Laminated resilient flexible barrier membranes

• US 6,620,472 B1
• Filed: 07/19/1996
• Issued: 09/16/2003
• Est. Priority Date: 08/31/1994
• Status: Expired due to Term

• Current Assignee: Nike, Inc., Tetra Plastics Incorporated
• Original Assignee: Nike, Inc., Tetra Plastics Incorporated
• Inventors: Mitchell, Paul H., Hartlerood, DeWayne R., Shepard, Erwin C.
• Primary Examiner(s): Nakarani, D. S.
• Application Number:
  US08/684,351
• Time in Patent Office: 2,615 Days
• Field of Search: 95/43, 96/4, 96/11, 138/26, 138/28, 138/30, 210/500.42, 210/500.36, 210/500.27, 210/490, 428/423.1, 428/424.2, 428/424.4, 428/424.8, 428/500, 428/332, 428/35.4, 428/36.6, 428/36.7, 428/36.8, 473/603, 473/604, 473/609, 473/FOR.145, 473/FOR.165, 473/FOR.152
• US Class Current: 428/35.4
• CPC Class Codes: A63B 2243/0025 Football American football A63B2243/007
• CPC Class Codes: B32B 27/08 of synthetic resin
• CPC Class Codes: B32B 27/40 comprising polyurethanes
• CPC Class Codes: C08J 5/12 Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives
• CPC Class Codes: Y10T 428/1341 Contains vapor or gas barrier, polymer derived from vinyl chloride or vinylidene chloride, or polymer containing a vinyl alcohol unit
• CPC Class Codes: Y10T 428/1379 Contains vapor or gas barrier, polymer derived from vinyl chloride or vinylidene chloride, or polymer containing a vinyl alcohol unit
• CPC Class Codes: Y10T 428/1383 Vapor or gas barrier, polymer derived from vinyl chloride or vinylidene chloride, or polymer containing a vinyl alcohol unit is sandwiched between layers [continuous layer]
• CPC Class Codes: Y10T 428/1386 Natural or synthetic rubber or rubber-like compound containing
• CPC Class Codes: Y10T 428/26 Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
• CPC Class Codes: Y10T 428/31573 Next to addition polymer of ethylenically unsaturated monomer
• CPC Class Codes: Y10T 428/31576 Ester monomer type [polyvinylacetate, etc.]
• CPC Class Codes: Y10T 428/31587 Hydrocarbon polymer [polyethylene, polybutadiene, etc.]

Abstract

The present invention relates to laminated membranes formed by multi-layer processing techniques including alternating layers of thermoplastic urethane and a copolymer of ethylene and vinyl alcohol. The membranes are characterized in that hydrogen bonds are formed between the layers of thermoplastic urethane and the copolymer of ethylene and vinyl alcohol. The membranes are characterized in that hydrogen bonds are formed between the layers of thermoplastic urethane and the copolymer of ethylene and vinyl alcohol.

Claims

1. A sealed bladder inflated with a media in the form of either a gas or liquid, comprising:

a laminated membrane comprising

a first layer including a thermoplastic urethane that provides elasticity to said laminated membrane; and

a second layer including at least one copolymer of ethylene and vinyl alcohol, said second layer providing selective imperviousness from gaseous fluids to said laminated membrane;

wherein contact between said first and second layers occurs upon laminating said first and second layers together at a temperature of between about 300°

to about 465°

F. and consists essentially of hydrogen bonding.

2. The bladder according to claim 1 wherein said second layer has an average thickness of between about 10-500 microns.

3. The bladder according to claim 1 wherein said laminated membrane further comprises a third layer of material including thermoplastic urethane, wherein the thermoplastic urethane of said third layer is in contact in the form of hydrogen bonding with at least one copolymer of ethylene and vinyl alcohol of second layer on the side opposite said first layer.

4. The bladder according to claim 3 wherein said laminated membrane further comprises a fourth layer including a copolymer of ethylene and vinyl alcohol which is in contact with either said first or third layers and a fifth layer including thermoplastic urethane which is in contact with said fourth layer.

5. The bladder according to claim 1 wherein said thermoplastic urethane includes at least one constituent selected from the group consisting of polyester, polyethers, polycaprolactone, polyoxypropylene, polycarbonate macrogels and mixtures thereof.

6. The bladder according to claim 1 wherein said at least one copolymer of ethylene and vinyl alcohol has an ethylene content of between about 27 mol. % to about 48 mol. %.

7. The bladder according to claim 1 wherein said second layer consists essentially of at least one copolymer of ethylene and vinyl alcohol.

8. A sealed bladder inflated with a media in the form of either a gas or liquid, comprising:

a laminated membrane comprising

first and third layers including a thermoplastic urethane; and

a second layer disposed between said first and third layers and formed from a material including a copolymer of ethylene and vinyl alcohol, said second layer having an average thickness of between about 10 microns to about 500 microns;

whereby said thermoplastic urethane of said first and third layers is in contact with one or more copolymers of ethylene and vinyl alcohol of said second layer, wherein said contact occurs upon laminating said layers together at a temperature of between about 300°

to about 465°

F. and consists essentially of hydrogen bonding.

9. The bladder according to claim 8 wherein said laminated membrane further comprises a fourth layer including a copolymer of ethylene and vinyl alcohol which is in contact with either said first or third layers and a fifth layer including thermoplastic urethane which is in contact with said fourth layer.

10. The bladder according to claim 8 wherein said thermoplastic urethane includes at least one constituent selected from the group consisting of polyester, polyether, polycaprolactone, polyoxypropylene, polycarbonate macrogels and mixtures thereof.

