Aqueous oil and water repellent compositions which cure at ambient temperature

• US 5,350,795 A
• Filed: 07/09/1993
• Issued: 09/27/1994
• Est. Priority Date: 07/10/1991
• Status: Expired due to Term

• Current Assignee: 3M Company
• Original Assignee: 3M Company
• Inventors: Smith, Richard S., Audenaert, Frans
• Primary Examiner(s): Michl, Paul R.
• Assistant Examiner(s): NILAND, PATRICK DENNIS
• Application Number:
  US08/089,041
• Time in Patent Office: 445 Days
• Field of Search: 524/507, 524/520, 524/544, 524/805, 528/70, 525/199, 525/200, 428/423.1
• US Class Current: 524/507
• CPC Class Codes: C08G 18/4825 Polyethers containing two hydroxy groups C08G18/4833 - C08G18/5096 take precedence
• CPC Class Codes: C08G 18/8087 containing halogen atoms
• CPC Class Codes: C08L 33/00 Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
• CPC Class Codes: C09D 175/04 Polyurethanes
• CPC Class Codes: D06M 15/277 containing fluorine
• CPC Class Codes: D06M 15/568 Reaction products of isocyanates with polyethers
• CPC Class Codes: D06M 15/576 containing fluorine
• CPC Class Codes: Y10T 428/31551 Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]

Abstract

Fluorochemical compositions for treating textile fibers and fabrics to impart oil and water repellency without thermal treatment are provided. The compositions comprise an aqueous, substantially organic solvent free, solution or dispersion of (a) a fluorochemical acrylate copolymer comprised of a fluorinated acrylate monomer, polyalkylene glycol acrylate or methacrylate, and polyalkylene glycol diacrylate or dimethacrylate; and (b) a polyalkoxylated polyurethane having pendant perfluoroalkyl groups comprised of an aliphatic or aromatic tri- or higher order isocyanate, a fluorinated alcohol, amine, or mercaptan, and a poly(oxyalkylene) diol or dithiol.

Claims

1. Fluorochemical compositions for treating textile fibers and fabrics to impart oil and water repellency without thermal treatment, comprising an aqueous, substantially organic solvent free, solution or dispersion of

(a) a fluorochemical acrylate copolymer comprising the reaction product of a fluorinated acrylate monomer, polyalkylene glycol acrylate or methacrylate, and polyalkylene glycol diacrylate or dimethacrylate;

and

(b) a polyalkoxylated polyurethane having pendant perfluoralkyl groups comprised of an aliphatic or aromatic tri- or higher order isocyanate, a fluorinated alcohol, amine, or mercaptan, and a poly(oxyalkylene) diol or dithiol, said polyalkyoxylated polyurethane having a weight average molecular weight of at least 40,000.

2. The composition of claim 1 wherein the polyalkoxylated polyurethane having pendant perfluoroalkyl groups is represented by the formula ##STR9## where R_f is a fluoroaliphatic radical,

R_h is a non-fluorinated hydrocarbon radical,

Q is an organic linking group,

A is a residue of a tri- or higher order isocyanate, i.e., the residue being that portion of the tri- or higher order isocyanate minus the reacted --NCO groups,

(R¹)_y is a poly(oxyalkylene) moiety, R¹ being an oxyalkylene group with 2 to 6 carbon atoms or a cyclic ether or ester moiety having 2 to 6 carbon atoms and y is a number of about 10 to 50,

X is O, S or a linking group terminating in O or S,

R² is a residue of a tri- or higher order isocyanate, two of the isocyanate groups of the tri- or higher order isocyanate forming the depicted urethane groups and the other isocyanate groups reacted to form pendant --QR_f or --QR_h groups,

s is a number of at least 1 and can be 3 or higher,

z is zero or a number of up to about 4,

s+z is a number of about 4 or higher, and

t is a number of at least about 10 and can be 40 or more.

3. The composition of claim 2 wherein t is 15 to 35.

4. The composition of claim 2 wherein the polyalkoxylated polyurethane having pendant perfluoroalkyl groups has a weight average molecular weight in the range of about 65,000 to 250,000.

