Use of amphiphilic copolymers containing a fluorinated monomer to impart waterproofness to leather

• US 6,294,103 B1
• Filed: 05/04/1999
• Issued: 09/25/2001
• Est. Priority Date: 11/07/1996
• Status: Expired due to Term

• Current Assignee: 3M Innovative Properties Company (3M Company)
• Original Assignee: 3M Innovative Properties Company (3M Company)
• Inventors: Coppens, Dirk M.
• Primary Examiner(s): GREEN, ANTHONY J
• Application Number:
  US09/297,814
• Time in Patent Office: 875 Days
• Field of Search: 252/8.57, 8 9/41.R, 8 9/421, 427/389, 525/199, 525/200, 106/2, 428/473
• US Class Current: 252/8.57
• CPC Class Codes: C14C 9/00 Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes

Abstract

The present invention provides an amphiphilic copolymer comprising recurring units (I) and (II), wherein: R_f represents a fluorinated alkyl group having at least 3 carbon atoms; Q and Q′ each independently represents an organic liking group or a chemical linkage; R¹ and R² each independently represents hydrogen or a C₁ to C₄ alkyl group; and R_h represents a hydrocarbon group having at least 8 carbon atoms and optionally containing 1 to 3 substituents; and a recurring unit comprising at least one carboxylic acid group or salt thereof. The present invention also provides a method for making the above amphiphilic copolymer. The amphiphilic copolymer can be used in a leather treatment to provide waterproofness to the leather.

Claims

1. Method of treating leather comprising contacting a leather with an amphiphilic copolymer, said amphiphilic copolymer comprising the following recurring units:

wherein;

R_f represents a fluorinated alkyl group having at least 3 carbon atoms;

Q and Q′

each independently represent an organic linking group or a bond;

R¹ and R² each independently represent hydrogen or a C₁ to C₄ alkyl group and;

R_h represents a hydrocarbon group having at least 8 carbon atoms and optionally containing 1 to 3 substituents selected from the group consisting of a halogen, an amino group, an aryl group, and an alkoxy group;

and a recurring unit comprising at least one carboxylic acid group or salt thereof.

2. Method according to claim 1 wherein said recurring unit comprising at least one carboxylic acid group or salt thereof is a recurring unit corresponding to the following formula:

wherein;

R³ represents hydrogen or a C₁ to C₄ alkyl group;

Y represents an organic linking group or a bond and;

M represents a hydrogen or a cation.

3. Method according to claim 1 wherein said amphiphilic copolymer further comprises siloxane containing recurring units.

4. Method according to claim 1 wherein R_h represents an unsubstituted alkyl group and R_f corresponds to C_nF_2n+1- wherein n is an integer between 3 and 14.

5. Method according to claim 2 wherein said amphiphilic copolymer comprises recurring units according to formula (I) in an amount of at least 1% by weight, said recurring units according to formula (I) in an amount of at least 20% by weight and said recurring units according to formula (III) in amount between 5% and 60% by weight, said weight percentages being relative to the total weight of recurring units according to formulas (I), (II) and (Ill).

6. Method according to claim 1 wherein said leather is also contacted with a water and/or oil repellent composition.

7. Method according to claim 1 wherein said amphiphilic copolymer is in the form of an aqueous dispersion.

8. Method according to claim 7 wherein said leather is contacted with said aqueous dispersion during retanning.

9. Method according to claim 2 wherein R_h represents an unsubstituted alkyl group and R_f corresponds to (C_nF_2n+1)- wherein n is an integer between 3 and 14.

10. An amphiphilic copolymer comprising the following recurring units:

wherein;

R_f represents a fluorinated alkyl group having at least 3 carbon atoms;

Q and Q′

each independently represent an organic linking group or a bond;

R¹ and R² each independently represent hydrogen or a C₁ to C₄ alkyl group and;

R_h represents a hydrocarbon group having at least 8 carbon atoms and optionally containing 1 to 3 substituents selected from the group consisting of a halogen, an amino group, an aryl group, and an alkoxy group;

and a recurring unit comprising at least one carboxylic acid group or salt thereof.

11. An amphiphilic copolymer according to claim 10 wherein said recurring unit comprising at least one carboxylic acid group or salt thereof is a recurring unit corresponding to the following formula:

wherein;

R³ represents hydrogen or a C₁ to C₄ alkyl group;

Y represents an organic linking group or a chemical linkage and;

M represents a hydrogen or a cation.

12. An amphiphilic copolymer according to claim 10 further comprising siloxane containing recurring units.

13. An amphiphilic copolymer according to claim 10 wherein R_h represents an unsubstituted alkyl group and R_f corresponds to C_nF_2n+1- wherein n is an integer between 3 and 14.

14. An amphiphilic copolymer according to claim 11 wherein said amphiphilic copolymer comprises recurring units according to formula (I) in an amount of at least 1% by weight, said recurring units according to formula (II) in an amount of at least 20% by weight and said recurring units according to formula (III) in amount between 5% and 60% by weight, said weight percentages being relative to the total weight of recurring units according to formulas (I), (11) and (III).

15. An aqueous composition comprising an amphiphilic copolymer according to claim 10.

16. An aqueous composition according to claim 15 further comprising a water and/or oil repellent composition.

17. An aqueous composition according to claim 16 wherein said water and/or oil repellent composition comprises fluoroaliphatic esters of dimer acids and/or trimer acids.

18. A leather treated with an amphiphilic copolymer according to claim 10.

19. An amphiphilic copolymer according to claim 11 wherein R_h represents an unsubstituted alkyl group and R_f corresponds to (C_nF_2n+1)- wherein n is an integer between 3 and 14.

20. An aqueous composition comprising an amphiphilic copolymer according to claim 11.

21. An aqueous composition comprising an amphiphilic copolymer according to claim 12.

22. An aqueous composition comprising an amphiphilic copolymer according to claim 13.

23. An aqueous composition comprising an amphiphilic copolymer according to claim 14.

24. A leather treated with an amphiphilic copolymer according to claim 11.

25. A leather treated with an amphiphilic copolymer according to claim 12.

26. A leather treated with an amphiphilic copolymer according to claim 13.

27. A leather treated with an amphiphilic copolymer according to claim 14.

28. A method for making an amphiphilic copolymer comprising a free radical polymerisation of a mixture comprising monomers (a), (b) and an ethylenically unsaturated monomer having at least one carboxylic acid group or a salt thereof or a precursor of a carboxylic acid group:

wherein;

at least 20% by weight of the total weight of recurring units is derived from monomer (b) and at least 1% by weight of the total weight of recurring units is derived from monomer (a);

R_f represents a fluorinated alkyl group having at least 3 carbon atoms;

Q and Q′

each independently represent an organic linking group or a chemical linkage;

R¹ and R² each independently represent hydrogen or a C₁ to C₄ alkyl group; and

R_h represents a hydrocarbon group having at least 8 carbon atoms and optionally containing 1 to 3 substituents.

29. A method according to claim 28 wherein said ethylenically unsaturated monomer corresponds to the following formula (c):

wherein;

Y represents an organic linking group or a chemical linkage;

R³ represents hydrogen or a C₁ to C₄ alkyl group and;

M represents hydrogen or a cation.