Substrates treated with polyfluoro nitrogen-containing organic compounds

• US 5,580,645 A
• Filed: 08/08/1995
• Issued: 12/03/1996
• Est. Priority Date: 12/29/1989
• Status: Expired due to Term

• Current Assignee: E. I. du Pont de Nemours and Company (Corteva, Inc.)
• Original Assignee: E. I. du Pont de Nemours and Company (Corteva, Inc.)
• Inventors: Kirchner, Jack R.
• Primary Examiner(s): Nakarani, D. S.
• Assistant Examiner(s): Chen, Vivian
• Application Number:
  US08/512,514
• Time in Patent Office: 483 Days
• Field of Search: 428/421, 428/422, 428/423.1, 428/424.6, 428/246, 428/260, 428/262, 428/289, 428/290, 428/224, 428/288, 560/335, 560/357, 560/356, 560/337, 560/358, 560/359, 560/349, 564/54, 564/38, 252/8.51, 252/8.6, 252/8.8, 252/8.7, 252/8.75, 528/70
• US Class Current: 442/80
• CPC Class Codes: C07C 275/62 Y being a nitrogen atom, e.g. biuret
• CPC Class Codes: Y10T 428/31551 Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
• CPC Class Codes: Y10T 442/2172 Also specified as oil repellent
• CPC Class Codes: Y10T 442/2189 Fluorocarbon containing
• CPC Class Codes: Y10T 442/2287 Fluorocarbon containing

Abstract

A substrate having oil-, water- and soil-repellency and/or soil release properties is produced by treating the substrate with a polyfluoro organic compound having at least 1 urea linkage derived from: (A) at least 1 polyisocyanate which contains at least three isocyanate groups per molecule, (B) at least 1 fluorochemical compound which contains (i) a single functional group having 1 or more Zerewitinoff hydrogen atom S and (ii) at least 2 carbon atoms each of which contains at least 2 fluorine atoms, and (C) sufficient water to react with from about 5% to about 60% of the isocyanate groups.

Claims

1. A substrate treated with, as a water-, oil- and soil-repellent or a soil-release agent, wherein said repellant or release agent comprises a polyfluoro organic compound in a form consisting of a water dispersion, a water emulsion, or an organic solvent solution, said polyfluoro organic compound having at least one urea linkage, and is prepared by reacting in solution in an organic solvent:

(A) at least one polyisocyanate which contains at least three isocyanate groups per molecule, with (B) at least one fluorochemical compound which contains per molecule (i) a single functional group having one or more Zerewitinoff hydrogen atoms and (ii) at least two carbon atoms each of which contains at least two fluorine atoms, and then with (C) water in an amount sufficient to react with from about 5% to about 60% of the isocyanate groups in said polyisocyanate, wherein said substrate is selected from the group consisting of films, fibers, yarns, fabrics, and articles made therefrom.

2. The substrate of claim 1 wherein the amount of water is sufficient to react with about 15% to 30% of said isocyanate groups.

3. The substrate of claim 1 wherein said fluorochemical compound is represented by the formula:

space="preserve" listing-type="equation">R.sup.f --R.sub.k --X--H

in which

R^f is a monovalent aliphatic group containing at least two carbon atoms each of which contains at least two fluorine atoms;

R is a divalent organic radical;

k is 0 or 1; and

X is --O--, --S--, or --N(R¹)-- in which R¹ is H, alkyl containing 1 to 6 carbon atoms or a R^f --R_k -- group.

4. The substrate of claim 3 wherein said fluorochemical compound can be represented by the formula:

space="preserve" listing-type="equation">R.sup.f --R.sub.k --R.sup.2 --X--H

in which

R is the divalent radical;

--C_m H_2m SO--, --C_m H_2m SO₂ --, --SO₂ N(R³)--, or --CON(R³)--;

m is 1 to 22, and R³ is H or alkyl of 1 to 6 carbon atoms;

R² is the divalent linear hydrocarbon radical;

--C_n H_2n --, ##STR10## n is 0 to 12, p is 1 to 50, and R⁴, R⁵ and R⁶ are the same or different H or alkyl containing 1 to 6 carbon atoms; and

X is --O--, --S--, or --N(R⁷)--;

R⁷ is H, alkyl containing 1 to 6 carbon atoms or a R^f --R_k --R² -- group.

5. The substrate of claim 4 wherein R^f is a perfluorinated straight or branched aliphatic radical of 3 to 20 carbon atoms wherein said aliphatic radical optionally contains oxygen atoms.

6. The substrate of claim 5 wherein said fluorochemical compound is represented by the formula:

space="preserve" listing-type="equation">R.sup.f --(CH.sub.2).sub.q --X--H

in which

R^f is a mixture of perfluoroalkyl groups, CF₃ CF₂ (CF₂)_r in which r is 2 to 18; and

q is 1, 2 or 3.

7. The substrate of claim 6 wherein

R^f is a mixture of said perfluoroalkyl groups, CF₃ CF₂ (CF₂)_r ;

and

r is 2, 4, 6, 8, 10, 12, 14, 16, and 18.

8. The substrate of claim 7 wherein X is oxygen and q is 2.

9. The substrate of claim 7 wherein r is predominately 4, 6 and 8.

10. The substrate of claim 7 wherein r is predominately 6 and 8.

11. The substrate of claim 7 wherein X is --N(R⁷)--, R⁷ is H, and q is 2.

12. The substrate of claim 3 wherein said fluorochemical compound is represented by the formula:

H(CF₂ CF₂)_w CH₂ OH in which w is 1-10.

13. The substrate of claim 3 wherein said fluorochemical compound is represented by the formula:

CF₃ (CF₃)CHOH.

14. The substrate of claim 1 further characterized in that between about 1% and about 60% of said isocyanate groups are reacted with at least one non-fluorinated organic compound which contains one Zerewitinoff hydrogen atom.

15. The substrate of claim 14 wherein said non-fluorinated compound is represented by the formula:

space="preserve" listing-type="equation">R.sup.10 --R.sup.11.sub.k --YH

in which

R¹⁰ is a C₁ -C₁₈ alkyl, a C₁ -C₁₈ omega-alkenyl radical or a C₁ -C₁₈ omega-alkenoyl;

R¹¹ is ##STR11## R⁴, R⁵ and R⁶ are the same or different H or alkyl radical containing 1 to 6 carbon atoms and p is 1 to 50; and

k is 0 or 1; and

Y is --O--, --S--, or --N(R⁷)-- in which R⁷ is H or alkyl containing 1 to 6 carbon atoms.

16. The substrate of claim 15 wherein said non-fluorinated compound is an alkanol, monoalkyl ether of a poly(oxyalkylene) glycol, monomethyl ether of a poly(oxyethylene) glycol, monoalkenyl ether of a poly(oxyethylene) glycol, or monoallyl ether of a poly(oxyethylene) glycol.

17. The substrate of claim 1 wherein said polyisocyanate is represented by the formula:

##STR12## in which x is an integer equal to or greater than 1.

18. The substrate of claim 17 wherein x is 1 to 8.

19. The substrate of claim 1 wherein said polyisocyanate is represented by the formula:

##STR13## in which R¹² is a divalent hydrocarbon group.

20. The substrate of claim 19 wherein said divalent hydrocarbon radical is an aliphatic, alicyclic, aromatic or arylaliphatic radical.

21. The substrate of claim 20 wherein R¹² is a hexamethylene radical, a toluene radical, or a cyclohexylene radical.

22. The substrate of claim 1 wherein said polyisocyanate is represented by the formula:

##STR14## in which R¹³ is a methyl or ethyl radical, and ##STR15##