Articles comprising aqueous dispersions of polyureaurethanes

• US 7,771,806 B2
• Filed: 11/04/2003
• Issued: 08/10/2010
• Est. Priority Date: 11/04/2002
• Status: Expired due to Fees

• Current Assignee: Invista North America Sarl (Invista)
• Original Assignee: Invista North America Sarl (Invista)
• Inventors: O'Neill, Michael, Yarborough, Portia D., Chen, Jiazhong, Kim, Young H.
• Primary Examiner(s): Tran; Thao T.
• Application Number:
  US10/700,857
• Publication Number:
  US 20050033003A1
• Time in Patent Office: 2,471 Days
• Field of Search: 428/35.7, 428/36.9, 428/423.1, 528/44, 528/59, 528/60, 528/65, 528/66, 528/71, 528/80, 528/83, 528/84, 528/85
• US Class Current: 428/36.9
• CPC Class Codes: C08G 18/0823 containing carboxylate salt groups or groups forming them
• CPC Class Codes: C08G 18/0866 the dispersing or dispersed phase being an aqueous medium
• CPC Class Codes: C08G 18/12 using two or more compounds having active hydrogen in the first polymerisation step
• CPC Class Codes: C08G 18/4854 Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
• CPC Class Codes: C08G 18/6692 with compounds of group C08G18/34
• CPC Class Codes: Y10T 428/1352 Polymer or resin containing [i.e., natural or synthetic]
• CPC Class Codes: Y10T 428/139 Open-ended, self-supporting conduit, cylinder, or tube-type article
• CPC Class Codes: Y10T 428/31551 Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]

Abstract

Stable aqueous poly(urea/urethane) polymers and dispersions are made that do not require the inclusion of chain extenders, curing agents or crosslinking agents. The disclosed poly(urea/urethane) dispersions can be used to make articles such as films and gloves with reduced chance of chemical and biological allergic reaction to skin, and which exhibit improved puncture and tear resistance when compared to such articles made with other materials.

Claims

1. A film prepared from a urea/urethane polymer comprising (a) repeating units derived from a hydroxy-terminated copolymer prepared from tetrahydrofuran and one or both of an alkylene oxide and a cyclic acetal and (b) repeating units derived from a polyisocyanate;

wherein the urea/urethane polymer contains less than about 2 mole percent of urea units described by the formula —

R—

N(R²)—

C(O)—

N(R²)—

R¹—

;

wherein R is an aromatic hydrocarbon radical, R¹ is an aliphatic hydrocarbon radical, and R² is H or an amide group that is described by the formula —

C(O)—

N(R²)—

R—

; and

wherein the tetrahydrofuran is described by the formula

2. A film according to claim 1 wherein the polyisocyanate is selected from the group consisting of toluene diisocyanate, methylene diphenyldiisocyanate and polymethylene polyphenylisocyanate.

3. A film according to claim 1 wherein the alkylene oxide is selected from the group consisting of 1,2-propylene oxide and ethylene oxide.

4. A film according to claim 1 wherein the alkylene oxide is ethylene oxide.

5. A film according to claim 1 wherein each R⁴ in the tetrahydrofuran is hydrogen.

6. A film according to claim 1 wherein each R⁴ in the tetrahydrofuran is hydrogen, the hydroxy-terminated copolymer is prepared from an alkylene oxide, and the alkylene oxide is ethylene oxide.

7. A film according to claim 1 wherein the urea/urethane polymer contains less than about 1 mole percent of the described urea units.

8. A film according to claim 1 wherein the urethane polymer further comprises repeating units derived from an ionic compound or a potentially ionic compound.

9. A film according to claim 1 that is prepared from an aqueous dispersion of the urea/urethane polymer of claim 1 and a surfactant.

28. A film according to claims 1, 10 or 20 that is fabricated in the form of a glove.

29. A glove according to claim 28 wherein the glove is not perforated or broken at the point of contact between the thumb and forefinger after the thumb and forefinger have dipped in isopropyl alcohol and rubbed together for a time of about 30 to about 60 seconds.

