Multilayer film having an active oxygen barrier layer with radiation enhanced active barrier properties
원문보기
IPC분류정보
국가/구분
United States(US) Patent
등록
국제특허분류(IPC7판)
A23L-003/00
B32B-027/00
H05B-006/00
B32B-027/08
B32B-027/18
B32B-027/30
B32B-027/32
B32B-027/34
출원번호
US-0845846
(2007-08-28)
등록번호
US-9452592
(2016-09-27)
발명자
/ 주소
Beckwith, Scott
Edwards, Frank Bryan
Rivett, Janet
Ebner, Cynthia Louise
Kennedy, Thomas
McDowell, Rachel
Speer, Drew V.
출원인 / 주소
Cryovac, Inc.
대리인 / 주소
Alston & Bird LLP
인용정보
피인용 횟수 :
0인용 특허 :
117
초록▼
The present invention is directed to a multilayer film having an active oxygen barrier layer that comprises an oxygen scavenging composition that is a blend of a thermoplastic resin (A) having carbon-carbon double bonds substantially in its main chain, a transition metal salt (B), and an oxygen barr
The present invention is directed to a multilayer film having an active oxygen barrier layer that comprises an oxygen scavenging composition that is a blend of a thermoplastic resin (A) having carbon-carbon double bonds substantially in its main chain, a transition metal salt (B), and an oxygen barrier polymer (C) having oxygen barrier properties that can be further enhanced by exposing the composition to a source of ionizing radiation e.g., electron beam radiation. Irradiation improves the oxygen scavenging abilities of the oxygen scavenging composition so that oxygen can be intercepted and scavenged as it passes through the film. The resulting irradiated multilayer film has improved active barrier properties in comparison to the same film prior to irradiation. As result, the multilayer film of the present invention can be used in packaging applications to help maintain a low oxygen atmosphere in the interior of a package.
대표청구항▼
1. An active oxygen barrier film comprising an irradiated multilayer film having an active oxygen barrier layer comprising an oxygen scavenging composition that is a blend of: (A) a thermoplastic resin having carbon-carbon double bonds substantially in its main chain;(B) a transition metal salt; and
1. An active oxygen barrier film comprising an irradiated multilayer film having an active oxygen barrier layer comprising an oxygen scavenging composition that is a blend of: (A) a thermoplastic resin having carbon-carbon double bonds substantially in its main chain;(B) a transition metal salt; and(C) an oxygen barrier polymer,wherein the oxygen scavenging composition has active oxygen barrier properties prior to irradiation, and the active oxygen barrier layer is disposed between an outer sealant layer and an outer abuse layer, wherein the multilayer film has been irradiated with an electron beam radiation dosage between about 2 and 200 kilo Gray, and wherein the film has an oxygen scavenging rate that is at least about 0.01 cc oxygen per day per gram of the oxygen scavenging composition blend; and the film exhibits a higher rate of oxygen scavenging in comparison to the same film prior to irradiation. 2. The active oxygen barrier film of claim 1, wherein the thermoplastic resin (A) comprises at least one of the units represented by formula (I) and formula (II): wherein R1,R2, R3 and R4 are the same or different, a hydrogen atom, a substituted or non-substituted alkyl group, a substituted or non-substituted aryl group, a substituted or non-substituted alkylaryl group, —COOR5, —OCOR6, a cyano group or a halogen atom, and R3 and R4 are capable of forming a ring via a methylene group or an oxymethylene group, and wherein R5 and R6 are a substituted or non-substituted alkyl group, a substituted or non-substituted aryl group, or a substituted or non-substituted alkylaryl group. 3. The active oxygen barrier film of claim 1, wherein the thermoplastic resin (A) comprises at least one of the units represented by formula (I) and formula (II): wherein R1, R2, R3 and R4 are hydrogen atoms. 4. The active oxygen barrier film of claim 1, wherein in the thermoplastic resin (A), has adjacent carbon-carbon double bonds that are separated by at least three methylenes. 5. The active oxygen barrier film of claim 1, wherein the thermoplastic resin (A) has a unit represented by a formula (III): wherein R7 and R8 are each independently a hydrogen atom, a substituted or nonsubstituted alkyl group, a substituted or non-substituted aryl group, a substituted or non-substituted alkylaryl group, —COOR9, —OCOR10, a cyano group, or a halogen atom, and R9 and R10 are each independently a hydrogen atom, or an alkyl group having 1 to 10 carbon atoms. 6. The active oxygen barrier film of claim 1, wherein the thermoplastic resin (A) is at least one resin selected from the group consisting of polybutadiene, polyisoprene, polychloroprene, and polyoctenylene. 7. The active oxygen barrier film of claim 6, wherein the thermoplastic resin (A) is at least one resin selected from the group consisting of polybutadiene and polyoctenylene. 8. The active oxygen barrier film of claim 7, wherein the thermoplastic resin (A) is polyoctenylene. 9. The active oxygen barrier film of claim 1, wherein the transition metal salt (B) is at least one metal salt selected from the group consisting of an iron salt, a nickel salt, a copper salt, a manganese salt and a cobalt salt, and combinations thereof. 10. The active oxygen barrier film of claim 1, wherein the oxygen absorption amount of the thermoplastic resin (A) is at least 1.6 mols per 1 mol of carbon-carbon double bonds of the thermoplastic resin (A). 11. The active oxygen barrier film of claim 1, wherein the oxygen absorption rate of the film is at least 0.01 ml/(g·day). 12. The active oxygen barrier film of claim 1, wherein the oxygen barrier polymer (C) has an oxygen transmission rate of 500 m1·20 μm/(m2·day ·atm)or less at 65% RH at 20° C. 13. The active oxygen barrier film of claim 12, wherein the oxygen barrier polymer (C) comprises a polymer selected from the group consisting of polyvinyl alcohol, polyamide, polyvinyl chloride, polyacrylonitrile, and combinations thereof. 