Peelable composite thermoplastic sealants in packaging films

- 1 PEELABLE COMPOSITE THERMOPLASTIC SEALANTS IN PACKAGING

FILMS

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of and claims priority to U.S. application Serial No. 12/031,450, filed February 14, 2008, the entire content of which is hereby incorporated herein by reference.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to package systems that include a peelable seal, and in particular, the present invention relates to compositions and methods for forming such peelable seals.

2. Background Art

Packaging is an important feature in selling and marketing most products. Food products, in particular, have rather stringent packaging requirements in order to preserve freshness and enhance shelf life. Certain medical devices also present strict packaging requirements in order to preserve sterility of such devices. Tn such applications, the package is typically vacuum-packed or gas-flushed and subsequently hermetically sealed. Although efficient packaging of products is mandatory, various aesthetic properties of u product package are also important. For example, the appearance of a product is important in uppccling to consumers. Moreover, in many applications and, in particular, for food products reusability and ease of opening of a package are also important considerations. In many applications, the ability to easily open a package will depend on the mechanical properties of the seal.

AUG 2010

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One particularly important packaging structure utilizes a peelable seal. In at least one prior art packaging system, a peelable seal is formed by coating a heat sealable polymeric material onto a metal foil. Since packaging incorporating such seals are often impervious to air and contaminants, peelable seals must also be impervious to these materials. When a package having a peelable seal is opened, a sealing layer may be peeled away from a substrate. It is desirable for such peeling to be achievable with a low and relatively constant peel force. The elastic properties of the peelable seal are such that failure of the seal does not occur from flexing and normal handling of the package. In some prior art packaging, peelable seals are constructed from multi-layered sheets. Examples of packaging systems having such seals include tray-type food packages, bottles or blister packages, and the like. Although some of the prior art peelable sealing packages work reasonably well, it has been difficult to construct packaging systems that consistently form hermetic seals that resist leaking while being easily opened by an end user. Moreover, such prior art peelable packaging systems tend to operate over relatively narrow ranges, and in particular narrow temperature ranges. Narrow sealing temperature ranges tend to result in packaging defects. For example, on the low end of the usable temperature range leaking seals may be formed (not hermetically sealed). On the high end of the usable temperature range, non-peelable seal are formed which tear when opened.

SUMMARY OF THE INVENTION

The present invention provides the following items 1 to 29:

I. A peelable sealing structure comprising: a thermoplastic polymer;

an organoclay dispersed within at least a portion of the thermoplastic polymer, wherein the peelable sealing structure includes a sealing layer that defines a sealing surface, the sealing surface formable into a peelable seal at all temperatures within a peelable seal temperature range, the peelable seal temperature range being from a seal initiation temperature to a temperature that is at least 37.8 °C (100 °F) above the seal initiation temperature wherein the seal initiation temperature is from 76.7 °C to 176.7 °C (170° F to 350° F) and the organoclay comprises platelets having an average separation of at least 20 angstroms, the sealing surface having a roughness average from 1500 to 5000 angstroms and the sealing layer having a tensile modulus from 500 to 2000 MPa.

2. The peelable sealing structure of item 1 wherein the organoclay comprises a plurality of particles having at least one spatial dimension less than 200 nm.

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3 SEP '2013

AMENDMENT

3. The peelable sealing structure of item 1 wherein the organoclay comprises platelets having an average separation of at least 30 angstroms.

4. The peelable sealing structure of item 1 wherein the organoclay comprises a clay 5 selected from the group consisting of kaolinite, montmorillonite-smectite clays, bentonite clays, iHite clays, and combinations thereof.

5. The peelable sealing structure of item 1 wherein the organoclay is present in an amount from 1 wt % to 20 wt % of the combined weight of the thermoplastic polymer and the organoclay.

6. The peelable sealing structure of item 1 wherein the organoclay is present in an amount from 2 wt % to 10 wt % of the combined weight of the thermoplastic polymer and the organoclay.

7. The peelable sealing structure of item 1 wherein the thermoplastic polymer comprises a 15 component selected from the group consisting of nylons, polyolefins, polystyrenes, polyester, polycarbonates, copolymers of ethylene, copolymers of propylene, ethylene vinyl acetate, and mixtures thereof.

8. The peelable sealing structure of item 1 wherein the thermoplastic polymer comprises a 20 component selected from the group consisting of ethylene acrylic acid, ethylene ethyl acrylate, ethylene ionomers, and combinations thereof.

9. The peelable sealing structure of item 1 wherein the thermoplastic polymer comprises ethylene vinyl acetate.

10. A peelable sealing structure comprising: a thermoplastic polymer;

an organoclay dispersed within at least a portion of the thermoplastic polymer, the organoclay having a surface area greater than 100 m²/gram and an aspect ratio greater than 10, wherein the peelable sealing structure defines a sealing surface, the sealing surface having a roughness average from 1500 to 5000 angstroms and the sealing surface having a tensile modulus from 500 to 2000 MPa and the organoclay comprises platelets having an average separation of at least 20 angstroms.

11. The peelable sealing structure of item 10 wherein the organoclay comprises a plurality of particles having at least one spatial dimension less than 200 nm.

12. The peelable sealing structure of item 11 wherein the organoclay is present in an amount,from 1 wt % to 20 wt % of the combined weight of the thermoplastic polymer and the organoclay.

&lt;3 SEP

13. The peelable sealing structure of item 10 wherein the thermoplastic polymer comprises a polymer selected from the group consisting of nylons, polyolefins, polystyrenes, polyesters, polycarbonates, copolymers of ethylene, copolymers of propylene, and mixtures thereof.

14. The peelable sealing structure of item 10 wherein the thermoplastic polymer comprises a component selected from the group consisting of ethylene acrylic acid, ethylene ethyl acrylate, ethylene ionomers, and combinations thereof.

