Membranes of polyurethane based materials including polyester polyols

• US 6,013,340 A
• Filed: 12/12/1995
• Issued: 01/11/2000
• Est. Priority Date: 06/07/1995
• Status: Expired due to Term

• Current Assignee: Nike, Inc., Tetra Plastics Incorporated (Nike, Inc.)
• Original Assignee: Nike, Inc.
• Inventors: Goldwasser, David, Bonk, Henry W.
• Primary Examiner(s): DYE, RENA
• Application Number:
  US08/571,160
• Time in Patent Office: 1,491 Days
• Field of Search: 428/35.7, 428/36.8, 428/423.1, 428/424.4, 428/35.4, 428/35.5, 428/35.2, 428/339, 428/423.7, 428/423.5, 36/28, 36/29, 36/35 R, 36/35 B, 5/706, 5/707, 5/655.3, 138/30, 297/452.48, 152/157, 152/155, 152/246, 152/450
• US Class Current: 428/35.2
• CPC Class Codes: A43B 1/0072 made at least partially of transparent or translucent materials
• CPC Class Codes: A43B 13/203 provided with a pump or valve
• CPC Class Codes: A43B 13/206 provided with tubes or pipes or tubular shaped cushioning members
• CPC Class Codes: A61F 5/01 Orthopaedic devices, e.g. splints, casts or braces
• CPC Class Codes: A63C 17/22 Wheels for roller skates
• CPC Class Codes: B29C 48/00 Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor extrusion blow-moulding B29C49/04
• CPC Class Codes: B29C 48/08 flexible, e.g. films
• CPC Class Codes: B29C 48/10 flexible, e.g. blown foils
• CPC Class Codes: B29C 49/041 using an accumulator head
• CPC Class Codes: B29C 67/24 characterised by the choice of material
• CPC Class Codes: B29D 7/01 Films or sheets
• CPC Class Codes: B29K 2075/00 Use of PU, i.e. polyureas or polyurethanes or derivatives thereof, as moulding material
• CPC Class Codes: B29K 2995/0067 non-permeable
• CPC Class Codes: B32B 1/08 Tubular products
• CPC Class Codes: B32B 2307/3065 Flame resistant or retardant, fire resistant or retardant
• CPC Class Codes: B32B 2307/54 Yield strength; Tensile strength
• CPC Class Codes: B32B 2307/544 Torsion strength; Torsion stiffness
• CPC Class Codes: B32B 2307/554 Wear resistance
• CPC Class Codes: B32B 2307/5825 Tear resistant
• CPC Class Codes: B32B 2307/724 Permeability to gases, adsorption
• CPC Class Codes: B32B 2307/7242 : Non-permeable
• CPC Class Codes: B32B 2309/105 : Thickness
• CPC Class Codes: B32B 2437/02 : Gloves, shoes
• CPC Class Codes: B32B 2437/04 : Caps, helmets
• CPC Class Codes: B32B 2571/00 : Protective equipment
• CPC Class Codes: B32B 27/08 : of synthetic resin
• CPC Class Codes: B32B 27/306 : comprising vinyl acetate or vinyl alcohol (co)polymers
• CPC Class Codes: B32B 27/40 : comprising polyurethanes
• CPC Class Codes: B32B 37/153 : at least one layer is extruded and immediately laminated while in semi-molten state
• CPC Class Codes: C08G 18/4202 : Two or more polyesters of different physical or chemical nature C08G18/44 takes precedence
• CPC Class Codes: C08G 18/4211 : derived from aromatic dicarboxylic acids and dialcohols
• CPC Class Codes: C08G 18/4238 : derived from dicarboxylic acids and dialcohols
• CPC Class Codes: C08G 18/664 : with compounds of group C08G18/3203
• CPC Class Codes: C08G 18/758 : containing two or more cycloaliphatic rings
• CPC Class Codes: C08G 18/7657 : containing two or more aromatic rings
• CPC Class Codes: C08G 2390/00 : Containers
• CPC Class Codes: Y10T 428/1334 : Nonself-supporting tubular film or bag [e.g., pouch, envelope, packet, etc.]
• 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 428/1345 : Single layer [continuous layer]
• CPC Class Codes: Y10T 428/1352 : Polymer or resin containing [i.e., natural or synthetic]
• 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 428/231 : Filled with gas other than air; or under vacuum
• CPC Class Codes: Y10T 428/269 : including synthetic resin or polymer layer or component
• CPC Class Codes: Y10T 428/31551 : Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
• CPC Class Codes: Y10T 428/31554 : Next to second layer of polyamidoester
• CPC Class Codes: Y10T 428/31562 : Next to polyamide [nylon, etc.]
• CPC Class Codes: Y10T 428/31565 : Next to polyester [polyethylene terephthalate, etc.]
• 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 428/3158 : Halide monomer type [polyvinyl chloride, etc.]
• CPC Class Codes: Y10T 428/31583 : Nitrile monomer type [polyacrylonitrile, etc.]
• CPC Class Codes: Y10T 428/31587 : Hydrocarbon polymer [polyethylene, polybutadiene, etc.]
• CPC Class Codes: Y10T 428/31931 : Polyene monomer-containing

Abstract

The present invention relates to membranes including an urethane including a polyester polyol, wherein the membrane has a gas transmission rate of 15.0 or less for nitrogen gas wherein the membrane has an average thickness of approximately 20.0 mils. Under certain embodiments, the membranes include blends of one or more polyester polyol based thermoplastic urethanes and one or more barrier materials. The membranes can be employed in a variety of applications and can be used as either monolayers or multi-layered laminates.

