Alkylated fluorochemical oligomers and use thereof in the treatment of fibrous substrates

• US 6,525,127 B1
• Filed: 11/08/2000
• Issued: 02/25/2003
• Est. Priority Date: 05/11/1999
• Status: Expired due to Term

• Current Assignee: 3M Innovative Properties Company (3M Company)
• Original Assignee: 3M Innovative Properties Company (3M Company)
• Inventors: Jariwala, Chetan P., Eggleston, James D., Dams, Rudolf J., Yandrasits, Michael A.
• Primary Examiner(s): Cain, Edward J.
• Application Number:
  US09/708,372
• Time in Patent Office: 839 Days
• Field of Search: 524/462, 524/544, 524/560, 525/276, 525/199, 525/200
• US Class Current: 524/462
• CPC Class Codes: C07C 323/52 the carbon skeleton being acyclic and saturated
• CPC Class Codes: C14C 9/00 Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes
• CPC Class Codes: D06M 13/156 containing halogen atoms
• CPC Class Codes: D06M 13/236 containing halogen atoms
• CPC Class Codes: D06M 13/256 Sulfonated compounds esters thereof, e.g. sultones
• CPC Class Codes: D06M 13/265 containing halogen atoms
• CPC Class Codes: D06M 15/277 containing fluorine
• CPC Class Codes: D06M 15/53 Polyethers polyacetals D06M15/39
• CPC Class Codes: D06M 2200/11 Oleophobic properties
• CPC Class Codes: D06M 2200/12 Hydrophobic properties

Abstract

This invention provides a method of treating fibrous substrates, such as leather, by contacting the substrate with a fluorochemical compound comprising: a fluorochemical oligomeric portion comprising an aliphatic backbone with a plurality of pendant fluoroaliphatic groups, each fluoroaliphatic group having a fully fluorinated terminal group and each independently linked to a carbon atom of the aliphatic backbone through an organic linking group; an aliphatic moiety; and a linking group which links the fluorochemical oligomeric portion to the aliphatic moiety. The fluorochemical compounds provide desirable oil, water and stain repellency to fibrous substrates.

Claims

1. A method of treating fibrous substrates comprising contacting the fibrous substrate with composition comprising an alkylated fluorochemical oligomeric compound comprising:

(i) a fluorochemical oligomeric portion comprising an aliphatic backbone with a plurality of fluoroaliphatic groups attached thereto, each fluoroaliphatic group having a fully fluorinated terminal group and each independently linked to a carbon atom of the aliphatic backbone through an organic linking group;

(ii) an aliphatic moiety having at least 12 carbon atoms; and

(iii) a linking group which links the fluorochemical oligomeric portion to the aliphatic moiety.

2. The method of claim 1 wherein said an alkylated fluorochemical oligomeric compound comprises:

(i) an oligomeric portion having both fluoroaliphatic and fluorine-free aliphatic pendent groups;

(ii) an aliphatic moiety having at least 12 carbon atoms; and

(iii) a linking group which links the oligomeric portion to the aliphatic moiety.

3. The method of claim 1 wherein said fluorochemical compounds are selected from the group consisting of:

4. The method of claim 2 wherein said fluorochemical compounds are selected from the group consisting of:

5. The method of claim 3 wherein a is 3 to 8.

6. The method of claim 4 wherein the sum of a+b is 3 to 8.

7. The method of claim 3 wherein R_f has the structure C_oF_2o+1, where o is 4 to 8.

8. The method of claim 3 wherein L is selected from the group of a covalent bond, straight chain, branched chain, or cyclic alkylene, arylene, aralkylene, oxy, oxo, hydroxy, thio, sulfonyl, sulfoxy, amino, imino, sulfonamido, carboxamido, carbonyloxy, urethanylene, ureylene, and combinations thereof.

9. The method of claim 3 wherein L is chosen from the group consisting of

10. The method of claim 2 comprising oligomerized units of compounds of the formula

wherein R₁, R₂, R_f and Q are as defined in claim 2.

11. The method of claim 3 wherein R_f is a pertfluorinated alkyl group having 4 to about 8 carbon atoms.

12. The method of claim 3 wherein Q is selected from the group consisting of

13. The method of claim 1 wherein R is an alkyl group having at least 12 carbon atoms.

14. The method of claim 3 wherein R is an alkyl group having from 12 to 75 carbon atoms.

15. The method of claim 1 wherein said substrate is leather.

16. The method according to claim 1 wherein said composition is in the form of an aqueous dispersion.

17. The method according to claim 16 wherein said leather is contacted with said aqueous dispersion during retanning.

18. The method of claim 1 wherein said fluorochemical oligomeric compounds have a receding contact angle to n-hexadecane of at least about 30°

.

19. The method of claim 1 wherein said fluorochemical oligomeric compounds have an receding contact angle to n-hexadecane of at least about 50°

.

20. The method of claim 1 wherein said composition is applied by spraying, pasting, padding, roll coating, brushing or exhausting.

21. A treated fibrous substrate comprising a coating of a composition comprising an alkylated fluorochemical oligomeric compound comprising:

(i) a fluorochemical oligomeric portion comprising an aliphatic backbone with a plurality of fluoroaliphatic groups attached thereto, each fluoroaliphatic group having a fully fluorinated terminal group and each independently linked to a carbon atom of the aliphatic backbone through an organic linking group;

(ii) an aliphatic moiety having at least 12 carbon atoms; and

(iii) a linking group which links the fluorochemical oligomeric portion to the aliphatic moiety.

22. The treated substrate of of claim 21 wherein said an alkylated fluorochemical oligomeric compound comprises:

(i) an oligomeric portion having both fluoroaliphatic and fluorine-free aliphatic pendent groups;

(ii) an aliphatic moiety having at least 12 carbon atoms; and

(iii) a linking group which links the oligomeric portion to the aliphatic moiety.

23. The method of claim 21 wherein said fluorochemical compounds are selected from the group consisting of:

24. The treated substrate of claim 21 wherein a is 3 to 8.

25. The treated substrate of claim 21 wherein R is an alkyl group having at least 12 carbon atoms.

26. The treated substrate of claim 21 wherein R is an alkyl group having from 12 to 75 carbon atoms.

27. The treated substrate of claim 21 wherein said substrate is leather.