15. The peelable sealing structure of item 10 wherein the thermoplastic polymer 10 comprises ethylene vinyl acetate.

16. A packaging system comprising: a container section; and a peelable sealing section attached to the container section, the sealing section having a sealing substrate and a first sealing layer, the first sealing layer being at least partially disposed over and contacting the sealing substrate, the first sealing layer comprising:

a thermoplastic polymer;

an organoclay dispersed within at least a portion of the thermoplastic polymer, wherein the peelable sealing section defines a sealing surface, the sealing surface formable into a peelable seal on a substrate surface at all temperatures in a peelable seal temperature range, the peelable seal temperature range being from a seal initiation temperature to a temperature at least 37.8 °C (100 °F) above the seal initiation temperature wherein the seal initiation temperature is from 76.7 °C to 176.7 °C (170° F to 350° F) and the organoclay comprises platelets having an average separation of at least 20 angstroms, the sealing surface having a roughness average from 1500 to 5000 angstroms and the sealing layer having a tensile modulus from 500 to 2000 MPa.

17. The packaging system of item 16 wherein the organoclay is dispersed within at least a portion of the thermoplastic polymer, the organoclay having a surface area greater than 100 m²/grain and an aspect ratio greater than 10, wherein the peelable sealing structure defines a sealing surface.

18. The packaging system of item 16 wherein the organoclay comprises a clay selected from the group consisting of kaolinite, montmorillonite-smectite clays, bentonite clays, illite clays, and combinations thereof.

19. The packaging system of item 16 wherein the organoclay is present in an amount from 1 wt % to 20 wt % of the combined weight of the thermoplastic polymer and the organoclay.

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20. The packaging system of item 16 wherein the organoclay comprises a plurality of particles having at least one spatial dimension less than 200 nm.

21. The packaging system of item 16 wherein the thermoplastic polymer comprises a 5 polymer selected from the group consisting of nylons, polyolefins, polystyrenes, polyesters, polycarbonates, copolymers of ethylene, copolymers of propylene, and mixtures thereof.

22. The packaging system of item 21 wherein the thermoplastic polymer comprises ethylene vinyl acetate.

23. The packaging system of item 16 wherein the sealing substrate comprises a second sealing layer contacting the first sealing layer.

24. The packaging system of item 23 wherein the second sealing layer comprises:

a thermoplastic polymer; and an organoclay dispersed within the thermoplastic polymer.

25. The packaging system of item 16 wherein the sealing section further comprises one or more additional polymer layers disposed over the first sealing layer.

26. The packaging system of item 16 further comprising a food product contained therein.

27. The packaging system of item 16 further comprising a sterilized object contained therein.

28. The packaging system of item 27 wherein the sterilized object is a medical device.

29. The packaging system of item 16 wherein the container section has a shape selected from the group consisting of blisters, trays, bags, pouches, and combinations thereof.

The present invention solves one or more problems of the prior art by providing in at least one embodiment a peelable sealing structure. The peelable sealing structure of this embodiment advantageously includes a sealing surface that is formable into a peelable seal upon contact with a sealing substrate at all temperatures in a peelable seal temperature range. Moreover, the peelable sealing structure of this embodiment comprises a thermoplastic polymer, and an additive dispersed within at least a portion of the thermoplastic polymer.

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3 SEP

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In another embodiment of the present invention, a peelable scaling structure is useful for forming a peeluble seal at the opening of a container. The peelable sealing structure of this embodiment comprises a sealing layer and one or more optional additional layers. Advantageously, the sealing layer includes a functionalized organoclay dispersed with a thermoplastic polymer. The incorporation of functionalized organoclay particles within commonly used heat sealable thermoplastic polymers is found to provide a consistent peel strength over a broad range of heat scaling conditions. Moreover, the blend of commercially available organoclay polymer concentrates with a wide range of polyolefin sealant resins advantageously exhibits a peel strength inversely proportional to the percent load of organoclay. Although sealed interfaces utilizing the sealing layer peels in a consistent pattern, the hermetic integrity of the seal is not compromised even when the seal specimens include wrinkles, pleats and gusset configurations in various bag/pouch package styles.

In another embodiment of the present invention, a packaging system incorporating the peelable sealing structures of the invention is provided. The packaging system of the invention includes a container section and a peelable sealing section attached to the container section. The sealing section includes the sealing layer of the invention set forth above.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGURE 1A is a schematic illustration of an Adhesive Type A failure;

FIGURE IB is a schematic illustration of an Adhesive Type B failure;

FIGURE IC is a schematic illustration of a Delamination Type C failure;

FIGURE ID is a schematic illustration of a Break Type D failure;

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FIGURE IF is a schematic illustration of an Elongation Type F failure;

FIGURE IG is a schematic illustration of a Peel + Elongation Type G failure;

FIGURE 2A is a schematic cross-section of a single layer sealing structure;

FIGURE 2B is a schematic cross-section of a two layer sealing section;

FIGURE 2C is a schematic cross-section of a three layer sealing layer;

FIGURE 3A is a schematic cross-section of a pouch-like packaging system incorporating an embodiment of the peelable seuling structure of the invention;

FIGURE 3B is a side view of the pouch-likc packaging system of

Figure 3A;

FIGURE 4A is a schematic cross-section of a refinement in which a sealing substrate includes a second sealing layer;

FIGURE 4B is a schematic cross-section of a refinement in which 15 scaling substrate 160 includes second sealing layer 170 with peelable seal 162 being formed between first sealing layer 152 and second sealing layer 186;

FIGURE 5A Is a schematic cross-section of a cup-iike packaging system that uses the peelable seeling structures of the invention;

FIGURE 5B is a schematic cross-section of a blister packaging system 20 that uses the peelable seeling structures of the invention and incorporates multiple cup-like containers;

FIGURE 6 is a diagram illustrating a method of forming the packaging systems of the invention;

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FIGURE 7A provides plots of the peel force versus temperature fora lop seal formed from a scaling layer having 5 wt % and 6 wt % organoclay;

FIGURE 7B provides plots of the peel force versus temperature for seals made by the three layer co-extrusion of HDPE, EVOH, and a blend of LLDPE and EVA with and without added organoclay;