Claims

1. A flexible membrane comprising:

a polyurethane including a polyester polyol, said membrane having a gas transmission rate of 15.0 or less for nitrogen gas;

wherein said membrane is sealed and in an inflated state.

2. The membrane according to claim 1, wherein said polyester polyol of said polyurethane is selected from the group consisting of the reaction product of (a) a carboxylic acid having six or less carbon atoms and (b) a diol having six or less carbon atoms, wherein the repeating units of the polyester polyol formed by the aforesaid reaction has eight carbon atoms or less.

3. The membrane according to claim 2, wherein the carboxylic acid is selected from the group consisting of adipic, glutaric, succinic, malonic and oxalic acids, and mixtures thereof.

4. The membrane according to claim 3, wherein the carboxylic acid employed includes adipic acid.

5. The membrane according to claim 2, wherein the diol is selected from the group consisting of ethylene glycol, propanediol, butanediol, neopentyldiol, pentanediol, hexanediol and mixtures thereof.

6. The membrane according to claim 5, wherein the diol employed includes ethylene glycol.

7. The membrane according to claim 2, wherein said polyurethane further comprises at least one extender.

8. The membrane according to claim 7, wherein said extender is selected from the group consisting of alcohols and amines.

9. The membrane according to claim 7, wherein said extender is selected from the group consisting of ethylene glycol, 1,3 propylene glycol, 1,4-butanediol and 1,6-hexanediol.

10. The membrane according to claim 7, wherein said at least one extender and said at least one polyester polyol include active hydrogen containing groups.

11. The membrane according to claim 7, wherein the ratio of polyester polyol to extender is between about 1:

0 to about 1;

12.

12. The membrane according to claim 11, wherein the ratio of polyester polyol to extender is between about 1:

1 to about 1;

8.

13. The membrane according to claim 10, wherein the ratio of isocyanate contained in said polyurethane to active hydrogen containing groups is between about 0.95:

1 to about 1.10;

1.

14. The membrane according to claim 13, wherein the ratio of isocyanate to active hydrogen containing groups is between about 0.98:

1 to about 1.04;

1.

15. The membrane according to claim 2, further comprising a hydrolytic stabilizer.

16. The membrane according to claim 15, wherein said hydrolytic stabilizer is present in an amount of up to 5.0 wt. %.

17. The membrane according to claim 15, wherein said hydrolytic stabilizer is selected from the group consisting of carbodiimides, polycarbodiimides and epoxidized soy bean oil.

18. The membrane according to claim 2, wherein said polyurethane includes at least one plasticizer, said plasticizer being present in an amount of up to 40.0 wt. %.

19. The membrane according to claim 2, wherein said polyurethane includes at least one flame retardant, said flame retardant being present in an amount of up to 40.0 wt. %.

20. The membrane according to claim 2, wherein said polyurethane includes at least one filler, said filler being present in an amount of up to 60 wt. %.

21. The membrane according to claim 2, wherein at least one additive is employed, said additive being selected from the group consisting of antioxidants, ultra-violet stabilizers, thermal stabilizers, light stabilizers, organic anti-block compounds, colorants, fungicides, mold release agents and lubricants, said at least one additive being present in an amount of up to 3.0 wt. %.

22. The membrane according to claim 2, further comprising at least one triol.

23. The membrane according to claim 22, wherein said at least one triol includes trimethyol propane.

24. The membrane according to claim 2, further comprising at least one material selected from the group consisting of co-polymers of ethylene and vinyl alcohol, polyvinylidene chloride, co-polymers of acrylonitrile and methyl acrylate, polyethylene terephthalate, aliphatic and aromatic polyamides, crystalline polymers and polyurethane engineering thermoplastics, said material being blended with said polyurethane prior to forming said membrane.

25. The membrane according to claim 24, wherein said membrane includes up to about 70.0 wt. % polyester polyol based urethane.

26. The membrane according to claim 25, wherein said membrane includes between about 5.0 wt. % to about 25.0 wt. % polyester polyol based urethane.

27. The membrane according to claim 24, wherein said material selected from said group includes at least one copolymer of ethylene and vinyl alcohol.

28. The membrane according to claim 27, wherein at least one of the copolymers of ethylene and vinyl alcohol has an ethylene content of between about 25 mol. % to about 48 mol. %.

29. The membrane according to claim 2, wherein said membrane includes at least one polyurethane including soft segments selected from the group consisting of polyether polyols, polyester polyols formed from the reaction product of a carboxylic acid and a diol wherein the repeating units of the reaction product have more than eight carbon atoms, or mixtures thereof.