10. A film prepared from an ionomeric urea/urethane polymer comprising (a) repeating units derived from an aliphatic polyether polyol having a molecular weight of about 700 to about 1500, and (b) repeating units derived from a polyisocyanate,

wherein the urea/urethane polymer contains less than about 2 mole percent of urea units described by the formula —

R—

N(R²)—

C(O)—

N(R²)—

R¹—

;

wherein R is an aromatic C₆-C₂₀ hydrocarbon radical, R¹ is an aliphatic C₁-C₂₀ hydrocarbon radical, and R² is H or an amide group that is described by the formula —

C(O)—

N(R²)—

R—

.

11. A film according to claim 10 which comprises repeating units derived from an ionic compound or a potentially ionic compound.

12. A film according to claim 11 wherein the ionic compound or potentially ionic compound comprises a hydroxy-carboxylic acid of the general formula (HO)_xR⁷(COOH)_y, wherein R⁷ represents a straight or branched hydrocarbon radical containing 1 to 12 carbon atoms, and x and y each independently represents values from 1 to 3.

13. A film according to claim 11 wherein the ionic compound or potentially ionic compound comprises 2,2′

dimethanolpropionic acid.

14. A film according to claim 10 wherein the polyisocyanate is selected from the group consisting of toluene diisocyanate, methylene diphenyldiisocyanate and polymethylene polyphenylisocyanate.

15. A film according to claim 10 wherein the polyether polyol is described by the formula HO—

[(CR⁵H)_m—

O—

]_n—

H, wherein R⁵ is hydrogen, a halogen or a C₁ to C₄ alkyl radical;

m is 3 or 4; and

n is in the range of about 8 to about 20.

16. A film according to claim 15 wherein R⁵ is hydrogen.

17. A film according to claim 10 wherein the polyether polyol has a molecular weight in the range of about 900 to about 1150.

18. A film according to claim 10 wherein the urea/urethane polymer contains less than about 1 mole percent of the described urea units.

19. A film according to claim 10 that is prepared from an aqueous dispersion of the urea/urethane polymer of claim 10 and a surfactant.

20. A film prepared from an ionomeric urea/urethane polymer comprising (a) repeating units derived from an aliphatic polyester polyol, and (b) repeating units derived from a polyisocyanate,

wherein the urea/urethane polymer contains less than about 2 mole percent of urea units described by the formula —

R—

N(R²)—

C(O)—

N(R²)—

R¹;

wherein R is a C₆-C₂₀ aromatic hydrocarbon radical, R¹ is a C₁-C₂₀ aliphatic hydrocarbon radical, and R² is H or an amide group that is described by the formula C(O)—

N(R²)—

R—

.

21. A film according to claim 20 which comprises repeating units derived from an ionic compound or a potentially ionic compound.

22. A film according to claim 21 wherein the ionic compound or potentially ionic compound comprises a hydroxy-carboxylic acid of the general formula (HO)_xR⁷(COOH)_y, wherein R⁷ represents a straight or branched hydrocarbon radical containing 1 to 12 carbon atoms, and x and y each independently represents values from 1 to 3.

23. A film according to claim 21 wherein the ionic compound or potentially ionic compound comprises 2,2′

dimethanolpropionic acid.

24. A film according to claim 20 wherein the polyisocyanate is selected from the group consisting of toluene diisocyanate, methylene diphenyldiisocyanate and polymethylene polyphenylisocyanate.

25. A film according to claim 20 wherein the polyester polyol is a dihydroxy-terminated polymer selected from the group consisting of an ethylene adipate, a butylene adipate, an ethylene/butylene adipate, and mixtures thereof.

26. A film according to claim 20 wherein the urea/urethane polymer contains less than about 1 mole percent of the described urea units.

27. A film according to claim 20 that is prepared from an aqueous dispersion of the urea/urethane polymer of claim 20 and a surfactant.