FIGURE 7C provides a plot of the peel force versus seal formation temperature for a seal made from a foil laminated to a sealing film;

FIGURE 8 is a scries of plots for determining the melting temperature (Tm);

FIGURE 9 is a series of plots for determining the crystallization temperature .(Tc); and

FIGURE 10A is a set of x-ray diffraction plots showing the dispersion of organoclay from Nanoblend 2001 within a sealing layer comprising polyethylene;

FIGURE 10B is u set of x-ray diffraction plots showing the dispersion 15 of organoclay from Nanoblend 2101 within a sealing layer comprising polyethylene;

FIGURE IJ provides plots of seal strength versus seal formation temperature for seals made by an impulse sealer;

FIGURE I2A provides plots of seal strength versus seal formation temperature for seals made from polyethylene or a blend of polyethylene and EVA made by a conduction scaling melhod;FIGURE I2B provides plots of seal strength versus seal formation temperature for seals in which at least one of the sealing layers includes a blend of polyethylene, EVA, and organoclay;

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3 SEP 2013 amendment

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FIGURE I3A provides Table 6 which summarizes the seal strength data for Figures 12A and 12B; and

FTGURE 13B is a continuation of Figure 13A;

FIGURE 14A is schematic cross-sections illustration of peelable seals 5 having one or more folds therein;

FIGURE 14B is schematic cross-sections illustration of peelable seals having one or more folds therein; and

FIGURE 15 is a top view of a packaging system that has folds or bends incorporated within Lhe seals.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT(S)

Reference will now be made in detail to presently preferred compositions, embodiments and methods of the present invention, which constitute the best modes of practicing the invention presently known to the inventors. The Figures arc not necessarily to scale. However, it is to be understood that the disclosed embodiments arc merely exemplary of the invention that may be embodied in various and alternative forms. Therefore, specific details disclosed herein arc not lo be interpreted as limiting, but merely as a representative basis for any aspect of the invention and/or as a representative basis for teaching one skilled in the art to variously employ the present invention.

Except in the examples, or where otherwise expressly indicated, all numerical quantities in this description indicating amounts of material or conditions of reaction and/or use are to be understood as modified by the word about in describing the broadest scope ofthe invention. Practice within the numerical limits stated is generally preferred. Also, unless expressly stated to the contrary, percent, pails of, and ratio values are by weight; the term polymer includes oligomer, copolymer, terpolymer, and the like; the description of a group or class of

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materials as suitable or preferred for a given purpose in connection with the invention implies that mixtures of any two or more of the members of the group or class are equally suitable or preferred; description of constituents in chemical terms refers to the constituents at the time of addition to any combination specified in the description, and does not necessarily preclude chemical interactions among the constituents of a mixture once mixed; the first definition of an acronym or other abbreviation applies to all subsequent uses herein of the same abbreviation and applies mutatis mutandis to normal grammatical variations of the initially defined abbreviation; and, unless expressly stated to the contrary, measurement of a property is determined by the same technique as previously or later referenced for the same property.

lt is also to be understood that this invention is not limited to the specific embodiments and methods described below, as specific components and/or conditions may, of course, vaiy. Furthermore, the terminology used herein is used only for the purpose of describing particular embodiments ofthe present invention and is nol intended to be limiting in any way.

It must also be noted that, as used in the specification and the appended claims, the singular form a, an, and the comprise plural referents unless the context clearly indicates otherwise. For example, reference to a component in the singular is intended to comprise a plurality of components.

Throughout this application, where publications are referenced, the disclosures of these publications in their entireties are hereby incorporated by reference into this application in their entirety to more fully describe the state of the art to which this invention pertains.

The term organoclay as used herein means organically modified clay. Typically, such modification renders a clay more compatible and therefore mixablc with polymers.

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The term roughness average (R_a) as used herein means the mean height of a surface as calculated over the entire measured length or area in accordance with ANSI B46.1. It is usually provided in micrometers or micro-inches.

The term peelable seal as used herein means a seal that has a peel force of between

0.2 kg per 2.5 cm (0.5 lbs per one inch) of sample width and a force that tears the seal. Typically, the upper limit is less than or equal to 2.3 kg per 2.5 cm (5 lbs per inch) of sample width. In other variation, the upper limit is less than or equal to 1.8 kg per 2.5 cm (4 lbs per inch) of sample width or less than the tear strength on the film substrate.

The term peel force as used herein means force to separate two layers as defined in ASTM F-88 which is incorporated by references. For example, this is the force necessary to separate two layers of one inch width by pulling.

The term seal initiation temperature as used herein refers to the lowest temperature at which a seal is formed with a peel force of 0.2 kg per 2.5 cm (0.5 lbs per inch). Specifically, the seal initiation temperature is the temperature of a surface (typically metal) contacting a layer or layers that are to be sealed thereby promoting such sealing. In some variations, the surface contacts the layer(s) with a dwell time from about 0.5 to 1 seconds with a pressure from 34.5 kPa to 8273.7 kPa (5 psi to 1200 psi).

The term peelable seal temperature range means the range of temperatures at which a seal between two materials is formed such that the peel force is between .2 kg per 2.5 cm (0.5 lbs per one inch) of sample width and a force that tears the seal as set forth above.

With reference to FIGS. 1A-1G, schematic illustrations are provided illustrating various seal failure mechanisms. In each variation of these figures, seal 100 is formed from contact of a section of first sealing layer 102 with a section of second sealing layer 104 to form a seal. FIG. 1A illustrates the behavior of a peelable seal in accordance with one or more embodiments of the present invention. When a seal between layers 102 and 104 is subjected to a force that acts to pull these layers apart, layers 102, 104 separate relatively cleanly at separation surfaces 106, 108.