30. The membrane according to claim 29, wherein said at least one polyurethane including soft segments selected from the group consisting of polyether polyols, polyester polyols formed from the reaction product of a carboxylic acid and a diol wherein the repeating units of the reaction product have more than eight carbon atoms, or mixtures thereof, is present in an amount of up to 30.0 wt. %.

31. The membrane according to claim 29, wherein the polyurethane including the polyester polyol formed from a carboxylic acid and a diol wherein the reaction product has more than eight carbon atoms is selected from the group consisting of ethylene glycol isophthalate, 1,4 butanediol isophalate and 1,6 hexanediol isophthalate.

32. The membrane according to claim 1, wherein said gas transmission rate is less than about 10.0 for nitrogen gas.

33. The membrane according to claim 32, wherein said gas transmission rate is less than about 7.5 for nitrogen gas.

34. The membrane according to claim 33, wherein said gas transmission rate is less than about 5.0 for nitrogen gas.

35. The membrane according to claim 34, wherein said gas transmission rate is less than about 2.5 for nitrogen gas.

36. The membrane according to claim 35, wherein said gas transmission rate is less than about 2.0 for nitrogen gas.

37. The membrane according to claim 1, wherein said membrane is elastomeric.

38. The membrane according to claim 37, wherein said membrane has an elongation of at least about 250%.

39. The membrane according to claim 38, wherein said membrane has a elongation of between 250% to about 700%.

40. The membrane according to claim 37, wherein said membrane has a tensile strength of at least about 2,500 psi.

41. The membrane according to claim 37, wherein said membrane has an 100% tensile modulus of between 350 to about 3,000 psi.

42. The membrane according to claim 1, wherein said membrane has a durometer hardness ranging from about 60 Shore A to about 65 Shore D.

43. The membrane according to claim 42, wherein said membrane has a durometer hardness ranging from about 80 Shore A to about 55 Shore D.

44. The membrane according to claim 43, wherein said membrane has a durometer hardness ranging from about 85 Shore A to about 50 Shore D.

45. The membrane according to claim 1, wherein said polyurethane is prepared from an isocyanate that is aromatic in nature.

46. The membrane according to claim 45, wherein said isocyanate is diphenylmethane diisocyanate.

47. The membrane according to claim 1, wherein said polyurethane includes:

(a) at least 50 wt. % of at least one barrier material selected from the group consisting of co-polymers of ethylene and vinyl alcohol, polyvinylidene chloride, co-polymers of acrylonitrile and methyl acrylate, polyethylene terephthalate, aliphatic and aromatic polyamides, crystalline polymers and polyurethane engineering thermoplastics, said at least one barrier material being blended with said polyurethane prior to forming said membrane;

(b) 1 wt. % to about 50 wt. % of at least one aliphatic thermoplastic urethane; and

(c) up to about 3 wt. % of one or more aromatic thermoplastic urethanes, wherein the total constituency of the blended layer is equal to 100 wt. %.

48. The membrane according to claim 47, wherein said aromatic thermoplastic urethane is selected from the group consisting of polyester, polyether, polycaprolactone, polyoxypropylene and polycarbonate macroglycol based materials and mixtures thereof.

49. The membrane according to claim 47, wherein said thermoplastic is based on aromatic 1,4,diphenylmethane diisocyanate.

50. The membrane according to claim 1, wherein said membrane forms a first layer of a multi-layer structure.

51. The membrane according to claim 50, further comprising a second layer formed from a material selected from the group consisting of co-polymers of ethylene and vinyl alcohol, polyvinylidene chloride, co-polymers of acrylonitrile and methyl acrylate, polyethylene terephthalate, aliphatic and aromatic polyamides, crystalline polymers, polyurethane engineering thermoplastics and mixtures thereof which is bonded to said first layer.

52. The membrane according to claim 51, wherein said first and second layers are formed together such that hydrogen bonding occurs between said first and second layers.

53. The membrane according to claim 1, wherein said membrane is formed at least in part from a thermoset material.

59. A membrane according to claim 1, wherein said membrane has an average thickness of from about 5 mils to about 200 mils.

60. A membrane according to claim 1, wherein said membrane has an average thickness of from about 5 mils to about 60 mils.

61. A membrane according to claim 1, wherein said membrane has an average thickness of from about 15 mils to about 40 mils.

54. A flexible membrane comprising:

a polyurethane including a polyester polyol, said membrane having a durability of at least 200,000 cycles under a KIM test analysis;

wherein said membrane is sealed and in an inflated state.

55. The membrane according to claim 54, wherein said membrane has a durability of more than 750,000 cycles under a KIM test analysis.

56. A flexible membrane comprising:

a polyurethane including a polyester polyol, said membrane having a yellowness index of 4.0 or less;

wherein said membrane is sealed and in an inflated state.

57. The membrane according to claim 56, wherein said yellowness index is 1.6 or less.

58. A flexible membrane comprising:

a polyurethane including a polyester polyol, said membrane having a total transmission of light at a level of at least 90.0%;

wherein said membrane is sealed and in an inflated state.