The present invention relates to a non-foil composite barrier structure for an improved container for citrus juices and other liquids. The container utilizes a paperboard barrier laminate for the containment of essential oils and the prevention of losses of vitamin C. Also disclosed is a process of making the laminate. The laminate makes use of an inner a buried barrier layer of a heat-sealable ethylene vinyl alcohol copolymer to enhance the barrier properties of the laminate.
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10. A container for liquids containing essential oils and flavors, said container having an interior and on exterior, constructed from a laminate comprising:
(a) a paperboard substrate with inner and outer surfaces, said inner surface being closer to the interior of the container than said outer surface; #10#
( #12# b) a thin 0.8 mil thick outer layer of a heat-sealable low density polyethylene polymer coated on exterior to said outer surface of said paperboard substrate; (c) an inner tie layer of an ethylene acrylic acid coated on interior to said inner surface of said paperboard substrate; (d) a 0.2 to 0.7 mil thick ethylene vinyl alcohol copolymer layer coated on interior to said tie layer; and (e) a thin 0.7 mil thick heat-sealable layer of low density polyethylene polymer coated on interior to said outer surface of said EVOH ethylene vinyl alcohol copolymer layer whereby said laminate can be heat-sealed on conventional equipment at temperatures ranging from 250° F- 500° F.
1. A container for liquids containing essential oils and flavors, said container having an interior and an exterior, said container constructed from a laminate comprising:
(a) a paperboard substrate with inner and outer surfaces, said inner surface being closer to the interior of the container than said outer surface; #10#
(b) a 12 lb. outer layer of a heat-sealable low density polyethylene polymer #12# coated on exterior to to said outer surface of said paperboard substrate; (c) an inner a coextruded sandwich layer comprising a 4.5 lb. tie layer, a 4.0 lb. heat-sealable ethylene vinyl alcohol copolymer layer and a 4.5 lb. tie layer extruded on interior to said inner surface of said paperboard substrate; and (d) a product-contact layer of a 10 lb. heat-sealable low density polyethylene polymer coextruded onto interior to said outer surface of said inner sandwich layer of tie layer--ethylene vinyl alcohol copolymer--tie layer whereby said laminate can be heat-sealed on conventional equipment at temperatures ranging from 250° F-500° F.
5. A container for liquids containing essential oils and flavors, said container having an interior and an exterior, said container constructed from a laminate comprising:
(a) a paperboard substrate with inner and outer surfaces, said inner surface being closer to the interior of the container than said outer surface; #10#
(b) a thin 0.8 mil thick outer layer of a heat-sealable low density polyethylene polymer #12# coated on exterior to said outer surface of said paperboard substrate; (c) an inner a coextruded thin tie layer and a 0.2 to 0.7 mil thick layer of a heat-sealable ethylene vinyl alcohol copolymer, coextruded on interior to said inner surface of said paperboard substrate, said heat-sealable ethylene vinyl alcohol copolymer layer being interior to said tie layer; and (d) a thin 0.7 mil thick product contact layer of a heat-sealable low density polyethylene polymer coated on an outer surface of interior to said tie material- ethylene vinyl alcohol copolymer layer whereby said laminate can be heat-sealed on conventional equipment at temperatures ranging from 250° F-500° F.
