Low swell, water vapour permeable poly(urethane-urea)s

• US 7,981,821 B2
• Filed: 01/11/2006
• Issued: 07/19/2011
• Est. Priority Date: 01/14/2005
• Status: Expired due to Fees

• Current Assignee: Baxenden Chemicals Ltd. (Lanxess AG)
• Original Assignee: Baxenden Chemicals Ltd. (Lanxess AG)
• Inventors: Eggington, Noel Thomas, Danes, Rosemary, Lomax, George Robert
• Primary Examiner(s): Salvatore; Lynda
• Application Number:
  US11/795,200
• Publication Number:
  US 20080102314A1
• Time in Patent Office: 2,015 Days
• Field of Search: 442/394, 442/85, 442/86
• US Class Current: 442/85
• 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. A poly(urethane-urea) comprising segments derived from

(a) a diisocyariate 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.

2. A poly(urethane-urea) according to claim 1 which comprises at least 80% by weight of polyether polyol segments.

3. A poly(urethane-urea) according to claim 1 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.

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

5. A poly(urethane-urea) according to claim 3 wherein m is 4 and n is from 25 to 45.

6. A poly(urethane-urea) according to claim 1, which comprises from 15 to 25% by weight of ether oxygen atoms.

7. A poly(urethane-urea) according to claim 1 having an amine end group content of from 0.005 to 0.15% by weight.

8. A poly(urethane-urea) according to claim 1 having an amine end group content of substantially zero.

9. A poly(urethane-urea) composition comprising a poly(urethane-urea) as claimed in claim 1 and a solvent.

10. A composition according to claim 9 having a solids content of from 10 to 50% by weight.

11. A composition according to claim 9 having a viscosity of from 100 to 500 poise.

12. A composition according to claim 9 which is a one component composition having capped amine end groups and an amine end group content of substantially zero.

13. A composition according to claim 9 additionally comprising one or more crosslinkers.

14. A composition according to claim 13 where the crosslinker is a melamine-formaldehyde precondensate.

15. A composition according to claim 13 where the crosslinker is a blocked isocyanate.

16. A composition according to claim 15 containing from 5 to 20% blocked isocyanate based on the dry weight of polymer.

17. A composition according to claim 15, wherein the blocked isocyanate is an isocyanate blocked with a blocking agent selected from alcohols caprolactams, phenols, oximes, pyrazoles and malonates.

18. A composition according to claim 17 wherein the blocked isocyanate is an isocyanate blocked with 3,5-dimethylpyrazole or diethyl malonate or a combination thereof.

19. A composition according to claim 9 further comprising one or more additives selected from anti-oxidants, uv stabilizers, matting agents, and pigments.

20. A composition according to claim 19 comprising from 10 to 20% matting agent based on the dry weight of polymer.

21. A composition according to claim 19 where the matting agent is silica with a particle size of from 2 to 5 microns.

22. A film comprising a poly(urethane-urea) as claimed in claim 1, optionally on a removable release substrate.

23. A coated material having a coating comprising a poly(urethane-urea) as claimed in claim 1.

24. A coated material according to claim 2, 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.

25. A coated material according to claim 24, wherein the first coated layer is the outer layer.

26. 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 24.

27. A process for producing (i) a film comprising a poly(urethane-urea) as claimed in claim 1, optionally on a removable release substrate, or (ii) a coated material having a coating comprising a poly(urethane-urea) as claimed in claim 1, which process comprises applying a composition comprising a poly(urethane-urea) as claimed in claim 1 and a solvent to a material or release substrate, removing the solvent, optionally curing the poly(urethane-urea) and optionally removing the release substrate.

28. A process for producing (i) a film comprising a poly(urethane-urea) as claimed in claim 1, optionally on a removable release substrate, or (ii) a coated material having a coating comprising a polyurethane-urea) as claimed in claim 1, 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 polymerizing

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

29. A process for producing a coated material having a coating comprising a poly(urethane-urea) as claimed in claim 1, which process comprises (a) bonding a film comprising a poly(urethane-urea) as claimed in claim 1 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.

30. A film or coated material obtained or obtainable by the process of claim 27.

31. A film or coated material obtained or obtainable by the process of claim 28.

32. A coated material obtained or obtainable by the process of claim 29.

33. 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 30.

34. 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 31.

35. 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 32.

36. A multi-layer film having a first film layer comprising a poly(urethane-urea) as claimed in claim 1 and one or more further layers, optionally on a removable release substrate.

37. A film according to claim 36, wherein the first film layer is the outer layer.