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ίο

This seal failure is referred to as an Adhesive Type A failure. FIG. IB illustrates a seal in which the structure integrity of layer 102 fails when the seal is stressed forming tear 109. This seal failure is referred to as an Adhesive Type B failure. FIG. 1C illustrates a seal which includes additional layers to form a multilayer laminate structure. Layer 110 is attached to layer 102 while layer 104 is attached to layer 112. The mode of failure illustrated in FIG. 1C is delamination at position 114. This seal failure is referred to as a Delamination Type C failure. FIG. ID illustrates a material failure in which layer 104 breaks at position 120 close to a region in which layers 102, 104 are still adhered to one another. This seal failure is referred to as a Break Type D failure. FIG. IE illustrates a material failure in which layer 104 breaks at position 122 remote from a region in which layers 102, 104 are still adhered to one another. This seal failure is referred to as a Break Type E failure. FIG. IF illustrates a material failure in which layers 102 and 104 stretch at sections 130, 132 that is not incorporated in seal 100. This seal failure is referred to as an Elongation Type F failure. Finally, FIG. 1G illustrates a material failure in which layers 102 104 separate at seal 100 by a peeling mechanism with a concurrent stretching at sections 136, 138. This seal failure is referred to as a Peel + Elongation Type G failure. Embodiments of the present invention advantageously form peelable seals that fail via the Adhesive Type A failure mechanism.

In all embodiment of the present invention, a peelable sealing structure is provided.

The peelable scaling structure of this embodiment comprises a thermoplastic polymer and an additive dispersed within at least a portion of the thermoplastic polymer. The peelable sealing structure defines a sealing surface that is formable into a peelable seal at all temperatures within a peelable seal temperature range. In a variation of this embodiment, the peelable seal temperature range is from a seal initiation temperature to a temperature that is that is at least 10.0 °C (50 °F) above the seal initiation temperature. In another embodiment of the present invention, the peelable seal temperature range is from a seal initiation temperature to a temperature that is that is at least 23.9 °C (75 °F) above the seal initiation temperature. In still another embodiment of the present invention, the peelable seal temperature range is from a seal initiation temperature to a temperature that is at least 37.8 °C (100 °F) above the seal initiation temperature. Typically, for packaging applications the seal initiation

3 SEP · \ temperature ranges from about 76.7 °C to about 176.7 °C (about 170 °F to about 350 °F). In another variation, for packaging applications the seal initiation temperature ranges from about

76.7 °C to about 121.1 °C (170 °F to about 250 ° F).

With reference to FIGS. 2A, 2B, and 2C, illustrations of a peelable sealing structure used in the packaging systems of the present invention is provided. In this embodiment, the peelable sealing structure is attached to a substrate to form a peelable seal or sealing section. FIG. 2A is a schematic cross-section of a single layer sealing structure. In this variation, peelable sealing structure 150 includes sealing layer 152. FIG. 2B is a schematic io cross-section of a two layer sealing structure. Peelable sealing structure 150 includes sealing layer 152 and additional layer 154. FIG. 2C is a schematic cross-section of a three layer sealing layer. In this variation, peelable sealing structure 150 includes sealing layer

152 and additional layers 154, 156.

It should be appreciated that in each of the variations of FIGS. 2A, 2B and 2C, sealing layer 152 comprises a thermoplastic polymer, and an additive dispersed within the thermoplastic polymer. In a variation of the present embodiments, useful additives have a surface area greater than 100 m²/gram and an aspect ratio greater than 10. Additionally, useful additions are crystalline or polycrystalline. Examples of useful additives include, but arc not limited to, organoclays. Sealing layer 152 is adapted to contact a substrate section of a container to form a peelable seal. Such containers may be of virtually any shape that is useful to package an object. Examples of such shapes include, but are not limited to, blisters, trays, bags, pouches, and combinations thereof.

It has surprisingly been discovered that sealing layers formed from this composition have improved and uniform peel performance as described more completely below. Scaled interfaces utilizing peelable sealing structure 150 peel in a consistent pattern, the hermetic integrity of the seal is not compromised even when the film specimens include wrinkles, pleats and gusset configurations in various bag/pouch package styles. Peelable sealing structure 150 exhibits a consistent peelable behavior in the following combinations: 1) sealing layer 152 contacting

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3 SEP 2013 j

I amendment/

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another sealing layer of analogous or the same composition; 2) sealing layer 152 contacting a structure formed from neat sealant (e.g. organoclay/polyethylene layer against a neat polypropylene layer, organoclay/polyethylene layer against neat polyester layer, organoclay/polyethylene layer against a neat polyethylene layer).

Processing aids such as antiblocking agents, antioxidants, slip additives, and the like arc optionally included into the sealing layers and do not affect the peel pattern of sealing structure 150.

Additional layers 154, 156 are used to provide a number of useful features to the present embodiment. For example, additional layers 154, 156 may 10 provide structural support, heat resistance, barrier properties, and improved appearance to packaging systems that incorporate peelable sealing sections, lt should also be appreciated that the present embodiment encompasses, in addition to single layer pcclable sealing structures, multilayer structures having any number of additional layers. In each variation of the present embodiment, the multilayer sealing structures include peelable sealing having the compositions described herein.

Sealing layer 152 is further characterized by various physical and structure variations and refinements which depend to some extent on the specific packaging desired. In one variation of the present embodiment, sealing layer 152 has a thickness from about 6 microns to about 120 microns. In another variation of the present embodiment, scaling layer 152 has a thickness from about 6 microns to about 30 microns. In still another variation of the present embodiment, sealing layer 152 has a thickness from about 40 microns to about 120 microns. Sealing layer 152 is further distinguished from analogous layers formed without or with insufficient amounts of organoclay in having a higher degree of surface roughness. In one refinement, sealing layer 152 has a surface roughness characterized by a roughness average from about 1500 to about 5000 angstroms. In another refinement, scaling layer 152 has a surface roughness characterized by a roughness average from about 2000 to about 4000 angstroms. It should be readily appreciated that in variations of the present invention, the degree and the quality of the surface roughness depends both on the methods and process parameters used lo form sealing layer 152. The sealing layers of various embodiments also exhibit somewhat higher tensile moduli than analogous layers

3 SEP KM ^WlENDWiENT without organoclay. In one refinement, the scaling layer 152 has a tensile modulus from about 500 to about 2000 MPa.