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6. The container as claimed in
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8. The container as claimed in
9. The container as claimed in
11. The container as claimed in
12. The container as claimed in
13. The container as claimed in
14. The container as claimed in
with functional groups. 16. The container as claimed in claim 10 wherein said tie layer is an ethylene based copolymer with functional groups. #10# 17. A container for liquids containinq essential oils and flavors, said container having an interior and an exterior, said container constructed from a laminate comprising: #12#
(a) a paperboard substrate with inner and outer surfaces, said inner surface being closer to the interior of the container than said outer surface; (b) a thin outer layer of a heat-sealable low density polyethylene polymer exterior to said outer surface of said paperboard substrate; (c) a coextruded sandwich layer comprising a 4.5 lb. tie layer, a 4.0 lb. heat-sealable ethylene vinyl alcohol copolymer layer and a 4.5 lb. tie layer interior to said inner surface of said paperboard substrate; and (d) a product-contact layer of a heat-sealable low density polyethylene poltmer interior to said outer surface of said inner sandwich layer of tie layer--ethylene vinyl alcohol copolymer--tie layer whereby said laminate can be heat-sealed on conventional equipment at temperatures ranging from 250° F- 500° F. 18. The container as claimed in claim 17 wherein said outer layer of low density polyethylene polymer is corona discharge treated to enhance printability of said laminate. 19. The container as claimed in claim 17 wherein said outer layer of low density polyethylene polymer is flame treated to enhance printability of said laminate. 20. The container as claimed in claim 17 wherein said tie layer is an ethylene based copolymer with functional groups. 21. A container for liquids containing essential oils and flavors, said container having an interior and an exterior, said container constructed from a laminate comprising: (a) a paperboard substrate with inner and outer surfaces, said inner surface being closer to the interior of the container than said outer surface; (b) a thin outer layer of a heat-sealable low density polyethylene polymer exterior to said outer surface of said paperboard substrate, (c) a coextruded thin tie layer and a 0.2 to 0.7 mil thick layer of a heat-sealable ethylene vinyl alcohol copolymer, interior to said inner surface of said paperboard substrate, said heat-sealable ethylene vinyl alcohol copolymer layer being interior to said tie layer; and (d) a thin product contact layer of a heat-sealable low density polyethylene polymer interior to said ethylene vinyl alcohol copolymer layer whereby said laminate can be heat-sealable on conventional equipment at temperatures ranging from 250° F- 500° F. 22. The container as claimed in claim 21 wherein said outer layer of low density polyethylene polymer is corona discharge treated to enhance printability of said laminate. 23. The container as claimed in claim 21 wherein said outer layer of low density polyethylene polymer is flame treated to enhance printability of said laminate. 24. The container as claimed in claim 22 wherein said surface of said inner layer of said heat-sealable ethylene vinyl alcohol copolymer is corona discharge treated to enhance adhesion of said thin heat-sealable LDPE layer. 25. The container as claimed in claim 23 wherein said surface of said inner layer of said heat-sealable ethylene vinyl alcohol copolymer is flame treated to enhance adhesion of said heat-sealable LDPE layer. 26. The container as claimed in claim 21 wherein said tie layer is an ethylene based copolymer with functional groups. 27. A container for liquids containing essential oils and flavors, said container having an interior and on exterior, constructed from a laminate comprising: (a) a paperboard substrate with inner and outer surfaces, said inner surface being closer to the interior of the container than said outer surface; (b) a thin outer layer of a heat-sealable low density polyethylene polymer exterior to said outer surface of said paperboard substrate: (c) an inner tie layer interior to said inner surface of said paperboard substrate: (d) a 0.2 to 0.7 mil thick ethylene vinyl alcohol copolymer layer interior to said tie layer: and (e) a thin heat-sealable layer of low density polyethylene polymer interior to said ethylene vinyl alcohol copolymer layer whereby said laminate can be heat-sealable on conventional equipment at temperatures ranging from 250° F- 500° F. 28. The container as claimed in claim 27 wherein said outer layer of low density polyethylene polymer is corona discharge treated to enhance printability of said aminate. 