USRE37699EExpiredUtilityPatentIndex 89

Film containing alpha-olefin/vinyl aromatic copolymer

Assignee: CRYOVAC INCPriority: May 25, 1994Filed: Jul 19, 1999Granted: May 14, 2002

Est. expiryMay 25, 2014(expired)· nominal 20-yr term from priority

Inventors:BRADFUTE JOHN G CHILDRESS BLAINE CLEMONS HAVENS MARVIN LULHAM CEDRIC MICHAEL MOFFITT RONALD D NELSON MARTINDALE NORPOTH LAWRENCE R ROBERTS WILLIAM PEYTON TONEY GLORIA GARCIA WOFFORD GEORGE DEAN

B32B 27/304B32B 2307/7244B32B 5/18C08F 210/16B32B 2307/736Y10T428/31913Y10T428/31725Y10T428/1379C08J 2323/08B32B 27/08C08L 23/06B32B 27/34B32B 2250/24B32B 2329/04Y10T428/2826B32B 2250/40C08F 210/02B32B 2327/06Y10T428/1341Y10T428/31928C08L 23/0823Y10T428/1328B32B 2439/06C08L 23/0853Y10T428/3192B32B 27/36B32B 2377/00B32B 27/32C08J 5/18B32B 27/306Y10T428/3175B32B 27/302B32B 2325/00Y10T428/1334B32B 2323/00B32B 2367/00Y10T428/1383B32B 2553/00B32B 27/065

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Claims

Abstract

Film and sheet materials, and articles made therefrom, such as bags, pouches, trays, etc., comprise one or more layers of a thermoplastic, homogeneous alpha-olefin/vinyl aromatic copolymer, preferably an ethylene/styrene copolymer. The alpha-olefin/vinyl aromatic copolymer has properties which can can provide a desired performance characteristics such as impact resistance, printability, RF sealability, free shrink, optics, as well as many others. The homogeneous alpha-olefin-vinyl aromatic copolymer may be present in a mono-layer film, either alone or in a blend, or may be included in one or more layers of a multilayer film. Also included is a multilayer thermoformable article comprising a web having a film of such alpha-olefin/vinyl aromatic copolymers thereto. Finally, also included is an RF-sealable film comprising such copolymers.

Claims

exact text as granted — not AI-modified

What is claimed is:

1. A multilayer film, comprising:
(A) a first outer layer comprising a first polypropylene;
(B) an inner layer between the first outer layer and the second outer layer, the inner layer comprising a composition comprising a thermoplastic, homogeneous alpha-olefin/vinyl aromatic copolymer comprising:
(i) recurring units of the formula:
wherein:
x≧y;
R 2 is a member selected from the group consisting of hydrogen, C 1 alkyl, C 2 alkyl, C 3 alkyl, C 4 alkyl, C 5 alkyl, C 6 alkyl, or and mixtures thereof: R 2 is a member selected from the group consisting of hydrogen, C 1 alkyl, C 2 alkyl, C 3 alkyl, C 4 alkyl, C 5 alkyl, C 6 alkyl, or and mixtures thereof; provided that R 1 and R 2 cannot both be alkyl; and
R 3 is a member selected from the group consisting of hydrogen, aromatic, or and mixtures thereof; R 4 is a member selected from the group consisting of hydrogen, aromatic,or and mixtures thereof; provided that one, and only one, member selected from the group consisting of R 3 and R 4 , is aromatic; and
(ii) provided that a copolymer portion between every two adjacent members selected from the group consisting of aromatic CHR 3 and aromatic CHR 4 comprises at least two —CH 2 —; and
(C) A second outer layer comprising a second polypropylene.

2. The multilayer film according to claim 1 , wherein the multilayer film has a substantially symmetrical structure.

3. The multilayer film according to claim 1 , wherein the film is heat-shrinkable.

4. The multilayer film according to claim 1 , wherein R 1 is H and R 2 is H.

5. The multilayer film according to claim 1 , wherein in
a first member, selected from the group consisting of R 3 and R 4 , is H; and
a second member, selected from the group consisting of R 3 and R 4 , is C 6 H 5 .

6. The multilayer film according to claim 5 , wherein in
a first member, selected from the group consisting of R 1 and R 2 , is H; and
a second member, selected from the group consisting of R 1 and R 2 , is CH 3 .

