Claims
- 1. An adhesive blend comprising a mixture of
- (a) a substantially non-elastomeric copolymer of propylene and ethylene wherein said ethylene comprises at least about 5 wt. % of said copolymer;
- (b) about 0.1 to 30 wt. % of said blend of a non-elastomeric graft copolymer comprising a propylene polymer backbone and a grafting monomer comprising at least one polymerizable ethylenically unsaturated carboxylic acid or acid derivative grafted onto said backbone; and
- (c) an adhesion-promoting effective amount of an ethylene homopolymer having a specific gravity in the range of about 0.915-0.930, inclusive, and a melt index of less than about 4 dg/min. as measured at 190.degree. C.
- 2. The blend of claim 1 wherein said blend is substantially free of elastomeric material.
- 3. The blend of claim 1 wherein said ethylene homopolymer of (c) comprises between about 2 and 30 wt. % of said blend.
- 4. The blend of claim 3 wherein said ethylene homopolymer of (c) comprises at least about 5 wt. % of said blend.
- 5. The blend of claim 4 wherein said ethylene homopolymer of (c) comprises at least about 10 wt. % of said blend.
- 6. The blend of claim 1 wherein said copolymer of (b) comprises about 5 to 25 wt. % of said blend, said homopolymer of (c) comprises about 10 to 30 wt. % of said blend, and said copolymer of (a) comprises the balance of said blend.
- 7. The blend of claim 6 wherein said copolymer of (b) comprises about 5 to 15 wt. % of said blend and said homopolymer of (c) comprises about 20 to 25 wt. % of said blend.
- 8. The blend of claim 1 wherein said copolymer of (b) comprises at least 10 wt. % of said blend.
- 9. The blend of claim 1 wherein said copolymer of (a) is selected from the group consisting of random, block and impact copolymers.
- 10. The blend of claim 1 wherein said copolymer of (a) is a terpolymer of propylene, ethylene and another 1-olefin.
- 11. The blend of claim 1 wherein said comonomer of (b) is selected from the group consisting of acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, maleic anhydride, 4-methyl cyclohex-4-ene-1,2-dicarboxylic acid anhydride, bicyclo(2.2.2.)oct-5-ene2,3-dicarboxylic acid anhydride, 1,2,3,4,5,8,9,10octahydronaphthalene-2,3-dicarboxylic acid anhydride, 2-oxa-1,3-diketospiro(4.4)non-7-ene, bicyclo(2.2.1)hept-5- ene-2,3-dicarboxylic acid anhydride, maleopimaric acid, tetrahydrophthhalic anhydride, norborn-5-ene-2,3-dicarboxylic acid anhydride, Nadic anhydride, methyl Nadic anhydride, Himic anhydride, methyl Himic anhydride, and x-methylbicyclo(2.2.1)hept-5-ene-2,3-dicarboxylic acid anhydride.
- 12. The blend of claim 1 wherein said propylene polymer of (b) is a crystalline propylene homopolymer.
- 13. The blend of claim 1 wherein said grafting monomer comprises between about 0.1 and 3.0 wt. % of said copolymer of (b).
- 14. The blend of claim 13 wherein said grafting monomer is maleic anhydride and said backbone is a crystalline propylene homopolymer.
- 15. The blend of claim 1 wherein said melt index is about 2 dg/min. or less.
- 16. The blend of claim 1 wherein said ethylene homopolymer has a narrow molecular weight distribution as measured by a ratio of weight average molecular weight (M.sub.w) to number average molecular weight (M.sub.n) of about 3 to 5, inclusive.
- 17. A composite structure, comprising:
- (A) a first substrate comprising a layer of gas barrier material adhered to
- (B) a second substrate comprising a layer of a propylene polymer by
- (C) an adhesive blend disposed between said first and second substrates, said adhesive blend comprising a mixture of:
- (a) a substantially non-elastomeric copolymer of propylene and ethylene wherein said ethylene comprises at least about 5 wt. % of said copolymer;
- (b) about 0.1 to 30 wt. % of said blend of a non-elastomeric graft copolymer comprising a propylene polymer backbone and a grafting monomer comprising at least one polymerizable ethylenically unsaturated carboxylic acid or acid derivative grafted onto said backbone; and
- (c) an adhesion-promoting effective amount of an ethylene homopolymer having a specific gravity in the range of about 0.915-0.930, inclusive, and a melt index of less than about 4 dg/min. as measured at 190.degree. C.