11. The bladder according to claim 8 wherein said at least one copolymer of ethylene and vinyl alcohol has an ethylene content of between about 27 mol. % to about 48 mol. %.

12. The bladder according to claim 8 wherein said second layer consists essentially of at least one copolymer of ethylene and vinyl alcohol.

13. A sealed bladder inflated with a media in the form of either a gas or liquid, comprising:

a laminated membrane being formed by extruding a first layer including a thermoplastic urethane that provides elasticity to said laminated membrane;

together with a second layer including at least one copolymer of ethylene and vinyl alcohol at a temperature of about 300 to about 465°

F., said second layer providing selective resistance to gas permeation to said laminated membrane, wherein contact between said thermoplastic urethane of said first layer and said at least one copolymer of ethylene and vinyl alcohol of said second layer consists essentially of hydrogen bonding.

14. The bladder according to claim 13 wherein said second layer has an average thickness of between about 10-500 microns.

15. The bladder according to claim 13 wherein said laminated membrane further comprises a third layer of material including thermoplastic urethane, wherein said thermoplastic urethane of said third layer is in contact in the form of hydrogen bonding with the at least one copolymer of ethylene and vinyl alcohol of said second layer on the side opposite said first layer.

16. The bladder according to claim 15 wherein said laminated membrane further comprises a fourth layer including a copolymer of ethylene and vinyl alcohol which is in contact with either said first or third layers and a fifth layer including thermoplastic urethane which is in contact with said fourth layer.

17. The bladder according to claim 13 wherein said thermoplastic urethane includes at least one constituent selected from the group consisting of polyester, polyether, polycaprolactone, polyoxypropylene, polycarbonate macrogels and mixtures thereof.

18. The bladder according to claim 13 wherein said at least one copolymer of ethylene and vinyl alcohol has an ethylene content of between about 27 mol. % to about 48 mol. %.

24. The bladder according to claim 15 wherein said at least one copolymer of ethylene and vinyl alcohol has an ethylene content of between about 27 mol. % to about 48 mol. %.

19. A sealed bladder inflated with a media in the form of either a gas or liquid, comprising:

a laminated membrane comprising

a first layer including a thermoplastic urethane that provides elasticity to said laminated membrane; and

a second layer including a barrier material selected from the group consisting of copolymers of ethylene and vinyl alcohol, aliphatic and aromatic polyamides, polyvinylidene chloride, copolymers of acrylonitrile and methyl acrylate, polyesters, liquid crystal polymers, polyurethane based thermoplastics and mixtures thereof;

whereby said first and second layers are brought into contact at a temperature of about 300°

to about 465°

F., wherein said contact consists essentially of hydrogen bonding occurring between said thermoplastic urethane of said first layer and at least one of said barrier materials.

20. The bladder according to claim 19 wherein said second layer has an average thickness of between about 10-500 microns.

21. The bladder according to claim 19 wherein said laminated membrane further comprises a third layer of material including thermoplastic urethane, wherein the thermoplastic urethane of said third layer is in contact in the form of hydrogen bonding with at least one of said barrier materials of second layer on the side opposite said first layer.

22. The bladder according to claim 21 wherein said laminated membrane further comprises a fourth layer including a barrier material selected from the group consisting of copolymers of ethylene and vinyl alcohol, aliphatic and aromatic polyamides, polyvinylidene chloride, copolymers of acrylonitrile and methyl acrylate, polyesters, liquid crystal polymers, polyurethane based thermoplastics and mixtures thereof which is in contact with either said first or third layers and a fifth layer including thermoplastic urethane which is in contact with said fourth layer.

23. The bladder according to claim 19 wherein said thermoplastic urethane includes at least one constituent selected from the group consisting of polyester, polyether, polycaprolactone, polyoxypropylene, polycarbonate macrogels and mixtures thereof.

25. A sealed bladder inflated with a media in the form of either a gas or liquid, comprising:

a laminated membrane comprising

a first layer including a thermoplastic urethane that provides elasticity to said laminated membrane; and

a second layer including a blended barrier material employing at least one copolymer of ethylene and vinyl alcohol and at least one other constituent selected from the group consisting of aliphatic and aromatic polyamides, polyvinylidene chloride, copolymers of acrylonitrile and methyl acrylate, polyesters, liquid crystal polymers, polyurethane based thermoplastics and mixtures thereof;

whereby said first and second layers are brought into contact consisting essentially of hydrogen bonding occurring between said thermoplastic urethane of said first layer and said at least one copolymer of ethylene and vinyl alcohol of said second layer at a temperature of about 300°

to about 465°

F., said laminated membrane having a gas transmission rate of 10.0 or less for nitrogen based on an average thickness of 20 mils.

26. The bladder according to claim 25 wherein said second layer has an average thickness of between about 10-500 microns.

27. The bladder according to claim 25 wherein said laminated membrane further comprises a third layer of material including thermoplastic urethane, wherein the thermoplastic urethane of said third layer is in contact in the form of hydrogen bonding with at least one copolymer of ethylene and vinyl alcohol of second layer on the side opposite said first layer.

28. The bladder according to claim 27 wherein said laminated membrane further comprises a fourth layer including a copolymer of ethylene and vinyl alcohol which is in contact with either said first or third layers and a fifth layer including thermoplastic urethane which is in contact with said fourth layer.

29. The bladder according to claim 25 wherein said thermoplastic urethane includes at least one constituent selected from the group consisting of polyester, polyether, polycaprolactone, polyoxypropylene, polycarbonate macrogels and mixtures thereof.

30. The bladder according to claim 25 wherein said at least one copolymer of ethylene and vinyl alcohol has an ethylene content of between about 27 mol. % to about 48 mol. %.