7. The multilayer film according to claim 6 , wherein
the first polypropylene comprises from about 99 to 90 mole percent propylene polymerization units, and from about 1 to 10 weight percent ethylene polymerization units; and
the second propylene comprises from about 99 to 90 mole percent propylene polymerization units, and from about 1 to 10 weight percent ethylene polymerization units.

8. A multilayer film comprising:
(A) a first layer, the first layer being an outer layer, the first layer being a heat sealing layer;
(B) a second layer, the second layer being an inner layer, the second layer comprising a composition comprising a thermoplastic, homogeneous copolymer of an alpha-olefin and a vinyl aromatic, wherein the copolymer comprises:
(i) recurring units of the formula:
wherein:
x≧y;
R 1 is a member selected from the group consisting of hydrogen, C 1 alkyl, C 2 alkyl, C 3 alkyl, C 4 alkyl, C 5 alkyl, C 6 alkyl, or and mixtures thereof; R 2 is a member selected from the group consisting of hydrogen, C 1 alkyl, C 2 alkyl, C 3 alkyl, C 4 alkyl, C 5 alkyl, C 6 alkyl, or and mixtures thereof; provided that R 1 and R 2 cannot both be alkyl; and
R 3 is a member selected from the group consisting of hydrogen, aromatic, or and mixtures thereof; R 4 is a member selected from the group consisting of hydrogen, aromatic, or and mixtures thereof; provided that one, and only one, member selected from the group consisting of R 3 and R 4 , is aromatic; and
(ii) provided that a copolymer portion between every two adjacent members selected from the group consisting or aromatic CHR 3 and aromatic CHR 4 comprises at least two —CH 2 —; and
(C) a third layer, the third layer being an inner layer, the third layer being a barrier to gaseous oxygen; and
(D) a fourth layer, the fourth layer being an outer layer.

9. The multilayer film according to claim 8 , wherein the multilayer film is heat-shrinkable.

10. The multilayer film according to claim 8 , wherein the third layer comprises a vinylidene chloride copolymer.

11. The multilayer film according to claim 8 , wherein R1 is H and R 2 is H.

12. The multilayer film according to claim 11 , wherein x represents at least about 75 mole percent, based on a total of x and y.

13. The multilayer film according to claim 8 , wherein in
a first member, selected from the group consisting of R 3 and R 4 , is H; and
a second member selected from the group consisting of R 3 and R 4 , is C 6 H 5 .

14. The multilayer film according to claim 8 , wherein the first layer comprises a copolymer comprising (a) ethylene polymerization units; and (b) polymerization units from a monomer comprising at least one member selected from the group consisting of alpha-olefin, vinyl acetate, alkyl acrylate, acrylic acid, and a metal neutralized salt of an acrylic acid.

15. The multilayer film according to claim 8 , further comprising:
(E) a fifth layer, the fifth layer being an inner layer, the fifth layer being between the third layer and the fourth layer, the fifth layer comprising a composition comprising a second thermoplastic, homogeneous alpha-olefin/vinyl aromatic copolymer, wherein the second copolymer comprises:
(i) recurring units of the formula:
wherein:
x≧y:
R 1 is a member selected from the group consisting of hydrogen, C 1 alkyl, C 2 alkyl, C 3 alkyl, C 4 alkyl, C 5 alkyl, C 6 alkyl, or and mixtures thereof; R 2 is a member selected from the group consisting of hydrogen, C 1 alkyl, C 2 alkyl, C 3 alkyl, C 4 alkyl, C 5 alkyl, C 6 alkyl, or and mixtures thereof, provided that R 1 and R 2 cannot both be alkyl;
R 3 is a member selected from the group consisting of hydrogen, aromatic, or and mixtures thereof; R 4 is a member selected from the group consisting of hydrogen, aromatic, or and mixtures thereof; provided that one, and only one, member selected from the group consisting of R 3 and R 4 , is aromatic; and
(ii) provided that a second copolymer portion between every two adjacent members selected from the group consisting of aromatic CHR 3 and aromatic CHR 4 comprises at least two —CH 2 —.

