Fluorochemical composition containing a condensation product of a fluorochemical polyether and a poly-isocyanate to impart stain release properties to a substrate

• US 6,485,789 B1
• Filed: 09/24/1999
• Issued: 11/26/2002
• Est. Priority Date: 05/14/1997
• Status: Expired due to Fees

• Current Assignee: 3M Innovative Properties Company (3M Company)
• Original Assignee: 3M Innovative Properties Company (3M Company)
• Inventors: Dams, Rudolf J., Vander Elst, Pierre J., Allewaert, Kathy E. M. L. A.
• Primary Examiner(s): Reddick, Judy M.
• Application Number:
  US09/381,871
• Time in Patent Office: 1,159 Days
• Field of Search: 524/503, 525/56, 525/58, 252/8.62, 427/386, 427/393, 427/389.9, 427/391, 427/392, 427/393.4, 427/385.5, 427/388.1, 427/388.4, 811/556, 811/564
• US Class Current: 427/393.4
• CPC Class Codes: C08G 18/2885 containing halogen atoms
• CPC Class Codes: C08G 18/3876 containing mercapto groups
• CPC Class Codes: C08G 18/5072 containing sulfur
• CPC Class Codes: C08G 18/6212 Polymers of alkenylalcohols; Acetals thereof; Oxyalkylation products thereof
• CPC Class Codes: C08G 18/758 containing two or more cycloaliphatic rings
• CPC Class Codes: D06M 15/576 containing fluorine

Abstract

The invention provides a method of treating of a substrate by contacting the substrate with a fluorochemical composition that comprises a condensation product of a di- or tri-isocyanate and at least one polyether, the polyether being obtained as the reaction product of a fluorochemical substituted epoxide. Substrates treated in accordance with the invention have good stain release properties, particularly to oil stains or tea stains, so stains can be more easily removed from the treated substrate in a laundering procedure.

Claims

1. A method of treatment of a fibrous substrate comprising the step of contacting said substrate with a fluorochemical composition comprising a condensation product of a di- or tri-isocyanate and at least one polyether provided by reacting a fluorochemical substituted epoxide of formula (I) with a compound of formula (III) or (III):

 

HX¹—

B—

X²H 

 

(II)

2. A method according to claim 1 wherein said condensation product is a condensation product of a di- or tri-isocyanate, said polyether, and a chain terminator selected from the group consisting of an alcohol, a thiol and an amine.

3. A method according to claim 2 wherein said chain terminator corresponds to formula (IV):

4. A method according to claim 3 wherein R⁶ is selected from the group consisting of a residue obtained by removing a hydroxyl group from an oxime, a linear or branched alkyl and a group corresponding to formula (V):

5. A method according to claim 1, wherein B represents an organic divalent linking group selected from the group consisting of an alkylene, a poly(oxyalkylene) with an oxyalkylene group having 2 to 4 carbon atoms and a divalent linking group according to formula (A):

wherein;

R_f″

represents a fluorinated aliphatic group that is perfluorinated or partially fluorinated;

L³ and L⁴ independently represent an organic divalent linking group;

R⁸ represents hydrogen or a methyl group;

Z represents the residue of a free radical initiator;

r represents a number of 1 to 10;

u and w independently represent an integer of 0 or 1; and

v represents an integer of 1, 2, 3 or 4.

6. A method according to claim 5 wherein B represents an alkylene group substituted with a fully- or partially-fluorinated aliphatic group that is optionally linked to said alkylene group via an organic divalent linking group.

7. A method according to claim 1 wherein L² in formula (III) corresponds to formula (B):

wherein;

L³ represents an organic divalent linking group;

L⁶ represents an organic divalent linking group;

R⁸ represents hydrogen or a methyl group;

Z represents the residue of a free radical initiator;

k represents a value of 1 to 10;

and u independently represents an integer of 0 to 1.