14. The active oxygen barrier film of claim 13, wherein the oxygen barrier polymer (C) is an ethylene-vinyl alcohol copolymer having an ethylene content of 5 to 60 mol % and a saponification degree of about 90% or more. 15. The active oxygen barrier film of claim 13, wherein the oxygen barrier polymer (C) is present in an amount of about 70 to 99 weight % and the thermoplastic resin (A) is present in an amount of 30 to 1 weight %, based on the combined weight of the thermoplastic resin (A) and the EVOH oxygen barrier polymer (C). 16. The active oxygen barrier film of claim 13, further comprising a compatibilizer (D). 17. The active oxygen barrier film of claim 16, wherein the oxygen barrier polymer (C) is present in an amount of 70 to 98.9 wt %, the thermoplastic resin (A) is present in an amount of about 1 to 29.9 weight %, and the compatibilizer (D) is present in an amount of about 0.1 to 29 weight %, based on the total weight of the thermoplastic resin (A), oxygen barrier polymer (C), and the compatibilizer (D). 18. The active oxygen barrier film of claim 1, wherein the film is heat shrinkable. 19. The active oxygen barrier film of claim 18, wherein the film has a total free shrink, at 185° F., of at least 20 percent. 20. The active oxygen barrier film of claim 18, wherein the film has a total free shrink, at 185° F., of less than 10 percent. 21. The active oxygen barrier film of claim 1, further comprising at least two intermediate adhesive layers, each of which are disposed between the core layer and a respective outer layer. 22. The active oxygen barrier film of claim 1, wherein the multilayer film has been irradiated with an electron beam radiation dosage between about 50 and 100 kilo Gray. 23. A multilayer coextruded active oxygen barrier film comprising: (a) a core layer comprising a blend of ethylene vinyl alcohol copolymer, an oxygen scavenging composition comprising a thermoplastic resin having carbon-carbon double bonds substantially in its main chain, and a transition metal salt, and wherein the oxygen scavenging composition has active oxygen barrier properties prior to irradiation;(b) two intermediate layers each comprising a polyamide;(c) two outer layers; and(d) two layers of adhesive polymeric material disposed between respective intermediate and outer layers, and wherein the film has been irradiated with an electron beam radiation dosage between about 2 and 200 kilo Gray, wherein the film has an oxygen scavenging rate that is at least about 0.01 ml/(g·day) of the core layer; and the film exhibits a higher rate of oxygen scavenging in comparison to the same film prior to irradiation. 24. The multilayer film according to claim 23, wherein the thickness of the film is between 0.5 and 30 mils, and the thickness of the core layer is between 5 and 25 percent of the overall thickness of the film. 25. The multilayer film according to claim 23, wherein the polyamide comprises nylon 6, amorphous nylon, nylon 12, and blends thereof. 26. The multilayer film according to claim 23, wherein the film exhibits a 5% decrease in oxygen ingress through the film after 35 days in comparison to the same film that has not been irradiated. 27. The multilayer film according to claim 23, wherein the film exhibits at least a 75% decrease in oxygen ingress through the film after 70 days in comparison to the same film that has not been irradiated. 28. A packaging article comprising the multilayer film according to claim 23. 29. The packaging article of claim 28, wherein an oxygen sensitive product is disposed in an interior of the packaging article. 30. A package comprising: a) a food article; andb) a film wrapped around at least a portion of the food article, the film comprising (i) a core layer comprising an oxygen scavenging composition that is a blend of ethylene vinyl alcohol copolymer, a thermoplastic resin having carbon-carbon double bonds substantially in its main chain, and a transition metal salt, and wherein the oxygen scavenging composition has active oxygen barrier properties prior to irradiation;(ii) two intermediate layers each comprising a polyamide;(iii) two outer layers; and(iv) two layers of adhesive polymeric material disposed between respective intermediate and outer layers, and wherein the film has been irradiated with an electron beam radiation dosage between about 20 and 200 kilo Gray, wherein the film has an oxygen scavenging rate that is at least about 0.01 cc oxygen per day per gram of the oxygen scavenging blend, and a total free shrink, at 185° F., of at least 20 percent; and the film exhibits a higher rate of oxygen scavenging in comparison to the same film prior to irradiation. 31. A method of packaging an oxygen-sensitive product comprising: (a) providing a film with at least one layer comprising blend of ethylene/vinyl alcohol copolymer, an oxygen scavenging composition that is a blend of ethylene vinyl alcohol copolymer, a thermoplastic resin having carbon-carbon double bonds substantially in its main chain, and a transition metal salt, and wherein the oxygen scavenging composition has active oxygen barrier properties prior to irradiation;(b) exposing the film to electron beam radiation of at least about 2 kilo Gray; the film exhibits a higher rate of oxygen scavenging in comparison to the same film prior to irradiation, and(c) placing the oxygen-sensitive product inside a container made from the film.
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이 특허에 인용된 특허 (117)
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McIntyre Deborah J. (Palatine IL) Reed Dwight E. (Barrington IL), Method of thermally processing low-acid foodstuffs in hermetically sealed containers and the containers having the foods.
McIntyre Deborah J. (Palatine IL) Reed Dwight E. (Barrington IL), Method of thermally processing low-acid foodstuffs in hermetically sealed containers and the containers having the foods.
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