers. The packaging material is then sealed to form a void space in between the layers.

[0049] In one or more embodiments, the barrier layer is applied in between the first and the second layers using any methods of chemical vapor deposition, cyclical deposition, atomic layer deposition, physical vapor deposition, spin-coating and physical vapor deposition. It would be understood by one having ordinary skill in the art that deposition methods are not limited to the above. In one or more embodiments the deposition is patterned to form a desired geometry such as honeycomb or any other geometry. In other embodiments the deposition may not have a pattern.

[0050] In one or more particular embodiments, the barrier layer is deposited on the first layer in a roll-roll process. The barrier layer is patterned using UV lithography in aroll-roll process. The plasma generated by UV facilitates a reactive-ion etching on the surface of the deposited barrier layer.

[0051] the first thermoresponsive material comprises a first lower critical solution temperature material and the second thermoresponsive material comprises a second lower critical solution temperature material.

[0052] Reference throughout this specification to "one embodiment," "certain embodiments," "one or more embodiments" or "an embodiment" means that a particular feature, structure, material, or characteristic described in connection with the embodiment is included in at least one embodiment of the disclosure. Thus, the appearances of the phrases such as "in one or more embodiments," "in certain embodiments," "in one embodiment" or "in an embodiment" in various places throughout this specification are not necessarily referring to the same embodiment of the disclosure. Furthermore, the particular features, structures, materials, or characteristics may be combined in any suitable manner in one or more embodiments.

[0053] Although the disclosure herein has been described with reference to particular embodiments, it is to be understood that these embodiments are merely illustrative of the principles and applications of the present disclosure. It will be apparent to those skilled in the art that various modifications and variations can be made to the method and apparatus of the present disclosure without departing from the spirit and scope of the disclosure. Thus, it is intended that the present disclosure include modifications and variations that are within the scope of the appended claims and their equivalents.

Claims

WHAT IS CLAIMED IS:

1. A packaging material comprising: a first layer comprising a first thermoresponsive material; a second layer comprising a second thermoresponsive material that has a property that is different from a property of the first thermoresponsive material; and a barrier layer between the first layer and the second layer, wherein the packaging material is configured to regulate a first temperature in the first layer and a second temperature in the second layer, the second temperature different from the first temperature.

2. The packaging material of claim 1, wherein the first thermoresponsive material and the second thermoresponsive material each comprises a phase change material.

3. The packaging material of claim 2, wherein the first thermoresponsive material comprises a lower critical solution temperature material and the second thermoresponsive material comprises an upper critical solution temperature material.

4. The packaging material of claim 3, wherein the first thermoresponsive material comprises a first lower critical solution temperature material and the second thermoresponsive material comprises a second lower critical solution temperature material.

5. The packaging material of claim 3, wherein the lower critical solution temperature material is selected from the group consisting of poly(N-isopropyl acrylamide), PEG-b-polyCacrylamide-co-acrylonitrile), poly(ethylene glycol)-poly(2- hydroxyethyl methacrylate), poly( / V, / V-diethyl acrylamide) and combinations thereof.

6. The packaging material of claim 3, wherein the first thermoresponsive material comprises a first upper critical solution temperature material and the secondthermoresponsive material comprises second upper critical solution temperature material.

7. The packaging material of claim 3, wherein the upper critical solution temperature material is selected from the group consisting of poly(N-acryloyi glycinamide), PEG-b-polyacrylamide-co-acrylonitrile, poly(ethylene oxide)-poly(vinyl methyl ether), poly(2-hydroxyethyl methacrylate) and combinations thereof.

8. The packaging material of claim 3, wherein the lower critical solution temperature material and the upper critical solution temperature material are both PEG-b-polyacrylamide-co-acrylonitrile.

9. The packaging material of claim 3, wherein the lower critical solution temperature material comprises PEG-b-poly(acryiamide-co-acrylonitrile) and the upper critical solution temperature material comprises poiy(N-acryloyl glycinamide).

10. The packaging material of claim 3, wherein the lower critical solution temperature material absorbs heat in a range of 5 to 200 J / g and the upper critical solution temperature material releases heat in a range of 50 to 200 J / g.

11. The packaging material of claim 1 , wherein the first layer, the second layer and the barrier layer comprise a laminar composite.

12. The packaging material of claim 11, wherein the packaging material comprises two or more of the laminar composite arranged in a stacked relationship.

13. The packaging material of claim 11 , wherein the barrier layer defines a volume comprising a barrier material and void space.