8. A method according to claim 5 wherein u is 1;

L³ corresponds to one of the following formulas;

wherein

R¹ represents a lower alkyl group containing 1 to 4 carbon atoms and R² represents a linear or branched alkylene group containing 2, 3 or 4 carbon atoms;

w is 1 and L4 corresponds to the following formula (C);

9. A method according to claim 5, wherein one or more of R_f, R_f′

or R_f″

is a fluorinated aliphatic group containing at least 6 carbon atoms.

10. A method according to claim 5, wherein R_f, R_f′

or R_f″

is a perfluorinated aliphatic group.

11. A method according to claim 1, wherein L¹ corresponds to the following formula:

wherein R⁵ represents a lower alkyl group containing 1 to 4 carbon atoms, R⁴ represents a linear or branched alkylene group containing 1, 2, 3 or 4 carbon atoms, and p represents 0 or 1.

12. A method according to claim 1, wherein said substrate comprises natural fibers.

13. A method according to claim 1, wherein said substrate consists of cellulose fibers or polyester fibers.

14. A method according to claim 1, wherein said substrate is textile or paper.

15. A method according to claim 1, wherein said fluorochemical composition further comprises a polymer selected from the group consisting of polyvinyl alcohols and non-ionic cellulose ethers.

16. A method according to claim 15 wherein said polymer is polyvinyl alcohol having a degree of hydrolysis between 65% by weight and 90% by weight.

26. The method of claim 1 wherein L¹ is selected from the group consisting of straight chain, branched chain or cyclic alkylene, arylene, aralkylene, oxy, oxo, thio, sulfonyl. sulfoxy, amino, imino, sulfonamido, carbonamido, carbonyloxy, urethanylene and ureylene groups and combinations thereof.

17. A fluorochemical composition comprising a condensation product of a di- or tri-isocyanate, and at least one polyether provided by reacting a fluorochemical substituted epoxide of formula (I) with a compound of formula (II) or (III):

 

HX¹—

B—

X²H 

 

(II)

18. A fluorochemical composition according to claim 17, wherein said chain terminator corresponds to formula (IV):

19. A fluorochemical composition according to claim 18, wherein R⁶ is selected from the group consisting of a residue obtained by removing a hydroxyl group from an oxime, a linear or branched alkyl, and a group corresponding to formula (V):

20. A fluorochemical composition according to claim 17, wherein B represents an organic divalent linking group selected from the group consisting of an alkylene, a poly(oxyalkylene) with an oxyalkylene group having 2 to 4 carbon atoms and a divalent linking group according to formula (A):

wherein;

R_f″

represents a fluorinated aliphatic group that is perfluorinated or partially fluorinated;

L³ and L⁴ independently represent an organic divalent linking group;

R⁸ represents hydrogen or a methyl group;

Z represents the residue of a free radical initiator;

r represents a value of 1 to 10;

u and w independently represent an integer of 0 or 1; and

v represents an integer of 1, 2, 3 or 4.

21. A fluorochemical composition according to claim 20, wherein B represents an alkylene group substituted with a partially fluorinated or perfluorinated aliphatic group that is optionally linked to said alkylene group via an organic divalent linking group.

22. A fluorochemical composition according to claim 17, wherein L² in formula (III) corresponds to formula (B):

wherein;

L³ represents an organic divalent linking group;

L⁶ represents an organic divalent linking group;

k represents a value of 1 to 10;

Z represents the residue of a free radical initiator;

R⁸ represents hydrogen or a methyl group;

and u represents an integer of 0 or 1.

23. A fluorochemical composition according to claim 20, wherein u is 1;

L³ corresponds to one of the following formulas;

wherein

R¹ represents a lower alkyl group containing 1 to 4 carbon atoms and R² represents a linear or branched alkylene group containing 2, 3 or 4 carbon atoms;

w is 1 and L⁴ corresponds to the following formula (C);

24. A fluorochemical composition according to claim 17, wherein said fluorochemical composition further comprises a polymer selected from the group consisting of polyvinyl alcohols and non-ionic cellulose ethers.

25. A fluorochemical composition according to claim 24 wherein said fluorochemical composition further comprises a polyvinyl alcohol having a degree of hydrolysis between 65% by weight and 90% by weight.