Fluorosilicones and fluorine- and silicon-containing surface treatment agent

1. A surface treatment agent for use on substrates, said surface treatment agent comprising a fluorine-containing polymer comprising repeating units derived from:

(A) a monomer which comprises;

(a) a fluorine-containing monomer of the formula:

CH 2 ═C(X)COOYRf,

wherein X is a hydrogen atom, a monovalent organic group, or a halogen atom,

Y is a direct bond or a divalent organic group, and

Rf is a fluoroalkyl group having 1 to 21 carbon atoms, and

(B) a mercapto functional organopolysiloxane; wherein said mercapto functional organopolysiloxane (B) is an amino-mercapto functional organopolysiloxane comprising siloxy units having the average formula:

(R 2 SiO) a (RR N SiO) b (RR S SiO) c

wherein a is 0-4000, b is 1-1000, c is 1-1000,

R is independently a monovalent organic group,

R N is a monovalent amino functional organic group, and

R S is a monovalent mercapto functional organic group.

2. The surface treatment agent of claim 1 wherein the fluorine-containing monomer (a) is a compound of the formula:

wherein X is a hydrogen atom, a linear or branched alkyl group having 1 to 21 carbon atoms, a halogen atom, a cyano group, a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenyl group, or a CFX 1 X 2 group,

wherein X 1 and X 2 is a hydrogen atom or a halogen atom,

Y is a direct bond,

an aliphatic group having 1 to 10 carbon atoms,

an aromatic or cycloaliphatic group having 6 to 10 carbon atoms,

a —CH 2 CH 2 N(R 1 )SO 2 — group,

wherein R 1 is an alkyl group having 1 to 4 carbon atoms, or —CH 2 CH(OY 1 )CH 2 — group,

wherein Y 1 is a hydrogen atom or an acetyl group, and

Rf is a linear or branched fluoroalkyl group having 1 to 21 carbon atoms.

3. The surface treatment agent of claim 1 wherein the amino-mercapto functional organopolysiloxane has the average formula:

where a is 0-4000, b is 1-1000, c is 1-1000, and R′ is H, an alkyl group having 1 to 40 carbon atoms, or Me 3 Si.

4. The surface treatment agent of claim 1 , wherein the monomer (A) further comprises:

(b) a fluorine-free monomer, and

(c) optionally, a crosslinkable monomer,

in addition to (a) the fluorine-containing monomer.

5. The surface treatment agent of claim 4 , wherein the fluorine-free monomer (b) is an acrylate of the general formula:

CH 2 ═CA 1 COOA 2

wherein A 1 is a hydrogen atom, a methyl group or a halogen atom other than a fluorine atom, and A 2 is a hydrocarbon group having 1 to 30 carbon atoms, particularly an alkyl group represented by C n H 2n+1 (n=1 to 30).

6. The surface treatment agent of claim 4 , wherein the crosslinkable monomer (c) is a monomer having at least two reactive groups, a monomer having at least two carbon-carbon double bonds, or a monomer having at least one carbon-carbon double bond and at least one reactive group.

7. The surface treatment agent of claim 4 , wherein the crosslinkable monomer (c) is fluorine-free.

8. The surface treatment agent of claim 1 wherein X is chlorine.

9. The surface treatment agent of claim 1 comprising a liquid.

10. The surface treatment agent of claim 1 comprising:

5 to 99.9 wt % of the monomer (A) and

0.1 to 95 wt % of the mercapto functional organopolysiloxane (B); wherein the sum of (A) and (B) equals 100%.

11. A method of treating a substrate comprising:

applying a surface treatment agent to said substrate, said surface treatment agent comprising a fluorine-containing polymer comprising repeating units derived from:

(A) a monomer which comprises;

(a) a fluorine-containing monomer of the formula:

CH 2 ═C(X)COOYRf,

wherein X is a hydrogen atom, a monovalent organic group, or a halogen atom,

Y is a direct bond or a divalent organic group, and

Rf is a fluoroalkyl group having 1 to 21 carbon atoms, and

(B) a mercapto functional organopolysiloxane; wherein said mercapto functional organopolysiloxane (B) is an amino-mercapto functional organopolysiloxane comprising siloxy units having the average formula:

(R 2 SiO) a (RR N SiO) b (RR S SiO) c

wherein a is 0-4000, b is 1-1000, c is 1-1000,

R is independently a monovalent organic group,

R N is a monovalent amino functional organic group, and

R S is a monovalent mercapto functional organic group.

12. The method of claim 11 wherein the fluorine-containing monomer (a) is a compound of the formula:

wherein X is a hydrogen atom, a linear or branched alkyl group having 1 to 21 carbon atoms, a halogen atom, a cyano group, a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenyl group, or a CFX 1 X 2 group,

wherein X 1 and X 2 is a hydrogen atom or a halogen atom,

Y is a direct bond,

an aliphatic group having 1 to 10 carbon atoms,

an aromatic or cycloaliphatic group having 6 to 10 carbon atoms,

a —CH 2 CH 2 N(R 1 )SO 2 — group,

wherein R 1 is an alkyl group having 1 to 4 carbon atoms, or —CH 2 CH(OY 1 )CH 2 — group,

wherein Y 1 is a hydrogen atom or an acetyl group, and

Rf is a linear or branched fluoroalkyl group having 1 to 21 carbon atoms.

13. The method of claim 11 wherein the amino-mercapto functional organopolysiloxane has the average formula:

where a is 0-4000, b is 1-1000, c is 1-1000, and R′ is H, an alkyl group having 1 to 40 carbon atoms, or Me 3 Si.

14. The method of claim 11 , wherein the monomer (A) further comprises:

(b) a fluorine-free monomer, and

(c) optionally, a crosslinkable monomer,

in addition to (a) the fluorine-containing monomer.

15. The method of claim 14 , wherein the fluorine-free monomer (b) is an acrylate of the general formula:

CH 2 ═CA 1 COOA 2

wherein A 1 is a hydrogen atom, a methyl group or a halogen atom other than a fluorine atom, and A 2 is a hydrocarbon group having 1 to 30 carbon atoms, particularly an alkyl group represented by C n H 2n+1 (n=1 to 30).

16. The method of claim 14 , wherein the crosslinkable monomer (c) is a monomer having at least two reactive groups, a monomer having at least two carbon-carbon double bonds, or a monomer having at least one carbon-carbon double bond and at least one reactive group.

17. The method of claim 14 , wherein the crosslinkable monomer (c) is fluorine-free.

18. The method of claim 11 wherein X is chlorine.

19. The method of claim 11 wherein said surface treatment agent is applied in liquid form.

20. The method of claim 11 wherein said surface treatment agent comprises:

5 to 99.9 wt % of the monomer (A) and

0.1 to 95 wt % of the mercapto functional organopolysiloxane (B); wherein the sum of (A) and (B) equals 100%.

21. The method of claim 11 wherein said substrate comprises a textile.