16. The multilayer film according to claim 8 , wherein the fourth layer is an abuse layer.

17. The multilayer film according to claim 9 , further comprising a tie layer.

18. A multilayer film, comprising a composition comprising:
(A) a first layer, the first layer being a gaseous oxygen barrier layer; and
(B) a second layer, the second layer being a heat sealing layer, the second layer comprising a composition a thermoplastic, homogeneous alpha- olefin/vinyl aromatic copolymer of an alpha-olefin and a vinyl aromatic , wherein the copolymer comprises:
(i) recurring units of the formula:
wherein:
x≧y;
R 1 is a member selected from the group consisting of hydrogen, C 1 alkyl, C 2 alkyl, C 3 alkyl, C 4 alkyl, C 5 alkyl, C 6 alkyl, or and mixtures thereof; R 2 is a member selected from the group consisting of hydrogen, C 1 alkyl, Cl 2 alkyl, C 3 alkyl, C 4 alkyl, Cl 5 alkyl, C 6 alkyl, or and mixtures thereof; provided that R 1 and R 2 cannot both be alkyl;
R 3 is a member selected from the group consisting of hydrogen, aromatic, or and mixtures thereof; R 4 is a member selected from the group consisting of hydrogen, aromatic, or and mixtures thereof; provided that one, and only one, member selected from the group consisting of R 3 and R 4 , is aromatic; and
(ii) provided that a copolymer portion between every two adjacent members selected from the group consisting of aromatic CHR 3 and aromatic CHR 4 comprises at least two —CH 2 —.

19. The multilayer film according to claim 18 , wherein the multilayer film is heat-shrinkable.

20. The multilayer film according to claim 18 , wherein R1 is H and R 2 is H.

21. The multilayer film according to claim 20 , wherein x represents at least about 75 mole percent, based on a total of x and y.

22. The multilayer film according to claim 18 , wherein in
a first member, selected from the group consisting of R 3 and R 4 , is H; and
a second member, selected from the group consisting of R 3 and R 4 , is C 6 H 5 .

23. The multilayer film according to claim 18 , wherein the first layer comprises vinylidene chloride copolymer.

24. The multilayer film according to claim 18 , further comprising an outer abuse layer.

25. The multilayer film according to claim 18 , further comprising a tie layer.

26. A multilayer film, comprising:
(A) a first layer, the first layer being an outer layer, the first layer comprising a composition comprising a first thermoplastic, homogeneous alpha-olefin/vinyl aromatic copolymer, wherein the copolymer comprises:
(i) recurring units of the formula:
wherein:
x≧y;
R 1 is a member selected from the group consisting of hydrogen, C 1 alkyl, C 2 alkyl, C 3 alkyl, C 4 alkyl, C 5 alkyl, C 6 alkyl, or and mixtures thereof; R 2 is a member selected from the group consisting of hydrogen, C 1 alkyl, C 2 alkyl, C 3 alkyl, C 4 alkyl, C 5 alkyl, C 6 alkyl, or and mixtures thereof; provided that R 1 and R 2 cannot both be alkyl; and
R 3 is a member selected form the group consisting of hydrogen, aromatic, or and mixtures thereof; R 4 is a member selected from the group consisting of hydrogen, aromatic, or and mixtures thereof; provided that one, and only one, member selected from the group consisting of R 3 and R 4 , is aromatic; and
(ii) provided that a second copolymer portion between every two adjacent members selected from the group consisting of aromatic CHR 3 and aromatic CHR 4 comprises at least two —CH 2 —:
(B) a second layer, the second layer being an inner layer; and
(C) a third layer, the third layer being an outer layer, the third layer comprising a second thermoplastic, homogeneous alpha-olefin/vinyl aromatic polymer, wherein the copolymer comprises:
(i) recurring units of the formula:
wherein:
x≧y;
R 1 is a member selected from the group consisting of hydrogen, C 1 alkyl, C 2 alkyl, C 3 alkyl, C 4 alkyl C 5 alkyl, C 6 alkyl, or and mixtures thereof; R 2 is a member selected from the group consisting of hydrogen, C 1 alkyl, C 2 alkyl, C 3 alkyl, C 4 alkyl, C 5 alkyl, C 6 alkyl, or and mixtures thereof; provided that R 1 and R 2 cannot both be alkyl; and
R 3 is a member selected from the group consisting of hydrogen, aromatic, or and mixtures thereof; R 4 is a member selected from the group consisting of hydrogen, aromatic, or and mixtures thereof; provided that one, and only one, number selected from the group consisting of R 3 and R 4 , is aromatic; and
(ii) provided that a second copolymer portion between every two adjacent members selected from the group consisting of aromatic CHR 3 and aromatic CHR 4 comprises at least two —CH 2 —.

