Low Swell, Water Vapour Permeable Poly(Urethane-Urea)S

• US 20080102314A1
• Filed: 01/11/2006
• Published: 05/01/2008
• Est. Priority Date: 01/14/2005
• Status: Active Grant

• Current Assignee: Baxenden Chemicals Ltd. (Lanxess AG)
• Original Assignee: Baxenden Chemicals Ltd. (Lanxess AG)
• Inventors: Eggington, Noel Thomas, Danes, Rosemary, Lomax, George Robert
• Granted Patent: US 7,981,821 B2
• Time in Patent Office: Days
• US Class Current: 428/704
• CPC Class Codes: C08G 18/10 Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
• CPC Class Codes: C08G 18/12 using two or more compounds having active hydrogen in the first polymerisation step
• CPC Class Codes: C08G 18/3225 Polyamines
• CPC Class Codes: C08G 18/4854 Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
• CPC Class Codes: C08G 18/71 Monoisocyanates or monoisothiocyanates
• CPC Class Codes: D06M 15/564 Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
• CPC Class Codes: D06M 15/568 Reaction products of isocyanates with polyethers
• CPC Class Codes: Y10S 428/913 Material designed to be responsive to temperature, light, moisture
• CPC Class Codes: Y10T 442/2213 Coating or impregnation is specified as weather proof, water vapor resistant, or moisture resistant
• CPC Class Codes: Y10T 442/2221 Coating or impregnation is specified as water proof
• CPC Class Codes: Y10T 442/674 Nonwoven fabric with a preformed polymeric film or sheet

Abstract

A poly(urethane-urea) comprising segments derived from

• • (a) a diisocyanate or mixture of diisocyanates;
  • (b) a polyether polyol comprising repeating units of general formula

—[(CH₂)_mO]—

• • wherein each m is the same or different and is 3 or 4, or a mixture of said polyether polyols; and
  • (c) a diamine or mixture of diamines,
    wherein said polyether polyol segment(s) (b) make up at least 70% by weight of the dry poly(urethane-urea) and wherein the ether oxygen atoms of said polyether polyol segment(s) (b) make up at least 15% by weight of the dry poly(urethane-urea); and wherein said poly(urethane-urea) has an amine end group content of up to 0.2% by weight.

These poly(urethane-urea)s can be manufactured and compounded to give one-component and two-component coating formulations, which can be used to produce materials with good barrier properties such as waterproof breathable fabrics, foul weather and protective clothing, and films for medical and other applications.

Claims

1-38. -38. (canceled)

38. A poly(urethane-urea) comprising segments derived from

(a) a diisocyanate or mixture of diisocyanates;

(b) a polyether polyol comprising repeating units of general formula

—

[(CH₂)_mO]—

wherein each m is the same or different and is 3 or 4, or a mixture of said polyether polyols; and

(c) a diamine or mixture of diamines,

wherein said polyether polyol segment(s) (b) make up at least 70% by weight of the dry poly(urethane-urea) and wherein the ether oxygen atoms of said polyether polyol segment(s) (b) make up at least 15% by weight of the dry poly(urethane-urea); and

wherein said poly(urethane-urea) has an amine end group content of up to 0.2% by weight.

39. A poly(urethane-urea) according to claim 38 which comprises at least 80% by weight of polyether polyol segments.

40. A poly(urethane-urea) according to claim 38 wherein said polyether polyol segment(s) (b) are of formula

—

[(CH₂)_mO]_n—

wherein each m is the same or different and is 3 or 4 and n represents the average number of ether monomer units in the segment and is an integer of from 10 to 70.

41. A poly(urethane-urea) according to claim 40 wherein m is 3 and n is from 35 to 55.

42. A poly(urethane-urea) according to claim 40 wherein m is 4 and n is from 25 to 45.

43. A poly(urethane-urea) according to claim 38, which comprises from 15 to 25% by weight of ether oxygen atoms.

44. A poly(urethane-urea) according to claim 38 having an amine end group content of from 0.005 to 0.15% by weight.

45. A poly(urethane-urea) according to claim 38 having an amine end group content of substantially zero.

46. A poly(urethane-urea) composition comprising a poly(urethane-urea) as claimed in claim 38 and a solvent.

47. A composition according to claim 46 having a solids content of from 10 to 50% by weight.

48. A composition according to claim 46 having a viscosity of from 100 to 500 poise.

49. A composition according to claim 46 which is a one component composition having capped amine end groups and an amine end group content of substantially zero.

50. A composition according to claim 46 additionally comprising one or more crosslinkers.

51. A composition according to claim 50 where the crosslinker is a melamine-formaldehyde precondensate.

52. A composition according to claim 50 where the crosslinker is a blocked isocyanate.

53. A composition according to claim 52 containing from 5 to 20% blocked isocyanate based on the dry weight of polymer.

54. A composition according to claim 52, wherein the blocked isocyanate is an isocyanate blocked with a blocking agent selected from alcohols, caprolactams, phenols, oximes, pyrazoles and malonates.

55. A composition according to claim 54 wherein the blocked isocyanate is an isocyanate blocked with 3,5-dimethylpyrazole or diethyl malonate or a combination thereof.