- 18. The composite structure of claim 17 wherein said gas barrier material is a polar material.
- 19. The composite structure of claim 17 wherein said gas barrier is selected from the group consisting of metals, nylon and ethylene vinyl alcohol copolymers.
- 20. The composite structure of claim 17 wherein said second substrate comprises a random, block or impact copolymer of propylene.
- 21. The composite structure of claim 17 wherein said second substrate is a propylene homopolymer.
- 22. The composite structure of claim 20 wherein said second substrate is a propylene copolymer.
- 23. The composite structure of claim 17 wherein said blend is substantially free of elastomeric material.
- 24. The composite structure of claim 17 wherein said ethylene homopolymer of (c) comprises between about 2 and 30 wt. % of said blend.
- 25. The composite structure of claim 24 wherein said ethylene homopolymer of (c) comprises at least about 5 wt. % of said blend.
- 26. The composite structure of claim 25 wherein said ethylene homopolymer of (c) comprises at least about 10 wt. % of said blend.
- 27. The composite structure of claim 17 wherein said copolymer of (b) comprises about 5 to 25 wt. % of said blend, said homopolymer of (c) comprises about 10 to 30 wt. % of said blend, and said copolymer of (a) comprises the balance of said blend.
- 28. The composite structure of claim 27 wherein said copolymer of (b) comprises about 5 to 15 wt. % of said blend and said homopolymer of (c) comprises about 20 to 25 wt. % of said blend.
- 29. The composite structure of claim 17 wherein said copolymer of (b) comprises at least 10 wt. % of said blend.
- 30. The composite structure of claim 17 wherein said copolymer of (a) is selected from the group consisting of random, block and impact copolymers.
- 31. The composite structure of claim 17 wherein said copolymer of (a) is a terpolymer of propylene, ethylene and another 1-olefin.
- 32. The composite structure of claim 17 wherein said comonomer of (b) is selected from the group consisting of acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, maleic anhydride, 4-methyl cyclohex-4-ene-1,2-dicarboxylic acid anhydride, bicyclo(2.2.2)oct-5-ene-2,3-dicarboxylic acid anhydride, 1,2,3,4,5,8,9,10-octahydronaphthalene-2,3-dicarboxylic acid anhydride, 2-oxa-1,3-diketospiro)4.4)non-7-ene, bicyclo(2.2.1)hept-5-ene-2,3-dicarboxylic acid anhydride, maleopimaric acid, tetrahydrophthhalic anhydride, norborn-5-ene-2,3-dicarboxylic acid anhydride, Nadic anhydride, methyl Nadic anhydride, Himic anhydride, methyl Himic anhydride, and x-methylbicyclo(2.2.1)hept-5-ene-2,3-dicarboxylic acid anhydride.
- 33. The composite structure of claim 17 wherein said propylene polymer of (b) is a crystalline propylene homopolymer.
- 34. The composite structure of claim 17 wherein said grafting monomer comprises between about 0.1 and 3.0 wt. % of said copolymer of (b).
- 35. The composite structure of claim 34 wherein said grafting monomer is maleic anhydride and said backbone is a crystalline propylene homopolymer.
- 36. The composite structure of claim 37 wherein said melt index is about 2 dg/min. or less.
- 37. The composite structure of claim 17 wherein said ethylene homopolymer has a narrow molecular weight distribution as measured by a ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) of about 3 to 5, inclusive.
- 38. A method of making a composite structure comprising the step of adhering:
- (A) a first substrate comprising a layer of gas barrier material to
- (B) a second substrate comprising a layer of a propylene polymer by
- (C) an adhesive blend disposed between said first and second substrates, said adhesive blend comprising a mixture of:
- (a) a substantially non-elastomeric copolymer of propylene and ethylene wherein said ethylene comprises at least about 5 wt. % of said copolymer;
- (b) about 0.1 to 30 wt. % of said blend of a non-elastomeric graft copolymer comprising a propylene polymer backbone and a grafting monomer comprising at least one polymerizable ethylenically unsaturated carboxylic acid or acid derivative grafted onto said backbone; and
- (c) an adhesion-promoting effective amount of an ethylene homopolymer having a specific gravity in the range of about 0.915-0.930, inclusive, and a melt index of less than about 4 dg/min. as measured at 190.degree. C.