5. The composition of claim 1 wherein the fluorochemical acrylate polymers have randomly arranged repeating units ##STR10## wherein R_f is a fluoroaliphatic radical, R³ is H or CH₃, R⁴ is an alkylene group having 2 to 4 carbon atoms, Q is an organic linking group and x is an integer of at least 5, generally 10 to 75 and can be as high as 100.

6. The composition of claim 1 further comprising a solid, non-tacky, water-soluble or water dispersible anti-soiling agent which, upon drying of the composition, is capable of rendering the substrate non-tacky and resistant to soiling.

7. The composition of claim 1 wherein said fluorochemical acrylate polymer comprises 10 to 50 weight percent and said polyalkoxylated polyurethane comprises about 50 to 90 weight percent of said composition.

8. The composition of claim 6 wherein said anti-soiling agent comprises up to 30 weight percent of said composition.

9. The composition of claim 6 wherein said anti-soiling agent is a styrene/maleic anhydride copolymer.

10. The composition of claim 1 further comprising a fluorochemical ester.

11. The composition of claim 10 wherein said fluorochemical ester comprises up to 30 weight percent of said composition.

12. The composition of claim 10 wherein said fluorochemical ester is a fluorochemical adipate ester.

13. The composition of claim 1 further comprising an anti-soiling agent and a fluorochemical ester.

14. The composition of claim 13 wherein said anti-soiling agent and said fluorochemical ester comprise up to 50 weight percent of said composition.

15. The composition of claim 1 wherein said fluorochemical acrylate polymers have randomly arranged repeating units ##STR11## where R_f is a fluoroaliphatic radical, R³ is H or CH₃, R⁴ is an alkylene group having 2 to 4 carbon atoms, Q is an organic linking group and x is an integer of at least 5, generally 10 to 75 and can be as high as 100.

16. The composition of claim 15 wherein said fluorochemical acrylate polymer is a polyoxyethylene terpolymer of ##STR12## preferably in a 1:

1 weight ratio of a;

(b+c) and a 3;

1 weight ratio of b;

c.

17. A method for imparting oil and water repellency to fibers and fabrics comprising (a) contacting said fiber or fabric at ambient temperature with the aqueous composition of claim 1 and (b) allowing said fiber or fabric to dry at ambient temperature.

18. Textile fibers and fabrics having oil and water repellency comprising said fibers and fabrics treated with the composition of claim 1.

23. The composition according to claim 2 in which y of the moiety (R¹)_y is 20 to 35.

19. Composition comprising a polyalkoxylated polyurethane having pendant perfluoroalkyl groups which is represented by formula I where ##STR13## R_f is a fluoroaliphatic radical, R_h is a non-fluorinated hydrocarbon radical,

Q is an organic linking group,

A is a residue of a tri- or higher order isocyanate, i.e., the residue being that portion of the tri- or higher order isocyanate minus the reacted --NCO groups,

R¹)_y is a poly(oxyalkylene) moiety, R¹ being an oxyalkylene group with 2 to 6 carbon atoms or a cyclic ether or ester moiety having 2 to 6 carbon atoms and y is a number of about 10 to 50,

X is O, S or a linking group terminating in O or S,

R² is a residue of a tri- or higher order isocyanate, two of the isocyanate groups of the tri- or higher order isocyanate forming the depicted urethane groups and the other isocyanate groups reacted to form pendant --QR_f or --QR_h groups,

s is a number of at least 2 and can be 3 or higher,

z is zero or a number of up to about 2,

s+z is a number of about 2 to 4 or higher, and

t is a number of at least about 10 and can be 40 or more, said polyalkyoxylated polyurethane having a weight average molecular weight of at least 40,000.

20. The composition of claim 19 wherein t is 15 to 35.

21. The composition of claim 19 wherein the polyalkoxylated polyurethane having pendant perfluoroalkyl groups has a weight average molecular weight in the range of about 65,000 to 250,000.

22. A method for imparting oil and water repellency to fibers and fabrics comprising (a) contacting said fiber or fabric at ambient temperature with an aqueous solution of the composition as claimed in claim 19 and (b) allowing said fiber or fabric to dry at ambient temperature.

24. The composition according to claim 19 in which y of the moiety (R¹)_y is 20 to 35.