56. A composition according to claim 46 further comprising one or more additives selected from anti-oxidants, uv stabilisers, matting agents, and pigments.

57. A composition according to claim 56 comprising from 10 to 20% matting agent based on the dry weight of polymer.

58. A composition according to claim 56 where the matting agent is silica with a particle size of from 2 to 5 microns.

59. A process for producing a poly(urethane-urea) according to claim 38 which comprises polymerising

(a) a diisocyanate or a mixture of diisocyanates;

(b) a polyether polyol comprising repeating units of general formula

—

[(CH₂)_mO]—

wherein each m is the same or different and is 3 or 4, or a mixture of said polyether polyols; and

(c) a diamine or a mixture of diamines.

60. A process according to claim 59, wherein diisocyanate component (a) is first reacted with polyether polyol component (b), and the resultant prepolymer is then reacted with diamine component (c).

61. A process according to claim 59 which further comprises capping the amine end groups.

62. A process according to claim 61, wherein the amine end groups are capped by reacting the poly(urethane-urea) with a monofunctional isocyanate.

63. A process for producing a composition according to claim 46 which process comprises polymerising

(a) a diisocyanate or a mixture of diisocyanates;

(b) a polyether polyol comprising repeating units of general formula

—

[(CH₂)_mO]—

wherein each m is the same or different and is 3 or 4, or a mixture of said polyether polyols; and

(c) a diamine or a mixture of diamines

in a solvent and optionally adding one or more crosslinkers and/or one or more additives selected from anti-oxidants, uv stabilisers, matting agents and pigments.

64. A poly(urethane-urea) obtained or obtainable by the process of claim 59.

65. A film comprising a poly(urethane-urea) as claimed in claim 38, optionally on a removable release substrate.

66. A coated material having a coating comprising a poly(urethane-urea) as claimed in claim 38.

67. A coated material according to claim 66, wherein the material is a textile and the coating comprises a first coated layer or film layer comprising said poly(urethane-urea) and optionally one or more further coated layers and/or film layers.

68. A coated material according to claim 67, wherein the first coated layer is the outer layer.

69. An article of clothing or footwear, a tent, bivouac bag, protective blanket, mattress cover, bed sheet, seat cover, wound dressing or drape comprising a coated material as claimed in claim 67.

71. A process for producing (i) a film comprising a poly(urethane-urea) as claimed in claim 38, optionally on a removeable release substrate, or (ii) a coated material having a coating comprising a poly(urethane-urea) as claimed in claim 38, which process comprises applying a composition comprising a poly(urethane-urea) as claimed in claim 38 and a solvent to a material or release substrate, removing the solvent, optionally curing the poly(urethane-urea) and optionally removing the release substrate.

72. A composition obtained or obtainable by the process of claim 63.

73. A process for producing (i) a film comprising a poly(urethane-urea) as claimed in claim 38, optionally on a removeable release substrate, or (ii) a coated material having a coating comprising a poly(urethane-urea) as claimed in claim 38, which process comprises applying a composition to a material or release substrate, removing the solvent, optionally curing the poly(urethane-urea) and optionally removing the release substrate, wherein said composition is obtained or obtainable by polymerising

(a) a diisocyanate or a mixture of diisocyanates;

(b) a polyether polyol comprising repeating units of general formula

—

[(CH₂)_mO]—

wherein each m is the same or different and is 3 or 4, or a mixture of said polyether polyols; and

(c) a diamine or a mixture of diamines

in a solvent and optionally adding one or more crosslinkers and/or one or more additives selected from anti-oxidants, uv stabilisers, matting agents and pigments.

74. A process for producing a coated material having a coating comprising a poly(urethane-urea) as claimed in claim 38, which process comprises (a) bonding a film comprising a poly(urethane-urea) as claimed in claim 38 optionally on a removable release substrate to a material using an adhesive layer, and (b) optionally removing the release substrate, said steps (a) and (b) being carried out in either order.

75. A film or coated material obtained or obtainable by the process of claim 72.

76. A film or coated material obtained or obtainable by the process of claim 73.

77. A coated material obtained or obtainable by the process of claim 74.

78. An article of clothing or footwear, a tent, bivouac bag, protective blanket, mattress cover, bed sheet, seat cover, wound dressing or drape comprising a coated material as claimed in claim 74.

79. An article of clothing or footwear, a tent, bivouac bag, protective blanket, mattress cover, bed sheet, seat cover, wound dressing or drape comprising a coated material as claimed in claim 75.

80. An article of clothing or footwear, a tent, bivouac bag, protective blanket, mattress cover, bed sheet, seat cover, wound dressing or drape comprising a coated material as claimed in claim 76.

81. A multi-layer film having a first film layer comprising a poly(urethane-urea) as claimed in claim 38 and one or more further layers, optionally on a removable release substrate.

82. A film according to claim 81, wherein the first film layer is the outer layer.

70. A process of providing water vapour permeable, low swellable coatings for fabrics using a poly(urethane-urea) comprising segments derived from polytetramethylene oxide and/or polytrimethylene oxide.