- 39. The method of claim 38 wherein said adhering step is carried out by coextrusion, blown film coextrusion, extrusion lamination or coextrusion blow molding.
- 40. The method of claim 38 wherein said gas barrier material is a polar material.
- 41. The method of claim 38 wherein said gas barrier material is selected from the group consisting of metals, nylon and ethylene vinyl alcohol copolymers.
- 42. The method of claim 38 wherein said second substrate comprises a random, block or impact copolymer of propylene.
- 43. The method of claim 38 wherein said second substrate is a propylene homopolymer.
- 44. The method of claim 38 wherein said second substrate is a propylene copolymer.
- 45. The method of claim 38 wherein said blend is substantially free of elastomeric material.
- 46. The method of claim 38 wherein said ethylene homopolymer of (c) comprises between about 2 and 30 wt. % of said blend.
- 47. The method of claim 46 wherein said ethylene homopolymer of (c) comprises at least about 5 wt. % of said blend.
- 48. The method of claim 47 wherein said ethylene homopolymer of (c) comprises at least about 10 wt. % of said blend.
- 49. The method of claim 38 wherein said copolymer of (b) comprises about 5 to 25 wt. % of said blend, said homopolymer of (c) comprises about 10 to 30 wt. % of said blend, and said copolymer of (a) comprises the balance of said blend.
- 50. The method of claim 49 wherein said copolymer of (b) comprises about 5 to 15 wt. % of said blend and said homopolymer of (c) comprises about 20 to 25 wt. % of said blend.
- 51. The method of claim 38 wherein said copolymer of (b) comprises at least 10 wt. % of said blend.
- 52. The method of claim 38 wherein said copolymer of (a) is selected from the group consisting of random, block and impact copolymers.
- 53. The method of claim 38 wherein said copolymer of (a) is a terpolymer of propylene, ethylene and another 1-olefin.
- 54. The method of claim 38 wherein said comonomer of (b) is selected from the group consisting of acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, maleic anhydride, 4-methyl cyclohex-4-ene-1,2-dicarboxylic acid anhydride, bicyclo(2.2.2.)oct-5-ene-2,3-dicarboxylic acid anhydride, 1,2,3,4,5,8,9,10-octahydronaphthalene-2,3-dicarboxylic acid anhydride, 2-oxa-1,3-diketospiro(4.4)non-7-ene, bicyclo(2.2.1.)hept-5-ene-2,3-dicarboxylic acid anhydride, maleoprimaric acid, tetrahydrophthhalic anhydride, norborn-5-ene-2,3-dicarboxylic acid anhydride, Nadic anhydride, methyl Nadic anhydride, Himic anhydride, methyl Himic anhydride, and x-methylbicyclo(2.2.1.)hept-5-ene-2,3-dicarboxylic acid anhydride.
- 55. The method of claim 38 wherein said propylene polymer of (b) is a crystalline propylene homopolymer.
- 56. The method of claim 38 wherein said grafting monomer comprises between about 0.1 and 3.0 wt. % of said copolymer of (b).
- 57. The method of claim 56 wherein said grafting monomer is maleic anhydride and said backbone is a crystalline propylene homopolymer.
- 58. The method of claim 38 wherein said melt index is about 2 dg/min. or less.
- 59. The method of claim 38 wherein said ethylene homopolymer has a narrow molecular weight distribution as measured by a ratio of weight average molecular weight (M.sub.w) to number average molecular weight (M.sub.n) of about 3 to 5, inclusive.
CROSS-REFERENCE TO RELATED APPLICATIONS
This is a continuation-in-part of application Ser. No. 133,191 filed Dec. 15, 1987 now U.S. Pat. No. 4,774,144 issued Sept. 27, 1988, which is a continuation of application Ser. No. 890,936 filed July 28, 1986, now abandoned.
US Referenced Citations (15)
Foreign Referenced Citations (1)
Number |
Date |
Country |
110505 |
Jun 1984 |
EPX |
Continuations (1)
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Number |
Date |
Country |
Parent |
890936 |
Jul 1986 |
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Continuation in Parts (1)
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Number |
Date |
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Parent |
133191 |
Dec 1987 |
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