With reference to Figures 3A and 3B, a packaging system incorporating the peelable sealing structures set forth above is described. Figure 3A is a crosssection of a pouch-like packaging system incorporating an embodiment of the peelable scaling structure of the invention. Figure 3B is a side view of a pouch-like packaging system incorporating an embodiment of the peelable sealing structure of the invention. Packaging system 160 includes container section 162 and peelable sealing section 164. Peelable sealing section 164 is attached to container section 162. Figure 3A depicts an example in which peelable sealing section 164 andcontainer section 162 are continuous, each being formed from the same multilayer structure (i.e., sheet). Container section 162 can have virtually any shape that is useful for packaging an object in a pouch. Scaling section 164 includes peelable sealing structure 150. In the variation depicted in Figure 3A, pcelable sealing structure 150 includes sealing layer 152 disposed on additional layer 154. As set forth above in connection with the descriptions of Figures 2A, 2B, and 2C, sealing layer 152 comprises a thermoplastic polymer and an additive such as an organoclay dispersed within the thermoplastic polymer.

Still referring to Figures 3A and 3B, packaging system 160 further includes a second sealing structure 150' contacting pcelable scaling structure 150 to form peelable seal 170. Seal 170 seals an opening at top side 172 of packaging system 160. Similar peelable seals are optionally positioned at bottom side 174, left side 176, and right side 178. Peelable sealing structure 150' also includes sealing layer 152 disposed on additional layer 154. Specifically, a first portion of the combination of scaling layer 152 disposed on additional layer 154 forms sealing structure 150 while a second portion of the combination of sealing layer 152 disposed on additional layer 154 forms sealing structure 150'. Sealing structures 150, 150* are continuous with container section 162. In a variation of the present embodiment, a third portion of the combination of sealing layer 152 disposed on additional layer 154 at least partially forms container section 162. Advantageously, packaging system 160 is adapted to contain objcct(s) J 80 (i.e., may be one or more objects). Examples of object(s) 180 that may be packaged include, but are not limited to, food products and sterilized objects (e.g., medical devices).

With reference to Figures 4A and 4B, variations of peelable sealing section 164 as used in a pouch-like packaging systems are illustrated. Figure 4A is a schematic cross-section of a refinement in which sealing layer 152 is substantially confined to the vicinity of pcelable sealing section 164. This variation is achieved by either confining the incorporation of organoclay or by depositing a distinct layer in the vicinity of sealing structure 164. This variation further includes inner layer 182 and one or more additional layer 154. Figure 4B is a schematic cross-section of a refinement in which packaging system 160 includes second sealing layer 186 with peelable seal 170 being formed between first sealing layer 152 and second sealing layer 186. In this latter refinement, sealing layer 152 extends minimally, if at all, into container section 162. Moreover, in this refinement, container section 162 optionally includes liner layer 182 which is different than first scaling layer 152. In a further refinement of this variation, sealing section 164 further includes one or more additional polymer layer(s) 154 disposed over first sealing layer 152 and/or second sealing layer 186. In a particularly useful example of this refinement, one or more additional polymer layer(s) 154 at least partially form container section 162.

With reference to Figures 5A and 5B, variations of packaging systems using the peelable sealing structures of the invention with rigid container sections arc illustrated. Figure 5A provides a schematic cross-section of a cup-like packaging system that uses the peelable seeling structures of the invention. Packaging system 190 includes peelable sealing structure 150 and sealing opening 192 of container section 194. A peripheral portion of peelablc sealing structure 150 is disposed over and contacts substrate section 196 of container section 194. Figure 5B provides a schematic cross-section of a blister packaging system that incorporates multiple cuplikc containers. Blister packaging system 200 includes peelable sealing structure 152 and sealing openings 202, 204 of container sections 206, 208. A portion of peelable sealing structure 152 is disposed over and. contacts substrate sections 210, 212 of container sections 206, 208.

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As set forth above, the peelable scaling structures of the various embodiments of the invention include an additive such as organoclays. Examples of useful organoclays include, but arc not limited to, kaolinite, montmorillonite-smectite clays, bentonite clays, illite clays, and combinations thereof. U.S. Patent Nos.

5,780,376, 5,739,087, 6,034,163, and 5,747,560 provide specific examples of nanoclays that are useful in practicing the present invention. The entire disclosure of each of these patents is hereby incorporated by reference. In one refinement of the present invention, the organoclay is present in an amount from 1 wt % to 20 wt %of the combined weight of the thermoplastic polymer and the organoclay. In another refinement of the present embodiment, the organoclay is present in an amount from 2 wt % to 10 wt % of the combined weight of the thermoplastic polymer and the organoclay.

The organoclay used in peelable sealing layer 152 typically comprises a plurality of particles, in one variation, the organoclay comprises a plurality of 15 particles having at least one spatial dimension less than 200 nm. In another variation, the organoclay comprises a plurality of particles having at least one spatial dimension less than 100 nm. In another variation, the organoclay comprises a plurality of particles having at least one spatial dimension less than 50 nm. In still another variation, the organoclay comprises a plurality of particles having spatial dimensions greater than or equal to I nm. In still another variation, the organoclay comprises a plurality of particles having spatial dimensions greater than or equal to 5 nm. In another variation, the organoclay comprises platelets having an average separation of at least 20 angstroms, ln yet another variation, the organoclay comprises platelets having an average separation of at least 30 angstroms. In still another variation, the organoclay comprises platelets having an average separation of at least 40 angstroms. Typicully, before combining with the thermoplastic polymer, the organoclay comprises platelets having an average separation between from 20 to 45 angstroms. Advantageously, upon combining with the thermoplastic, the organoclay remains in this exfoliated state such that the average separation is maintained or increased.