27. The multilayer film according to claim 26 , wherein the multilayer film has a substantially symmetrical structure.

28. The multilayer film according claim 26 , wherein the multilayer film is heat-shrinkable.

29. The multilayer film according to claim 21 26
wherein R 1 is H and R 2 is H.

30. The multilayer film according to claim 29 , wherein each of the first thermoplastic homogeneous alpha-olefin/vinyl aromatic copolymer and the second thermoplastic homogeneous alpha-olefin/vinyl aromatic copolymer, comprise at least 75 mole percent of:
have R 1 being H and R 2 being H.

31. The multilayer film according to claim 26 , wherein both the first thermoplastic homogeneous alpha-olefin/vinyl aromatic copolymer and the second thermoplastic homogeneous alpha-olefin/vinyl aromatic copolymer comprise:
a first member, selected from the group consisting of R 3 and R 4 , is H; and
a second member, selected from the group consisting of R 3 and R 4 , is C 6 H 5 .

32. The multilayer film according to claim 26 , wherein the second layer comprises a copolymer comprising:
(a) ethylene polymerization units; and
(b) polymerization units from a monomer comprising at least one member selected from the group consisting of alpha-olefin, vinyl acetate, alkyl acrylate, acrylic acid, and a metal neutralized salt of an acrylic acid.

33. The heat-shrinkable film according to claim 26 , wherein the second layer comprises polypropylene.

34. The multilayer film according to claim 26 , wherein the second layer is a gaseous oxygen barrier.

35. The multilayer film according to claim 34 , wherein the second layer comprises ethylene/vinyl alcohol copolymer.

36. The multilayer film according to claim 26 , further comprising:
a fourth layer directly adhered to the second layer, the fourth layer being between the first layer and the second layer;
a fifth layer directly adhered to the second layer, the fifth layer being between the second layer and the third layer.

37. The multilayer film according to claim 36 , wherein the fourth layer comprises polyamide, and the fifth layer comprises polyamide.

38. The multilayer film according to claim 37 , further comprising:
a sixth layer between the first layer and the fourth layer, the sixth layer being a tie layer; and
a seventh layer between the third layer and the fifth layer, the seventh layer being a tie layer.

39. The multilayer film according to claim 26 , wherein the first layer comprises at least two thermoplastic polymers, and the third layer comprises at least two thermoplastic polymers.

40. A multilayer thermoformable article, comprising:
(A) a first layer comprising a polystyrene web; and
(B) a second layer comprising a multilayer, heat-resistant film comprising a composition comprising a thermoplastic, homogeneous alpha-olefin/vinyl aromatic copolymer, wherein the copolymer comprises:
(i) recurring units of the formula:
wherein:
X≧y;
R 1 is a member selected from the group consisting of hydrogen, C 1 alkyl, C 2 alkyl, C 3 alkyl, C 4 alkyl, C 5 alkyl, C 6 alkyl, or and mixtures thereof; R 2 is a member selected from the group consisting of hydrogen, C 1 alkyl, C 2 alkyl, C 3 alkyl, C 4 alkyl, C 5 alkyl, C 6 alkyl, or and mixtures thereof; provided that R 1 and R 2 cannot both be alkyl; and
R 3 is a member selected from the group consisting of hydrogen, aromatic, or and mixtures thereof; R 4 is a member selected from the group consisting of hydrogen, aromatic, or and mixtures thereof; provided that one, and only one, member selected from the group consisting of R 3 and R 4 , is aromatic; and
(ii) provided that a copolymer portion between every two adjacent members selected from the group consisting of aromatic CHR 3 and aromatic CHR 4 comprises at least two —CH 2 —.

41. A multilayer article comprising a heat-shrinkable patch member on a thermoplastic bag, the heat shrinkable patch member comprising a composition comprising an a thermoplastic homogeneous alpha-olefin/vinyl aromatic copolymer comprising:
(A) recurring units of the formula:
wherein:
x≧y;
R 1 is a member selected from the group consisting of hydrogen, C 1 alkyl, C 2 alkyl, C 3 alkyl, C 4 alkyl, C 5 alkyl, C 6 alkyl, or and mixtures thereof; R 2 is a member selected from the group consisting of hydrogen, C 1 alkyl, C 2 alkyl, C 3 alkyl, C 4 alkyl, C 5 alkyl, C 6 alkyl, or and mixtures thereof; provided that R 1 and R 2 cannot both be alkyl; and
R 3 is a member selected from the group consisting of hydrogen, aromatic, or and mixtures thereof; R 4 is a member selected from the group consisting of hydrogen, aromatic, or and mixtures thereof; provided that one, and only one, member selected from the group consisting of R 3 and R 4 , is aromatic; and
(B) provided that a copolymer portion between every two adjacent members selected from the group consisting of aromatic CHR 3 and aromatic CHR 4 comprises at least two —CH 2 —.