29. The container as claimed in claim 27 wherein said outer layer of low density polyethylene polymer is flame treated to enhance printability of said laminate. 30. The container as claimed in claim 28 wherein said inner layer of ethylene vinyl alcohol copolymer is corona discharge treated to enhance adhesion of said subsequent heat-sealable LDPE coating. 31. The container as claimed in claim 29 wherein said inner layer of ethylene vinyl alcohol copolymer is flame treated to enhance adhesion of said subsequent heat-sealable LDPE coating. 32. The container as claimed in claim 27 wherein said tie layer is an ethylene based copolymer with functional groups. 33. A container for liquids containing essential oils and flavors, said container having an interior and an exterior, said container constructed from a laminate comprising: (a) a paperboard substrate with inner and outer surfaces, said inner surface being closer to the interior of the container than said outer surface; (b) a thin outer layer of a heat-sealable, low density polyethylene polymer exterior to said outer surface of said paperboard substrate; (c) a 0.2 to 0.7 mil thick ethylene vinyl alcohol copolymer layer interior to said inner surface of said paperboard substrate; and (d) a thin heat-sealable layer of low density polyethylene polymer interior to said ethylene vinyl alcohol copolymer layer whereby said laminate can be heat-sealed on conventional equipment at temperatures ranging from 250° F.- 500° F. 34. The container as claimed in claim 33 wherein said outer layer of low density polyethylene polymer is corona discharged treated to enhance printability of said laminate. 35. The container as claimed in claim 33 wherein said outer layer of low density polyethylene polymer is flame treated to enhance printability of said laminate. 36. The container as claimed in claim 34 wherein said inner layer of ethylene vinyl alcohol copolymer is corona discharged treated to enhance adhesion of said subsequent heat-sealable low density polyethylene polymer coating. 37. The container as claimed in claim 35 wherein said inner layer of ethylene vinyl alcohol copolymer is flame treated to enhance adhesion of said subsequent heat-sealable low density polyethylene polymer coating. 38. A container for liquids containing essential oils and flavors, said container from a laminate comprising: (a) a paperboard substrate with inner and outer surfaces, said inner surface being closer to the interior of the container than said outer surface; (b) a thin 0.8 mil thick outer layer of a heat-sealable low density polyethylene polymer exterior to said outer surface of said paperboard substrate; (c) a 0.2 to 0.7 thick ethylene vinyl alcohol copolymer layer interior to said inner surface of said paperboard substrate; and (d) a thin 0.7 mil thick heat-sealable layer of low density polyethylene polymer interior to said ethylene vinyl alcohol copolymer layer whereby said laminate can be heat-sealed on conventional equipment at temperatures ranging from 250° F.- 500° F. 39. The container as claimed in claim 38 wherein said outer layer of low density polyethylene polymer is corona discharged treated to enhance printability of said laminate. 40. The container as claimed in claim 38 wherein said outer layer of low density polyethylene polymer is flame treated to enhance printability of said laminate. 41. The container as claimed in claim 39 wherein said inner layer of ethylene vinyl alcohol copolymer is corona discharged treated to enhance adhesion of said subsequent heat-sealable low density polyethylene polymer coating. 42. The container as claimed in claim 40 wherein said inner layer of ethylene vinyl alcohol copolymer is flame treated to enhance adhesion of said subsequent heat-sealable low density polyethylene polymer coating. |
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Density Polyethylene density polyethylene (HDPE) 22-LDPE 24. The laminate disclosed exhibits large losses of essential oils during its shelf life of six weeks, namely 60.5%, while also exhibiting large losses of vitamin C during the six week period, namely 87% (see Table 1). The economics and ease of fabrication of the laminates of FIG. 3 are outweighed by the poor barrier properties exhibited.
FIG. 4 discloses the preferred embodiment of U.S. Pat. No. 4,513,036, namely a barrier laminate comprising LDPE 26-Paperboard 28-Polypropylene 30-LDPE 32. The additional polypropylene layer 30 and to the barrier properties at relatively low additional costs. The barrier properties still are extremely deficient in resistance to the passage of oxygen and loss of vitamin C, namely 71% after six weeks. The polypropylene laminate structure loses 39.5% of its essential oils (d-Limonene) after six weeks (see Table 1).
