The present invention relates generally to packaging. More specifically, this invention relates to packaging for food, medicine, and other perishable items.
Shelf life in packaging is often determined by the level of oxidation of perishable items inside a package. The presence of oxygen inside the package can cause anything from rancidity to discoloration to bacterial growth. It is therefore desirable to produce containers that have limited oxygen transmission.
Barrier layers have been used to reduce the transmission of oxygen and other detrimental gases through packaging. In plastic packaging, highly crystalline polymers, such as EVOH, are often used in a multi-layer structure to serve as a barrier to the transmission of oxygen and other detrimental gases. Even high quality barrier layers, however, will allow some transmission of gas and moisture. And, when moisture reaches a crystalline polymer barrier material, that material may become less crystalline (e.g., amorphous). When this occurs, the barrier material may lose its barrier properties (or at least experience a decrease in such properties), at which point the packaging may lose much of its ability to block the transmission of oxygen and other detrimental gases.
It would be desirable to provide packaging that is active insofar as being able to capture gas, moisture, or both. It would be particularly desirable to provide active packaging wherein the active component is incorporated into plural layers of a multi-layer packaging wall. Preferably, the active component would be incorporated into particular layers of the multi-layer wall in an arrangement that optimizes the wall's barrier performance. Ideally, the active component would not adversely impact the layers into which it is incorporated or other layers of the packaging wall. Instead, the packaging wall would preferably include multiple active layers that work synergistically with a plurality of barrier layers in the wall.
Certain embodiments of the invention provide a packaging wall containing an active component to capture moisture and/or gas that may otherwise pass through the packaging wall. The packaging wall comprises a multi-layer wall that includes at least six layers. The multi-layer wall includes a desired sequence of at least three layers, and this sequence is found at least twice in the packaging wall. Preferably, the active component is incorporated into the two outermost layers of the desired sequence, such that at least four layers comprising the active component are provided in the multi-layer wall.
In some embodiments, the invention provides a method for producing a packaging wall containing an active component to capture moisture and/or gas that may otherwise pass through the packaging wall. The method involves forming a multi-layer wall that includes at least six layers. The multi-layer wall is formed so as to comprise a desired sequence of at least three layers, and this sequence is found at least twice in the packaging wall. Preferably, the active component is incorporated into the two outermost layers of the desired sequence, such that at least four layers comprising the active component are provided in the multi-layer wall.
The following detailed description is to be read with reference to the drawings, in which like elements in different drawings have like reference numerals. The drawings, which are not necessarily to scale, depict selected embodiments and are not intended to limit the scope of the invention. Skilled artisans will recognize that the given examples have many useful alternatives, which fall within the scope of the invention.
The invention provides a multi-layer wall comprising an active component to capture moisture and/or gas. Many packaging containers must meet demanding barrier performance requirements. One notable example is retortable packaging. In retort, the contents of a container may include liquid, oxygen, moisture entrained oxygen, etc., and the atmosphere outside the container will typically include moisture and atmospheric oxygen. Moisture and oxygen thus may penetrate the packaging wall from both sides (i.e., from inside the container and from outside the container). Conventional barrier layers can reduce the transmission of oxygen and other detrimental gases through packaging walls. However, the performance of existing packaging systems (which commonly include at least one barrier layer) could be improved considerably.
The present invention provides a packaging wall that contains an active component to capture moisture and/or gas that may otherwise pass through the packaging wall. The active component in the packaging wall is particularly advantageous when the wall includes one or more barrier layers (e.g., oxygen barrier layers, such as EVOH). In such embodiments, the active component can protect the barrier layer(s) from environmental impact. As noted above, when moisture reaches a crystalline polymer barrier material, the material may become less crystalline (e.g., amorphous). If this occurs, then the barrier material may lose (or experience a decrease in) its barrier properties, at which point the packaging may lose much of its ability to block the transmission of oxygen and other detrimental gases. Thus, in preferred embodiments of the invention, the active component in the packaging wall prevents, reduces, or delays moisture reaching one or more barrier layers embedded within the wall.
The packaging wall can define, or be part of, a container or another packaging system for perishable items (e.g., oxygen-sensitive products). Examples of perishable items include food, medicine, beverages, and corrodible materials or devices, such as electronic devices. In many cases, the container or other packaging system holds an oxygen-sensitive food or beverage, such as juice, wine, beer, meat, fruit, vegetable, and/or dairy product, to name just a few. In some embodiments, the container or other packaging system defines, or is part of, a substantially air-tight enclosure around the perishable item. Reference is made to
The invention provides a packaging component comprising a multi-layer wall 1. In some embodiments, the multi-layer wall includes at least six layers, or more preferably at least ten layers. In the present embodiments, the multi-layer wall 1 includes a desired sequence (i.e., a “core sequence”) of at least three layers, or more preferably at least five layers, and this sequence occurs at least twice in the packaging wall. Reference is made to the exemplary embodiment of
protective boundary layer/tie layer/barrier layer/tie layer/protective boundary layer
Thus,
In the present embodiments, the core sequence can be found in the multi-layer wall 1 two times, three times, four times, six times, ten times, etc., depending upon the requirements of the particular application of interest. Thus, the multi-layer wall 1 may be characterized as “2×,” “3×,” “4×,” “5×” . . . “8×,” etc., where the number preceding the “×” refers to the number of periods of the core sequence that exists in the wall.
