IP Library Granted Patent US 8,309,622
Granted Patent B2
US 8,309,622 · App. 13/349,069 · Granted Nov 13, 2012

Enhanced oxygen-scavenging polymers, and packaging made therefrom

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Quick Facts
Patent No.
US 8,309,622
App. No.
13/349,069
Granted
Nov 13, 2012
Kind
B2
Abstract

Oxygen-scavenging polymers and packaging for holding oxygen-sensitive products. A heat treatment process has been found to significantly increase the oxygen-scavenging performance of the polymer. The enhanced scavenging polymer can be effectively incorporated into various packaging, including transparent multilayer containers for beer and juice. In one embodiment, a multilayer package made from the scavenger provides an actual reduction in oxygen content of a contents of the package, over a long period of time (e.g., 24 weeks). The package can be stored unfilled for an extended period (without significant loss of scavenging capability) and will scavenge substantially immediately upon filling with a liquid product. The package may incorporate a relatively low weight percentage of the scavenger, thus providing enhanced scavenging in a cost-effective manner.

Claims (37)

1. A composition comprising:

an oxygen scavenging composition comprising a solid-stated polyamide and a transition metal in an amount of at least 200 ppm in the polyamide,

the solid-stated polyamide formed by heat treatment at a temperature above the glass transition temperature and below the melting temperature of the polyamide while under a low oxygen content atmosphere and in the presence of the metal or the metal being added to the polyamide after being solid-stated, and

having an oxygen scavenging performance greater by a factor of at least 1.3 as compared to a composition of the transition metal and non solid-stated polyamide.

2. The composition of claim 1 , wherein the composition comprises 200 to 2000 ppm of the transition metal.

3. The composition of claim 2 , wherein the composition comprises 300 to 1000 ppm of the transition metal.

4. The composition of claim 1 , wherein the polyamide is selected from an aromatic polyamide, an aliphatic polyamide, nylon, an MXD polyamide and a xyliene-substituted polyamide.

5. The composition of claim 4 , wherein the transition metal is selected from a cobalt compound, cobalt carboxylate and cobalt neodecorate.

6. The composition of claim 1 , wherein the polyamide comprises an MXD polyamide and the comprises cobalt carboxylate.

7. The composition of claim 1 , wherein the oxygen scavenging performance is greater by a factor of at least 2.

8. The composition of claim 1 , wherein the oxygen scavenging performance is greater by a factor of at least 4.

9. A package having a wall, the wall including an internal layer comprising the oxygen-scavenging composition of claim 1 , wherein the package when filled with an aqueous liquid having an oxygen concentration of 9000 ppb or less and sealed, removes dissolved oxygen from the liquid.

10. The package of claim 9 , wherein the package maintains the oxygen content of the liquid below 200 ppb for at least 3 months.

11. The package of claim 9 , maintains the oxygen content of the liquid below 100 ppb for at least 3 months.

12. The package of claim 9 , wherein the package reduces the oxygen content of the liquid at a rate of at least 50 ppb/day.

13. The package of claim 9 , wherein the package can be stored unfilled in an ambient atmosphere containing 21% oxygen for at least 3 months prior to said filling with an aqueous liquid.

14. The package of claim 9 , wherein the wall comprises one or more internal layers of the oxygen-scavenging composition between one or more layers of aromatic polyester polymers.

15. The package of claim 9 , wherein the wall includes at least one layer of the oxygen-scavenging composition between polyethylene terephthalate layers.

16. The package of claim 9 , wherein the wall of the package is substantially transparent and biaxially-oriented.

17. The package of claim 9 , wherein the package is a substantially transparent and biaxally-oriented multilayer plastic bottle.

18. The package of claim 17 , wherein the bottle includes at least one internal layer of the oxygen-scavenging composition between layers of aromatic polyester polymers.

19. The package of claim 18 , wherein the package is filled with a food or beverage product.

20. The package of claim 18 , wherein the product is selected from a tomato-based food product, beer and juice.

21. The package of claim 18 , wherein the oxygen-scavenging composition comprises no more than 10% of the weight of the package.

22. A plastic package comprising:

at least one internal layer comprising an oxygen-scavenging composition comprising a solid-stated polyamide and a transition metal in an amount of at least 200 ppm in the polyamide,

the solid-stated polyamide formed by heat treatment at a temperature above the glass transition temperature and below the melting temperature of the polyamide while under a low oxygen content atmosphere and in the presence of the metal or the metal being added to the polyamide after being solid stated, and

the composition having an oxygen scavenging performance greater by a factor of at least 1.3 as compared to a composition of the transition metal and non solid-stated polyamide.

23. The package of claim 22 , wherein the package is stored unfilled in an ambient atmosphere for at least 3 months prior to filling with an aqueous liquid.

24. The package of claim 23 , wherein the package is filled with an aqueous liquid having an oxygen concentration of 200 ppb or less and sealed, and the sealed container reducing and maintaining the oxygen concentration of the liquid below 200 ppb for 32 weeks.

25. the package of claim 24 , the package having a substantially transparent, biaxially-oriented multi-layer wall including the at least one internal layer of the oxygen-scavenging composition and one or more layers of polyester.

26. The package of claim 24 , wherein the aqueous liquid comprises beer, juice or a tomato-based food product.

27. A plastic package comprising:

a package having at least one internal layer comprising an oxygen scavenging composition comprising a solid-stated polyamide and a transition metal in an amount of at least 200 ppm in the polyamide, and

the package being filled with an aqueous liquid having an oxygen concentration of 100 ppb or less and sealed, the sealed package reducing and maintaining the oxygen concentration of the liquid below 100 ppb for 32 weeks; and

the solid-stated polyamide formed by heat treatment at a temperature above the glass transition temperature and below the melting temperature of the polyamide while under a low oxygen content atmosphere and in the presence of the metal or the metal being added to the polyamide after being solid stated, and

the composition having an oxygen scavenging performance greater by a factor of at least 1.3 as compared to a composition of the transition metal and non solid-stated polyamide.

Assignments (4)
RELEASE OF SECURITY INTEREST Recorded Jan 26, 2026
From: UBS AG, STAMFORD BRANCH, AS COLLATERAL AGENT
To: GRAHAM PACKAGING COMPANY, L.P.; GRAHAM PACKAGING PET TECHNOLOGIES INC.; GRAHAM PACKAGING PLASTIC PRODUCTS LLC
Reel/Frame 074480/0105 →
RELEASE OF SECURITY INTEREST IN CERTAIN PATENT COLLATERAL Recorded Aug 4, 2020
From: THE BANK OF NEW YORK MELLON, AS THE COLLATERAL AGENT AND TRUSTEE
To: GRAHAM PACKAGING PET TECHNOLOGIES INC.
Reel/Frame 053396/0497 →
SECURITY INTEREST Recorded Aug 4, 2020
From: GRAHAM PACKAGING COMPANY, L.P.; GRAHAM PACKAGING PET TECHNOLOGIES INC.; GRAHAM PACKAGING PLASTIC PRODUCTS LLC
To: CREDIT SUISSE AG, CAYMAN ISLANDS BRANCH, AS ADMINISTRATIVE AGENT
Reel/Frame 053398/0381 →
PATENT SECURITY AGREEMENT Recorded Mar 22, 2012
From: GRAHAM PACKAGING PET TECHNOLOGIES INC.
To: THE BANK OF NEW YORK MELLON
Reel/Frame 027910/0567 →