Both embodiments disclosed in the patent cited above do not adequately preserve the flavor/aroma and vitamin C content of the juice. The structure of the existing commercial constructions have all faced the same problem due to the necessity for heat sealing the seams and closures while forming the carton blank and while filling the cartons with juice or the like. The necessity of forming a heat seal from the front to the back of the laminate has resulted in the use of a thick exterior layer of LDPE and a thick interior layer of LDPE, both non-polar compounds which exhibit excellent heat-sealing characteristics to one another (see FIGS. 1-4).
Referring to FIG. 5, the preferred embodiment of the laminate of the present invention is shown as comprising a paperboard substrate 36 of varying thickness which is most suitably high-grade paperboard stock, for example, 282 lb Milk Carton Board, to which is applied on one side a coating of low density polyethylene (LDPE) 34, in a coating weight ranging from about 9 to about 15 pounds per ream. Any commercial extrusion coating grade LDPE is suitable for use herein. On the back or interior portion of the laminate, namely onto the paperboard layer 36, is coextruded a sandwich 44 of a 4.5 lb tie material (Plexar 177) 38/4.0 lb EVOH (EVAL) 40/4.5 lb tie material (Plexar 177) 42. The EVOH being a barrier layer composed of EVAL Company of America's EVAL EP resins. Extruded thereon is a coating of 10 lbs LDPE 46.
Referring to FIG. 6, the alternate embodiment of the laminate of the present invention is shown as comprising a paperboard substrate 54 of varying thickness which is suitably high grade paperboard stock, i.e., 282 lb milk carton board, to which is applied on one side a very thin 0.8 mil coating of low density polyethylene (LDPE) 52, in a coating weight range averaging 12 lbs per 3000 square feet. Any commercial extrusion coating grade LDPE is suitable for use herein. On the back or interior portion of the laminate, namely onto the paperboard layer 54, a (Plexar 177) tie layer 56 and a layer of 0.2 to 0.7 mil of EVOH 56 are applied by coextrusion. The EVOH being a barrier layer composed of EVAL Company of America's EVAL EP resins. Extrusion coated thereon is a very thin 0.7 mil layer 58 of a non-polar LDPE.
Referring to FIG. 7, a third embodiment of the laminate of the present invention is shown as comprising a paperboard substrate 66 of varying thickness which is suitably high grade paperboard stock, i.e. 282 lb milk carton board, to which is applied on one side a very thin 0.8 mil coating of LDPE 64, a 0.2 to 0.7 mil layer of EVOH 68 is applied by extrusion coating. Extrusion coated thereon is a thin layer 70 of a non-polar LDPE.
Referring now to FIG. 8, wherein a block diagram discloses the method of forming the heat-sealable barrier laminate of FIG. 5.
The laminate can be easily fabricated. In Step A, the paperboard is flame treated two sides. Step B, a molten layer of the LDPE 34 is extrusion coated onto the paperboard substrate 36. Stop C, the LDPE layer 34 is corona discharge or flame treated in preparation for subsequent printing. Step D, the web is turned over to facilitate Step E, which has a sandwich layer 44 of Plexar 38/EVAL 40/Plexar 42 coextruded onto the paperboard substrate 36. In Step F, extrusion coating of a layer of LDPE 46 onto the sandwich layer 44 completes the laminate.
Referring now to FIG. 9, wherein a block diagram discloses the method of forming the heat sealable barrier laminate of FIG. 6.
In Step A, the paperboard is flame treated on two sides. Step B, a molten layer of LDPE 52 is extrusion coated onto the paperboard substrate 54. Step C, the LDPE layer 52 is corona discharge or flame treated to provide subsequent inner layer adhesion. Step D, the web is turned over to facilitate Step E, which has a layer of molten tie layer 56 and EVOH 56 coextruded onto the paperboard substrate 54. Step F, the tie/EVOH layer 60 has its surface corona discharge treated or flame treated to facilitate the adhesion of a subsequent interior product-contact thin LDPE coating 62 to complete the laminate.