42. The multilayer film according to claim 1 , wherein the vinyl aromatic is present from about 2 mol % to 50 mol % in the copolymer.

43. The multilayer film according to claim 42 , wherein the vinyl aromatic is present from about 25 mol % to 50 mol % in the copolymer.

44. The multilayer film according to claim 43 , wherein the vinyl aromatic is present from about 25 mol % to 40 mol % in the copolymer.

45. The multilayer film according to claim 43 , wherein the vinyl aromatic is present from about 35 mol % to 50 mol % in the copolymer.

46. The multilayer film according to claim 42 , wherein the alpha- olefin is ethylene and the vinyl aromatic is styrene.

47. The multilayer film according to claim 8 , wherein the vinyl aromatic is present from about 2 mol % to 50 mol % in the copolymer.

48. The multilayer film according to claim 47 , wherein the vinyl aromatic is present from about 25 mol % to 50 mol % in the copolymer.

49. The multilayer film according to claim 48 , wherein the vinyl aromatic is present from about 25 mol % to 40 mol % in the copolymer.

50. The multilayer film according to claim 48 , wherein the vinyl aromatic is present from about 35 mol % to 50 mol % in the copolymer.

51. The multilayer film according to claim 47 , wherein the alpha- olefin is ethylene and the vinyl aromatic is styrene.

52. The multilayer film according to claim 18 , wherein the vinyl aromatic is present from about 2 mol % to 50 mol % in the copolymer.

53. The multilayer film according to claim 52 , wherein the vinyl aromatic is present from about 25 mol % to 50 mol % in the copolymer.

54. The multilayer film according to claim 53 , wherein the vinyl aromatic is present from about 25 mol % to 40 mol % in the copolymer.

55. The multilayer film according to claim 53 wherein the vinyl aromatic is present from about 35 mol % to 50 mol % in the copolymer.

56. The multilayer film according to claim 52 , wherein the alpha- olefin is ethylene and the vinyl aromatic is styrene.

57. The multilayer film according to claim 26 , wherein the vinyl aromatic is present from about 2 mol % to 50 mol % in the copolymer.

58. The multilayer film according to claim 57 , wherein the vinyl aromatic is present from about 25 mol % to 50 mol % in the copolymer.

59. The multilayer film according to claim 58 , wherein the vinyl aromatic is present from about 25 mol % to 40 mol % in the copolymer.

60. The multilayer film according to claim 58 , wherein the vinyl aromatic is present from about 35 mol % to 50 mol % in the copolymer.

61. The multilayer film according to claim 57 , wherein the alpha- olefin is ethylene and the vinyl aromatic is styrene.

62. The multilayer thermoformable article according to claim 40 , wherein the vinyl aromatic is present from about 2 mol % to 50 mol % in the copolymer.

63. The multilayer thermoformable article according to claim 62 , wherein the vinyl aromatic is present from about 25 mol % to 50 mol % in the copolymer.

64. The multilayer thermoformable article according to claim 63 , wherein the vinyl aromatic is present from about 25 mol % to 40 mol % in the copolymer.

65. The multilayer thermoformable article according to claim 63 , wherein the vinyl aromatic is present from about 35 mol % to 50 mol % in the copolymer.

66. The multilayer thermoformable article according to claim 58 , wherein the alpha- olefin is ethylene and the vinyl aromatic is styrene.

67. The multilayer thermoformable article according to claim 40 , wherein the first layer is a foamed polystyrene web.

68. The multilayer thermoformable article according to claim 62 , wherein the first layer is a foamed polystyrene web.

69. The multilayer article according to claim 41 , wherein the vinyl aromatic is present from about 2 mol % to 50 mol % in the copolymer.

70. The multilayer article according to claim 69 , wherein the vinyl aromatic is present from about 25 mol % to 50 mol % in the copolymer.

71. The multilayer article according to claim 70 , wherein the vinyl aromatic is present from about 25 mol % to 40 mol % in the copolymer.

72. The multilayer article according to claim 70 , wherein the vinyl aromatic is present from about 35 mol % to 50 mol % in the copolymer.

73. The multilayer article according to claim 69 , wherein the alpha- olefin is ethylene and the vinyl aromatic is styrene.

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