Fluorochemical composition comprising a urethane having a fluorochemical oligomer and a hydrophilic segment to impart stain release properties to a substrate

• US 6,239,247 B1
• Filed: 09/24/1999
• Issued: 05/29/2001
• Est. Priority Date: 05/14/1997
• Status: Expired due to Term

• 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): GORR, RACHEL F
• Application Number:
  US09/381,865
• Time in Patent Office: 613 Days
• Field of Search: 560/26, 560/132, 560/115, 528/49, 528/75, 528/70, 525/129, 427/389.9, 106/2, 524/591
• US Class Current: 528/49
• CPC Class Codes: C08G 18/4063 Mixtures of compounds of group C08G18/62 with other macromolecular compounds
• CPC Class Codes: C08G 18/4825 Polyethers containing two hydroxy groups C08G18/4833 - C08G18/5096 take precedence
• CPC Class Codes: C08G 18/6279 containing fluorine atoms
• CPC Class Codes: C08G 18/6295 Polymers of silicium containing compounds having carbon-to-carbon double bonds
• CPC Class Codes: C08G 18/672 Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
• CPC Class Codes: C08G 18/8077 Oximes

Abstract

The present invention provides a method for preparing a fluorochemical composition comprising a urethane by reacting: (A) fluorochemical oligomer of the formula (I): M^f_mM_n—Q¹—T¹ wherein M^f_mM_n represents a fluorochemical oligomer comprising m units derived from fluorinated monomer and n units derived from fluorine-free monomer and wherein the fluorinated monomers and fluorine-free monomers may be the same or different; m is a value of about 2 to 40; n is a value of about 0 to 20; T¹ is an —OH or —NH₂ moiety; Q¹ and T¹ together represent an organic residue obtained by removing a hydrogen atom from a chain transfer agent that is functionalized with T¹; (B) monofunctional compound capable of reacting with an isocyanate and comprising a poly(oxyalkylene) group; (C) isocyanate blocking agent or a fluorine-free oligomer; and (D) isocyanate-reactive compound other than said fluorochemical oligomer, said isocyanate blocking agent, said fluorine-free oligomer and said monofunctional compound; with (E) diisocyanate or a triisocyanate, wherein 33% to 67% of the number of isocyanate groups are reacted with the fluorochemical oligomer according to the formula (I), 33% to 67% of the number of isocyanate groups are reacted with said monofunctional compound, 0 to 33% of the number of isocyanate groups are reacted with an isocyanate blocking agent or a fluorine-free oligomer and 0 to 10% of the number of isocyanate groups are reacted with said isocyanate-reactive compound.

Claims

1. A method for preparing a fluorochemical composition comprising a urethane by reacting:

(A) a fluorochemical oligomer of formula (I)

2. A method according to claim 1, wherein said fluorinated monomer corresponds to the following formula:

3. A method according to claim 2, wherein E is an acrylate or a methacrylate group, L¹ is selected from the group consisting of alkylene groups, poly(oxyalkylene) groups having 1 to 4 oxyalkylene moieties, and organic divalent linking groups according to the following formula:

wherein;

R³ is selected from the group consisting of linear or branched alkylene groups having 2 to 4 carbon atoms, and

R⁴ represents an alkyl group having 1 to 4 carbon atoms.

4. A method according to claim 1, wherein Q¹ corresponds to the formula:

5. A method according to claim 1, wherein said monofunctional compound corresponds to the following formula:

6. A method of treatment of a substrate comprising the step of contacting said substrate with a fluorochemical composition comprising a urethane obtainable by the method of claim 1.

7. A method according to a claim 6, wherein said substrate is a fibrous substrate.

8. A method according to claim 7, wherein said substrate comprises natural fibers.

9. A method according to claim 7, wherein said substrate is fibrous and the fibers are selected from the group consisting of cellulose fibers, polyester fibers and combinations thereof.

10. A method according to claim 6, wherein said fluorochemical composition further comprises a polymer selected from the group consisting of polyvinyl alcohols, copolymers of (meth)acrylic acid and alkyl esters of (meth)acrylic acid, polyethylene glycols and non-ionic cellulose ethers.

11. A fluorochemical composition comprising a urethane obtained by the method of claim 1.

12. A fluorochemical composition according to claim 11, further comprising a polymer selected from the group consisting of polyvinyl alcohols, copolymers of (meth)acrylic acid and alkyl esters of (meth)acrylic acid, polyethylene glycols and non-ionic cellulose ethers.

13. A substrate comprising on at least part of at least one surface a fluorochemical composition as defined in claim 12.

14. The method of claim 6, wherein said fluorochemical composition is used in amounts sufficient to provide 0.01 to 5 weight percent of said fluorochemical composition on said substrate.

15. An emulsion comprising the composition of claim 11 further comprising water, and a surfactant in an amount sufficient to stabilize the emulsion.

16. The emulsion of claim 15 comprising 100 parts by weight fluorochemical composition, 70 to 2000 parts by weight water and 1 to 25 parts by weight surfactant.

17. The method of claim 2 wherein said fluorochemical monomer is selected from the group consisting of:

wherein R=methyl, ethyl or n-butyl.