In the present embodiments, the active component preferably is incorporated into the two outermost layers 50′ of the core sequence. In addition, the active component preferably is contained in a plurality of layers 50 embedded within the wall 1. Thus, the wall 1 of the present embodiments preferably includes at least four layers 50 comprising the active component, as can be appreciated by referring to
With continued reference to
In embodiments like those of
As can be appreciated from the foregoing discussion, at least two of the layers comprising the active component preferably are embedded layers (i.e., layers having no major surface exposed to either the package's interior contents or the environment outside the package). Moreover, when the packaging wall includes at least three periods of the core sequence, the multi-layer wall 1 preferably includes at least four embedded active layers, when the wall includes at least four periods of the core sequence, there will preferably be at least six embedded active layers, and so on.
The multi-layer wall 1 preferably includes at least one oxygen barrier layer. The embodiments of
The oxygen barrier layers 10 can comprise any material that serves as an effective barrier to the transmission of oxygen or other detrimental gases through the packaging wall. Polymers and copolymers are preferred. Preferably, the oxygen barrier material has an oxygen permeability of less than 500 cm3 O2/m2·day·atmosphere (tested at 1 mil thick and at 25° C. according to ASTM DS 3985, the salient teachings of which are incorporated herein by reference). Particularly preferred are barrier materials like ethylene vinyl alcohol copolymer (EVOH), polyvinyl alcohol (PVOH), polyamide (PA), polyvinylidene dichloride (PVDC), polyacrylonitrile (PAN), polyethylene napthalate (PEN), metaxylylene adipamide (MXDX), hexamethylene adipamide (nylon 66), and blends. Useful ethylene vinyl alcohol copolymers are commercially available from Kuraray and Nippon Gohsei, both of Japan, as well as EVAL Company of America and Noltex, both of the United States. While polymers will generally be preferred, skilled artisans will appreciate that metal foils and certain other materials may also be used.
When the packaging wall is intended for retort applications, the polymer used should be one that is retortable (e.g., retortable ethylene vinyl alcohol copolymer). Commercially available retortable grades of EVOH include SG372 from Nippon Gohsei and XEP 335 from Kuraray and EVAL Company of America. Thus, in certain embodiments, the multi-layer wall 1 is retortable. Accordingly, certain embodiments provide a retortable container or another retortable packaging system 5. A retortable wall of packaging system remains clear without distortion after conditioning at 121° C. for 30 minutes.
When the multi-layer wall 1 includes one or more oxygen barrier layers, each oxygen barrier layer 10 preferably is separated, by at least one layer 30, from each active layer 50. Reference is made to
Conventional oxygen barrier materials, such as EVOH, tend not to adhere well to other layers. Therefore, it may be desirable to provide adhesive tie layers between the barrier layers 10 and the protective boundary layers 50. Tie layers are well known in the present art. Particularly preferred are tie layers formed of ionomers, vinyl chloride copolymers, polystyrene copolymers, or anhydride-grafted polymers. Examples are maleic-anhydride- or rubber-modified polymers, such as the Plexar series from Quantum Chemical Corp. In particularly preferred embodiments, maleic anhydride grafted olefin tie resins are used.
In certain embodiments, the multi-layer wall 1 includes at least four tie layers 30. This is the case in the embodiments of
Thus, multi-layer wall 1 includes an active component to capture moisture and/or gas. Preferably, the active component (or “active ingredient”) is one that absorbs, reacts with, or otherwise captures moisture, oxygen (and/or another detrimental gas), or both. The presence of the active component prevents or reduces moisture and/or gas penetration, and thus eliminates or reduces degradation of any barrier layers in the packaging wall (thereby preventing, or at least reducing, deterioration of the product inside the packaging).
The active component can be an oxidation catalyst, such as a transition metal catalyst that can readily interconvert between at least two oxidation states. In some embodiments, the active component comprises (or consists essentially of) a transition metal salt or organometal. In some cases, the active component is selected from the group consisting of an iron salt, a nickel salt, a copper salt, a manganese salt, and a cobalt salt.
If desired, the active component can be a functional, oxidizable polydiene, which serves as an oxygen scavenger. Non-limiting examples of functional, oxidizable polydiene as oxygen scavengers include epoxy functionalized polybutadiene (1,4 and/or 1,2), maleic anhydride grafted or copolymerized polybutadiene (1,4 and/or 1,2), epoxy functionalized polyisoprene, and maleic anhydride grafted or copolymerized polyisoprene.
Additionally, or alternatively, the active component can comprise water absorptive agents, such as polyacrylic-type compounds, zeolites, alkaline earth metal oxides, silica, or the like.