As set forth above, peelable sealing layer 152 also includes a thermoplastic polymer. Suitable thermoplastic polymers include, but are nol limited----1 3 SEP 2013 amendment

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IO to, nylons, polyolefins, polystyrenes, polyesters, polycarbonates, and mixtures thereof. In a variation, the thermoplastic polymer comprises a component selected from the group consisting of ethylene acrylic acid, ethylene ethyl acrylate, ethylene ionomers (e.g., the Surlyn® line of resins available from E.l. du Pont de Nemours and Company), and combinations thereof. Polyolefins are particularly useful thermoplastic polymers in the practice of the invention, ln one variation, the polyolefin is selected from the group consisting of homopolymers and copolymers of ethylene, propylene, vinyl acetate, and combinations thereof. A blend of polyolefins with ethylene vinyl acetate (EVA) is found to be particularly useful in forming peelable seals especially when the additive is an organoclay.

The container sections of the various embodiments of the invention are formed from virtually any material used for packaging. Such materials include, but are not limited to, paper, metal foil, polymeric sheets, metalized polymeric sheets, and combinations thereof. More specific examples include, oriented or non-oriented polyester, oriented or non-oriented polypropylene, oriented or non-oriented nylon, and combinations thereof. Each of these materials may be coated or uncoated. Examples of useful coatings include, but are not limited to, varnishes, lacquers, adhesives, inks, and barrier materials (i.e., PVDC). Useful materials for packaging medical devices include high density polyolefins. Tyvek® (a synthetic material made of high-density polyethylene fibers) commercially available from Dupont, Inc. is an example of a such a material used for packaging medical devices.

In yet another embodiment of the present invention, a method of forming the packaging systems set forth above is provided. With reference to Figure 6, a diagram illustrating the method of this embodiment is provided. A thermoplastic polymer (TP) is combined with an organoclay (OC) to form an organoclay-polymer blend (OCB) in step a). In one variation, this combining occurs in extruder 220. Sealing layer 152 is then fonned by extrusion from die 222 in step b) from the organoclay-polymer blend. In a variation, additional layer are formed by providing material from additional extruders (such as extruder 230) to die 222. In a refinement of the present embodiment, the thermoplastic polymer and the organclay are premixed in mixer 224 and then introduced into extruder 220. Typically, scaling— \ ( U SEP 2013 j \ amendment /

<img file="MY158291A_D0021.tif" />

layer 152 will be formed along with or onto one or more additional layers 154, 156 (as shown in Figure 2). Opened packaging system 160 is then formed in step c). This process may include steps in which the sides are sealed to produce the pouch structures of Figures 3-4. In a variation, the formation of opened packaging system

160 occurs during step b).

In a variation of the present embodiment, a thermoplastic polymer is combined with an organoclay by mixing a master batch with a neat polymer. In this variation, the master batch comprising the organoclay and at least a portion of the thermoplastic polymer. In this refinement, the master batch typically includes from

10 to 80 wt % organoclay.

The step of forming sealing layer 152 is accomplished by any method capable of producing layers or films from thermoplastic compositions. Examples of such methods include, but are not limited to, extrusion, co-extrusion, blow molding, casting, extrusion blow molding, and film blowing.

Still referring to Figure 6, the method of the present embodiment optionally further comprises placing object(s) 180 within open packaging system 160 (stepd). Typically, objcct(s) 180 reside within container section 162. After object(s) 180 arc placed within container section 162, sealing layer 152 is contacted with a sealing substrate (i.e., sealing structure 150') during step e) to form a seal. Sealing may be accomplished by any number of sealing methods known in the art. Examples, include, but are not limited to, conduction heat sealing, ultrasonic sealing, and induction sealing.

The following examples illustrate the various embodiments of the present invention. Those skilled in the art will recognize many variations that arc within the spirit of the present invention and scope of the claims.

Figure 7A provides plots of the peel force versus temperature for a seal formed from a sealing layer made from a co-extruded HDPE and a LLDPE/EVA and organoclay blend (i.e, a bi-layer). In these experiments, the seal of a sealed bag is

<img file="MY158291A_D0022.tif" />

3 SEP 7.015 ' .-..'JiNDWlEN'i

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ίο pulled apart. Plots for organoclay loadings of 5 and 6 wt % are provided. FIG. 7A demonstrates that the seals of the invention can be opened by a consistent opening force over a seal forming temperature range of 10.0 °C (50 °F). Moreover, the seal strength is observed to be peelable and relatively flat over the temperature range 93.3 °C to 121.1 °C (200 °F to 250 °F). FIG. 7B provides plots of the peel force versus seal formation temperature. Plots for a reference without organoclay and for a test sample with 5 wt % organoclay are provided. The reference sample consisted of a 2.4 mil film formed from a three layer coextrusion of high density polyethylene (HDPE), ethylene vinyl alcohol, linear low density polyethylene (EVOH), and a blend of ethylene vinyl acetate blend and LLDPE. The test sample consisted of a 2.4 mil film formed from a three layer coextrusion of HDPE, EVOH, and a blend of LLDPE EVA and 5 wt % organoclay. The reference and test samples were sealed in a Sentinal sealer. Peel force is determined in accordance with ASTM F-88. The seal time for the points in FIG. 7B is 0.50 sec and the seal jaw pressure is 206.8 kPa (30 psi). It is observed that the variation of the peel force over the temperature range 79.4 °C to 129.4 °C (175 °F to 265 °F) varied less for the sample with organoclay. Moreover, the seal formed with organoclays is peelable over that entire range of seal formation. FIG. 7C provides a plot of the peel force versus seal formation temperature for a seal made from a foil laminated to a sealing film. In this experiment, 48 ga PET/50 ga Foil is adhesively laminated to 3.2 mil test film. The test film is made from a LDPE/LLDPE/organoclay blend. The seal is made to a film of the same construction. The reference and test samples are sealed in a Sentinal sealer with peel force being determined in accordance with ASTM F-88. FIG. 7C clearly show a consistent peelable seal being formed at temperatures from 148.9 °C to 218.3 °C (300 °F to 425 °F).

