Substrates treated with polyfluoro nitrogen containing organic compounds

• US 5,411,766 A
• Filed: 12/10/1993
• Issued: 05/02/1995
• 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): Lusignan, Michael
• Application Number:
  US08/166,331
• Time in Patent Office: 508 Days
• Field of Search: 8/115.51, 8/115.6, 8/45.66, 8/45.64, 252/8.75, 427/393.4
• US Class Current: 427/393.4
• CPC Class Codes: C07C 275/62 Y being a nitrogen atom, e.g. biuret
• CPC Class Codes: C08G 18/2825 having at least 6 carbon atoms
• CPC Class Codes: C08G 18/283 Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds
• CPC Class Codes: C08G 18/2885 containing halogen atoms
• CPC Class Codes: C08G 18/6715 Unsaturated monofunctional alcohols or amines
• CPC Class Codes: C08G 18/725 Combination of polyisocyanates of C08G18/78 with other polyisocyanates
• CPC Class Codes: C08G 18/765 alpha, alpha, alpha', alpha', -tetraalkylxylylene diisocyanate or homologues substituted on the aromatic ring
• CPC Class Codes: C08G 18/7831 containing biuret groups
• CPC Class Codes: C08G 18/792 formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
• CPC Class Codes: C08G 18/794 formed by oligomerisation of aromatic isocyanates or isothiocyanates
• CPC Class Codes: C08G 18/8029 Masked aromatic polyisocyanates
• CPC Class Codes: C08G 18/8032 Masked aliphatic or cycloaliphatic polyisocyanates not provided for in one single of the groups C08G18/8016 and C08G18/8025
• CPC Class Codes: D06M 15/576 containing fluorine

Abstract

Process for imparting oil-, water- and soil-repellency and/or soil release properties to a substrate, and substrates so-treated, which comprises applying to the substrate 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 H'"'"'s and (ii) at least 2 C'"'"'s each of which contains at least 2 F'"'"'s, and (C) sufficient water to react with from about 5% to about 60% of the --NCO groups.

Claims

1. A process for imparting oil-repellency, water-repellency, soil-repellency, or soil release properties to a substrate which comprises applying to the substrate a polyfluoro organic compound comprising a compound having at least one urea linkage which compound is prepared by reacting:

(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 with (C) water in an amount sufficient to react with from about 5% to about 60% of the isocyanate groups in said polyisocyanate.

2. The process of claim 1 wherein the amount of water is sufficient to react with about 10% to about 35% of said isocyanate groups.

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

4. The process of claim 1 wherein said fluorochemical compound which contains a single functional group 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.

5. The process of claim 4 wherein said fluorochemical compound is 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.

6. The process of claim 5 wherein R^f is a fully-fluorinated straight or branched aliphatic radical of 3 to 20 carbon atoms which can be interrupted by oxygen atoms.

7. The process of claim 6 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.

8. The process of claim 7 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.

9. The process of claim 8 wherein X is oxygen and q is 2.

10. The process of claim 8 wherein r is predominately 4, 6 and 8.

11. The process of claim 8 wherein r is predominately 6 and 8.

12. The process of claim 8 wherein X is --N(R⁷)--, R⁷ is H, and q is 2.

13. The process of claim 4 wherein said fluorochemical compound is represented by the formula:

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

14. The process of claim 4 wherein said fluorochemical compound is represented by the formula:

CF₃ (CF₃)CHOH.

15. The process 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.

16. The process of claim 15 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.

17. The process of claim 16 wherein said non-fluorinated compound is an alkanol.

18. The process of claim 16 wherein said non-fluorinated compound is a monoalkyl ether of a poly(oxyalkylene)glycol.

19. The process of claim 18 wherein said non-fluorinated compound is a monomethyl ether of a poly(oxyethylene)glycol.

20. The process of claim 16 wherein said non-fluorinated compound is a monoalkenyl ether of a poly(oxyalkylene)glycol.

21. The process of claim 20 wherein said non-fluorinated compound is a monoallyl ether of a poly(oxyethylene)glycol.

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

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

23. The process of claim 22 wherein x is 1 to 8.

24. The process of claim 1 wherein said polyisocyanate is represented by the formula:

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

25. The process of claim 23 wherein said divalent hydrocarbon radical is an aliphatic, alicyclic, aromatic or arylaliphatic radical.

26. The process of claim 25 wherein R¹² is a hexamethylene radical.

27. The process of claim 25 wherein R¹² is a toluene radical.

28. The process of claim 25 wherein R¹² is a cyclohexylene radical.

29. The process of claim 1 wherein said polyisocyanate is represented by the formula:

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