In some embodiments, the active component is an iron-based material, such as the ShelfPlus O2 material, which is commercially available from the Albis Plastic company, which is located in Hamburg, Germany. In some cases, using such an iron-based material may render the resulting product non-recyclable. Therefore, it may be preferred embodiment for certain applications to use the DEHA (N,N Diethylhydroxylamine) scavenging material, which is commercially available from the Chevron Phillips company, which is located in The Woodlands, Tex.
The active component may be incorporated into the protective boundary layers 50 by mixing or blending it with a desired carrier resin during formation of the multi-layer wall. For example, the active component can be provided in the form of particles distributed (e.g., uniformly) throughout the polymer of the protective boundary layer material. Additional details on useful active materials, useful polymer compositions for the protective boundary layers, and useful methods of incorporating the active component into the protective boundary layers can be found in U.S. Pat. Nos. 5,820,956 (Mitsubishi Gas Chemical Company, Inc.) and 6,793,994 (Honeywell International Inc.), as well as U.S. Patent Application No. US2009/0061057 (Cryovac), the salient teachings of each of which are incorporated herein by reference.
Thus, the protective boundary layers 50 comprise one or more active components. As a result, these layers 50 capture moisture and/or oxygen passing through the packaging wall 1. In preferred embodiments, the protective boundary layers 50 capture moisture, so as to prevent barrier layer(s) 10 in the wall from losing their good barrier properties. This can preserve the barrier properties of the packaging wall, thus providing an improved packaging system.
The protective boundary layers 50 can be based on a polymer or copolymer. The material selected preferably facilitates processing (e.g., does not stick to metal dies during extrusion). Useful resins for the protective boundary layers include PE, PP, Nylon, PC, PET, EEA, and the like. In one group of embodiments, each protective boundary layer 50 comprises a maleated polymer. If desired, an acid copolymer, such as DuPont's Surlyn® product, can be used. Skilled artisans in this technology area will be able to select other suitable polymer materials.
In certain embodiments, the multi-layer wall 1 includes the following layers:
protective boundary layer/tie layer/oxygen barrier layer/tie layer/protective boundary layer/protective boundary layer/tie layer/oxygen barrier layer/tie layer/protective boundary layer
Here, the protective boundary layers each comprise the active component, and the oxygen barrier layers each comprise a crystalline polymer or another oxygen barrier material.
The core sequence of layers can be formed by any suitable process. Coextrusion is preferred, and any known coextrusion methods can be used, including blown film or flat die techniques. Many useful techniques for producing multi-layer polymer structures are known to those skilled in the present technology area.
The core sequence of layers can be multiplied, so as to have the desired number of periods, using any suitable layer multiplier technology. Reference is made to U.S. Pat. Nos. 3,239,197 (Tollar) and 5,094,793 (Schrenk et al.), the teachings of each of which are incorporated herein by reference.
One particular non-limiting example, which is expected to be particularly advantageous, will now be described. The multi-layer wall would comprise a coextrusion composite consisting of (by volume values): 10% copolymer polypropylene/3% tie materials/5% Ethylene Vinyl Alcohol/3% tie material/10% copolymer polypropylene. The initial total thickness of the composite would be maintained throughout the multiplication process. The composite would be divided vertically into segments, spread to a width equal to the original composite width, thinned to half the original thickness and stacked upon each other. The process would be repeated as often as necessary to achieve the desired properties of the composite. The 10% copolymer polypropylene layers act as the protective boundary layers and contain 5% by volume ShelfPlus O2 oxygen scavenger. After the composite has been produced with the desired number of repeats of the initial structure, a final layer or multiple layers would be added to the multiplied composite. In the event the final outer layers are not completely compatible with the composite, a tie layer may be added to the multiplied composite to insure adhesion of the outer layers to the multiplied composite. The overall thickness of the total structure could range from 0.005″ to 0.125″ or greater. The outer layers or structural layer would generally comprise from 5% to 35% each of the total thickness.
One preferred method for creating the initial composite is by using a coextrusion feedblock. Those skilled in the present art would be fully able to perform such coextrusion, particularly given the present teaching as a guide. As already explained, the composite is divided vertically (could be divided into two segments, four segments, or however many is desired), spread, thinned, and stacked. Down stream of the multiplier, another feedblock or multi-cavity die can add final outer layers (using another feedblock may be preferable). The final combination of layers is fed into an extrusion die for shaping the final product. The shaping process involves spreading and thinning the composite, for example, from 1″ to 6″ in width by 0.375″ to 1″, to a finished product from 6″ in width to 120 inches in width by the above thicknesses of 0.005″ to 0.125″ or greater. These details are merely exemplary; they are by no means limiting.
While a preferred embodiment of the present invention has been described, it should be understood that various changes, adaptations and modifications may be made therein without departing from the spirit of the invention and the scope of the appended claims.
This application claims the benefit of U.S. Provisional Application No. 61/440,062, filed on Feb. 7, 2011, the content of which is hereby incorporated by reference in its entirety.
Number | Date | Country | |
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61440062 | Feb 2011 | US |