Nanoblend.TM. MB 2001 or Nanoblend.TM. M MB 2101 (master batches) is mixed with a commercial polyethylepe (PE) blend pouch sealant in a singlescrew extruder with the sealant layer of tjie invention formed in a second film blowing operation. The tensile properties of the resulting films are evaluated in accordance to ASTM D638 (Table 1) with a test speed of 50 mm/min. Prior to testing, all samples are annealed for 21 days at 30.degree. C. Films that include an organoclay are found to have a higher modulus than films without organoclay without sacrificing strength or max.

<img file="MY158291A_D0024.tif" />

·&gt;

j 3 SEP 2013

AMENDMENT y elongation. The inereusc in modulus being 75% for 3 wt % organoclay, 150% for 6 wt % organoclay, and 240% for 9 wt % organoclay.

Table 1. Tensile properties of films formed with no added organoclay and various 5 amounts of organoclay.

<td colspan="2"></td><td> Tensile Modulus (MPa)</td><td> Tensile Strength (MPa)</td><td> Elongation at break (%)</td>

<td></td><td> unfilled (0% Clay)</td><td> 306 (±15)</td><td> 24(+1)</td><td> 324 (±11)</td>

<td></td><td> unfilled-TS* (0% Clay)</td><td> 329 (+5)</td><td> 24 (±1)</td><td> 291 (+5)</td>

<td> 2001</td><td> 3% Clay</td><td> 587 (±9)</td><td> 23 (±1)</td><td> 325(±11)</td>

<td></td><td> 6% Clay</td><td> 825 (±17)</td><td> 24(+1)</td><td> 396 (+ 6)</td>

<td></td><td> 9% Clay</td><td> 1129 (+25)</td><td> 23 (±1)</td><td> 295 (±23)</td>

<td> 2101</td><td> 3% Clay</td><td> 581 (±32)</td><td> 22(+1)</td><td> 316 (±17)</td>

<td></td><td> 6% Clay</td><td> 842 (+33)</td><td> 25 (±1)</td><td> 400 (± 1)</td>

<td></td><td> 9% Clay</td><td> 1106 (+66)</td><td> 22 (±1)</td><td> 294 (+13)</td>

*Unfilled-TS: Twin-screw extruded pure PE

Table 2 summarizes the results of VICAT Heat Deflection Testing.

The Vicat Softening Temperature is observed to increase with increasing organoclay content with a sample having 9 wt % nanoclay exhibiting a 23 C increase in softening temperature. The data of Table 2 implies that crystallinity is substantially uneffecled by the addition of organoclay to the polyethylene sealant composition.

Table 2. Vicat Softening Temperature as a function of organoclay content.

<img file="MY158291A_D0025.tif" />

22.

<td> Composition</td><td> HDT CC)</td>

<td> unfilled (0% clay)</td><td> 64.5</td>

<td> 3% by Nano200l</td><td> 70.5</td>

<td> 6% by Nano2001</td><td> 80.9</td>

<td> 9% by Nano200l</td><td> 87.0</td>

<td> 3% by Nano2101</td><td> 70.5</td>

<td> 6% by Nano2I01</td><td> 80.5</td>

<td> 9% by Nano2101</td><td> 87.0</td>

Crystallization temperature and melting temperature are also evaluated. These measurements are performed by measuring the enthalpies of fusion and crystallization in accordance with ASTM D 3417. Figure 8 provides plots for determining the melting temperature (Tm) while Figure 9 provides plots for determining the crystallization temperature (Tc) for layers containing varying amounts of Nanoblend™ MB 2001. Tm and Tc are observed to be substantially uncffected by the addition of nanoclay as compared to a pure polyethylene sample. Figure 10A provides a set of x-ray diffraction plots showing the dispersion of organoclay from Nunoblend 2001 within a sealing layer comprising polyethylene. Figure 10B provides a set of x-ray diffraction plots showing the dispersion of organoclay from Nanoblend 2101 within a sealing layer comprising polyethylene. The x-ray diffraction data demonstrates the mean separation of organoclay platelets is preserved (i.e., minimal agglomeration). Such preservation of separation allows for the achieved properties regarding pcelability, tensile strength, HDT, and the elongation of break of embodiments of the present invention.

Tables 3 and 4 provide surface roughness measurements for sealing layers formed by the present invention. In these examples, a coextruded bi-layer is formed. The smoother side is from an HDPE layer nol having organoclay. The rougher side is a LLDPE/EVA layer having organoclay. The organoclay-containing layers of the present invention arc found to have a higher degree of roughness than analogous samples not having organoclay. Moreover, the sample having 6 wt % organoclay has a greater amount of surface roughness than the.sample having 5 wt \a MEND Wl c Μ1 /

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I

I

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organoclay thereby showing that the amount of surface roughness tends to increase in the range of about 10% or less.

Table 3. Smoother side of the bi-layer sample having 5 wt % organoclay in the sealant layer

<td> Scan speed(pm/S), vertical range (um)</td><td> 10,13</td><td> 50,13</td><td> 10,1048</td><td> 50,1048</td>

<td> Average roughness (Ra)/A'</td><td> 2406</td><td> 2428</td><td> 2343</td><td> 2303</td>

<td> Maximum roughness (Mas Ra) /A'</td><td> 2538</td><td> 2617</td><td> 2343</td><td> 2279</td>

<td> Roughness (RMS) /A'</td><td> 2991</td><td> 3040</td><td> 2857</td><td> 3096</td>

Table 4. Rougher side of the bi-layer sample having 5 wt % organoclay in the sealant layer

<td> Scan speed (μιτι/S), vertical range (um)</td><td> 10,13</td><td> 50,13</td><td> 10,1048</td><td> 50,1048</td>

<td> Average roughness (R_A) /A</td><td> 6217</td><td> 5413</td><td> 5871</td><td> 5979</td>

<td> Maximum roughness (Max RJ /A</td><td> 5059</td><td> 4499</td><td> 5775</td><td> 574J</td>

<td> Roughness (RMS) /A'</td><td> 7947</td><td> 6917</td><td> 7571</td><td> 7648</td>