Referring now to FIG. 10, wherein a block diagram discloses the method of forming the heat-sealable barrier laminate of FIG. 7.
In Step A, the paperboard 66 is flame treated on two sides. Step B, a layer of LDPE 64 is extrusion coated onto the paperboard substrate 66. Step C, the LDPE layer 64 is corona discharge or flame treated to provide subsequent inner layer adhesion. Step D, the web is turned over to facilitate Step E, which has a layer of molten EVOH 68 extrusion coated onto the paperboard substrate 66. Step F, EVOH layer 68 is corona discharge treated or flame treated to facilitate the adhesion of a subsequent interior product-contact thin LDPE coating to complete the laminate.
Although specific coating techniques have been described, any appropriate technique for applying the layers onto the paperboard substrate can be suitably employed, such as extrusion, coextrusion, or adhesive lamination or of single and/or multilayer films to paperboard to achieve the stated inventions of this patent.
The unique barrier effect provided by the laminate of the present invention to the % loss of essential oils and to the % loss of vitamin C is clearly demonstrated by the following example outlined in Table 1.
Standard 1/2 half gallon juice containers were prepared and filled with juice. A typical essential oil in the juice was d-Limonene d-limonene. The filled cartons were stored for a test period of six weeks after which the juice was analyzed to determine the percentage loss by weight of the essential oil d-Limonene and the percentage loss by weight of vitamin C.
All weights shown in lbs are given in as lbs per 3000 square feet.
| TABLE 1 |
| ______________________________________ |
| Test Sample % Loss of |
| 1/2 Gallon Juice % Loss of [Essential Oil] |
| Container Essential Oil |
| Vitamin C |
| ______________________________________ |
| LDPE/BOARD/LDPE 60.5 84 |
| (FIG. 1) |
| LDPE/BOARD/LDPE/FOIL/ |
| 35.5 24 |
| LDPE (FIG. 2) |
| LDPE/BOARD/HDPE/LDPE |
| 60.5 87 |
| (FIG. 3) |
| LDPE/BOARD/POLYPRO- |
| 39.5 71 |
| PYLENE/LDPE (FIG. 4) |
| LDPE/BOARD/PLEXAR- |
| 16.5 46 |
| EVOH-PLEXAR/LDPE |
| (FIG. 5) |
| ______________________________________ |
It can be clearly seen that the container prepared from a laminate of the present invention provides an almost complete barrier to the loss of essential oils far greater than has been present in existing structures. Additionally, the oxygen passage or percentage loss of vitamin C has been greatly reduced over all prior laminates not containing aluminum foil.
The effectiveness of the laminate of the present invention as a barrier to migration of essential oils and flavors, as well as a barrier to a loss of vitamin C permits a significant extension of shelf life of juice products packaged in containers constructed therefrom.
Gibbons, Charles E., Tanner, Cynthia L., Whillock, Allan A.
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| Executed on | Assignor | Assignee | Conveyance | Frame | Reel | Doc |
| Nov 13 1989 | International Paper Company | (assignment on the face of the patent) | / | |||
| Jan 31 2007 | International Paper Company | EVERGREEN PACKAGING INC | ASSIGNMENT OF ASSIGNORS INTEREST SEE DOCUMENT FOR DETAILS | 018883 | /0696 | |
| Jan 31 2007 | EVERGREEN PACKAGING INC | CREDIT SUISSE, SYDNEY BRANCH, AS SECURITY AGENT | SECURITY AGREEMENT | 018898 | /0613 | |
| May 04 2010 | BRPP, LLC | THE BANK OF NEW YORK MELLON, AS COLLATERAL AGENT | SECURITY AGREEMENT | 024411 | /0880 | |
| May 04 2010 | EVERGREEN PACKAGING, INC | THE BANK OF NEW YORK MELLON, AS COLLATERAL AGENT | SECURITY AGREEMENT | 024411 | /0880 |
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