14. The packaging material of claim 11, wherein the barrier layer comprises a web or a plurality of pillars.

15. The packaging material of claim 11, wherein the barrier layer further comprises a fluid or a vacuum.

16. The packaging material of claim 15, wherein the fluid comprises a gas.

17. The packaging material of claim 11, wherein the barrier layer comprises a metal, a metal oxide, a polymer or a composite material.

18. The packaging material of claim 1, wherein the packaging material is reusable.

19. The packaging material of claim 1, wherein the packaging material is recyclable.

20. A packaging system comprising a container having an interior and an interior surface including the packaging material of claim 1.

21. The packaging system of claim 20, wherein the packaging material is configured to regulate a temperature of the interior of the container in a range of about 4 °C to 37 °C.

22. The packaging system of claim 21 , wherein the packaging material is configured to regulate the temperature of the interior of the container at 32 °C.

23. The packaging system of claim 20, wherein the packaging material is configured to regulate a temperature of the interior of the container in a range of 13 °C23 °C.

24. The packaging system of claim 20, wherein the packaging material is configured to regulate the temperature of the interior of the container in a range of 2 °C - 8 °C for at least 40 days.

25. The packaging system of claim 20, wherein the packaging material is configured to preserve chemical, medical, electrical, biochemical, cosmetic or biological materials.

26. The packaging system of claim 20, wherein the packaging material is configured to regulate the temperature of the interior to a desired temperature range of a product selected from the group consisting of a pre-filled syringe, a flush syringe, coated catheters, diagnostic reagents and diagnostic dyes.

27. A method of manufacturing a packaging material, comprising: applying a barrier layer on a first surface of a first layer comprising a first thermoresponsive material; and applying a second layer comprising a second thermoresponsive material that has a property different from a property of the first thermoresponsive material on the barrier layer.

28. The method of claim 27, the method further comprising patterning the barrier layer.

29. The method of claim 27, wherein applying the barrier layer comprises depositing the barrier layer on the first surface of the first layer comprises a method selected from the group consisting of chemical vapor deposition, cyclical deposition, atomic layer deposition, physical vapor deposition, spin-coating and physical vapor deposition.

30. The method of claim 27, wherein the first layer, the second layer and the barrier layer form a laminar composite.

31. The method of claim 27, wherein the barrier layer comprises a plurality of pillars.

32. The method of claim 28, wherein patterning the barrier layer includes an ultraviolet lithography process.

33. The method of claim 27, wherein the first thermoresponsive material and the second thermoresponsive material each comprises a phase change material.

34. The method of claim 33, wherein the first thermoresponsive material comprises a lower critical solution temperature material and the second thermoresponsive material comprises an upper critical solution temperature material.

35. The method of claim 33, wherein the first thermoresponsive material comprises a first lower critical solution temperature material and the second thermoresponsive material comprises a second lower critical solution temperature material .

36. The method of claim 34, wherein the lower critical solution temperature material is selected from the group consisting of poly(N- isopropyl acrylamide), PEG-b- poly(acrylamide-co-acrylonitrile), polyethylene glycol)-poly(2-hydroxyethyl methacrylate), poly(A / ,A / -diethyl acrylamide) and combinations thereof.

37. The method of claim 33, wherein the first thermoresponsive material comprises a first upper critical solution temperature material and the second thermoresponsive material comprises second upper critical solution temperature material.

38. The method of claim 37, wherein the upper critical solution temperature material is selected from the group consisting of poly(N-acryloyl glycinamide) and and PEG-b-polyacrylamide-co-acrylonitrile.

39. The method of claim 34, wherein the lower critical solution temperature material and the upper critical solution temperature material are both PEG-b-polyacrylamide- co-acrylonitrile .

40. The method for manufacturing a packaging materia! of claim 34, wherein the lower critical solution temperature material comprises PEG-b-polyfacrylamide-co- acrylonitrile) and the upper critical solution temperature material comprises poly(N- acryloyl glycinamide).

41. The method for manufacturing a packaging material of claim 34, wherein the lower critical solution temperature material absorbs heat in a range of 5 to 200 J / g and the upper critical solution temperature material releases heat in a range of 50 to 200 J / g.

42. The method of claim 34, wherein the lower critical solution temperature material is tunable by copolymerization with at least one of a hydrophilic polymer and a hydrophobic polymer and the upper critical solution temperature material is insoluble below a critical temperature and soluble above the critical temperature.

43. The method of claim 30, wherein the method comprises forming a stack of multiple laminar composites.

44. The method of claim 30, the laminar composite has a thickness is in a range of from 1 mm to 3 mm.

45. The method of claim 44, wherein each of the first thermoresponsive layer, the second thermoresponsive layer, and the barrier layers has a thickness in a range of from 0.5 mm to 1mm.

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