Table 5. Smoother side of the bi-layer sample having 6 wt % organoclay in the sealant layer

<td> Scan speed(pm/S), vertical range (um)</td><td> 10.13</td><td> 50.13</td><td> 10.1048</td><td> 50.1048</td>

<td> Average roughness (Ra)(A‘)</td><td> 2564</td><td> 2275</td><td> 3110</td><td> 3210</td>

<td> Maximum roughness (Max RJ (A’)</td><td> 1994</td><td> 1762</td><td> 2333</td><td> 2543</td>

<td> Roughness (RMS) (A*)</td><td> 3351</td><td> 2999</td><td> 3843</td><td> 3445</td>

Tabic 6. Rougher side of the bi-layer sample having 6 wl % organoclay in the sealant layer

<td> Scan speed (μηι/S), vertical range (um)</td><td> 10,13</td><td> 50,13</td><td> 10,1048</td><td> 50,1048</td>

<img file="MY158291A_D0028.tif" />

AMENDMENT

<td> Average roughness (Ra) (A”)</td><td> 7069</td><td> 6935</td><td> 7974</td><td> 6897</td>

<td> Maximum roughness (Max R_a)(A”)</td><td> 8081</td><td> 6977</td><td> 6600</td><td> 6412</td>

<td> Roughness (RMS) / A”</td><td> 9100</td><td> 8990</td><td> 9955</td><td> 8951</td>

FIG. 11 provides plots of seal strength versus seal formation temperature. In these experiments an impulse sealer is used for forming the seals. In such sealers the temperature is set by a dial position. FIG. 11 provides the seal strength as a function of dial position. Estimated temperatures are provided at the top of FIG. 11. FIG. 11, again, demonstrates the synergistic effect of the combination polyethylene, EVA, and organoclay with seals formed from this combination being peelable over a wide seal formation temperature range.

io

A series of 25.4 mm seals are made at a pressure of about 6894.8 kPa (1000 psi) with a sealing time of about 8 seconds. In these experiments a hydraulic press is used. Although these conditions are harsher than the conditions used in typical commercial scaling operations, the formations of peelable seals at these conditions further illustrates the ability of the formulations of the present invention to form peelable seal. FIGS. 12A and 12B provides plots of the seal strength versus seal formation temperature for various combinations of seal layers. In these experiments a seal is formed between a first sealing layer and a second sealing layer. In FIG. 12A each sealing layer includes polyethylene or a blend of polyethylene and EVA. In general, the seal strength increases with increasing temperature for these combinations over the temperature range 110 °C to 140 °C. In FIG. 12B, at least one of the scaling layers includes a blend of polyethylene, EVA, and organoclay. For seals formed in this manner, FIG. 12B illustrates the formation of peelable seals over a temperature range from 110 °C to 140 °C. FIGS. 13A and 13B provide Table 6 which summarizes the seal strength data for FIGS. 12A and 12B while characterizing the type of failure mode (see FIGS. 1A-1G). Table 6 clearly shows the formation of peelable seals over a wide range of temperatures.

In still another embodiment of the present invention, a peelable seal adapted to provide a leak-proof seal having one or more wrinkles incorporated therein is provided. With reference to FIGS. 14A and 14B, schematic cross-sections illustration of peelable

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3 SEP 2013

<img file="MY158291A_D0030.tif" />

seals incorporating one or more folds are provided. Peelable seal 250 includes first sealing layer 252 and second sealing layer 254. First sealing layer 252 include bends 258, 260 and fold 262. Similarly, second sealing layer 254 includes bends 264, 266. First layer sealing layer 252 includes first sealing surface 270 while second sealing layer 254 includes second sealing surface 272. Outer sealing surfaces 274, 276 are attached to additional layers as set forth above in connection with the descriptions of FIGS. 1-5. First sealing surface 270 contacts the second sealing surface 272 to form seal 280. FIG. 14B provides an illustration in which second sealing layer 254 includes minimal bends or folds.

io The details of the composition of sealing layers 252 and 254 are the same as those set forth above. In particular, at least one of the first sealing layer 252 and second sealing layer 254 include a thermoplastic polymer and an additive dispersed within the thermoplastic polymer. In a variation, the additive is present in a sufficient amount to form peelable seal 280 between the first sealing layer 252 and second sealing layer 254 at all temperatures within a peelable seal temperature range. As set forth above, in a refinement, the peelable seal temperature range is from a seal initiation temperature to a temperature that is at least 37.8 °C (100 °F) above the seal initiation temperature. In a particularly useful variation, the additive is an organoclay dispersed within at least a portion of the thermoplastic polymer. In such a variation, one or both of first sealing layer 252 and second sealing layer 254 have a seal initiation temperature from about 76.7 °C to about 176.7 °C (170 °F to about 350 °F). Additional details for the additive, the organoclay and the thermoplastic polymer are set forth above.

With reference to FIG. 15, a top view of a packaging system that tends to have folds or bends incorporated within the seals is provided. Package 290 includes peelable seals 292, 294, 296. It should be appreciated that packaging with only one or two side halving a peelable seal are also possible. Package 290 is depicted as containing food item 298. The presence of food item 298 within container section 300 during the packaging process causes a lifting of container wall 302. This lifting of container wall 302 induces the fonnation of bends and fold within peelable seals 292, 294, 296 as set forth in connection with the descriptions of FIGS. 14A and 14B. Packages such as those depicted in FIG. 15 are found to have a reduced incidence of leaks. For example, oxygen levels in a package using the organoclay compositionsrsel·^

3 SEP 2013

AMENDMENT

<img file="MY158291A_D0031.tif" />

forth above arc found lo be on average lower than a commercially available sealing composition. Moreover, test with liquids containing dyes are also found to have low incidence of leaks.

While embodiments of the invention have been illustrated and 5 described, it is not intended that these embodiments illustrate and describe all possible forms of the invention. Rather, the words used in the specification are words of description rather than limitation, and it is understood that various changes may be made without departing from the spirit and scope of the invention.