Fluorosilicone polymers and surface treatment agent

1. A fluorine-containing polymer for a water- and oil-repellent agent comprising repeating units derived from:

component (A) which comprises;

(A1) a fluorine-containing monomer of the formula:

CH2=C(—X)—C(═O)—Y—Z—Rf

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

Y is —O— or —NH—,

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

Rf is a fluoroalkyl group having 1 to 20 carbon atoms, and

(A2) a (meth) acrylate monomer having a cyclic hydrocarbon group,

(A3-1) a non-crosslinkable monomer of the formula: CH2=CA1COOA2,

wherein A1 is a hydrogen atom, a methyl group, a chlorine atom, a bromine atom, or an iodine atom, and A2 is an alkyl group represented by CnH2n+1, where n is from 1 to 30,

(A3) at least one monomer selected from the group consisting of vinyl halide and vinylidene halide, and

(B) an amino-mercapto-functional organopolysiloxane having 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 Me3Si and wherein Me is a methyl group;

wherein the amino-mercapto-functional organopolysiloxane (B) functions as a chain transfer agent; and

wherein the amino-mercapto-functional organopolysiloxane (B) is bonded to the fluorine-containing monomer through the mercapto group of the amino-mercapto-functional organopolysiloxane.

2. A fluorine-containing polymer according to claim 1 , wherein the fluorine-containing monomer (A1) is an acrylate ester of the formula:

CH2=C(—X)—C(═O)—Y—Z—Rf  (I)

wherein X is a hydrogen atom, a linear or branched alkyl group having 1 to 21 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, a iodine atom, a CFX 1 X 2 group (wherein X 1 and X 2 is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or a iodine atom), a cyano group, a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group;

Y is —O— or —NH—;

Z is a direct bond, an aliphatic group having 1 to 10 carbon atoms, an aromatic or cycloaliphatic group having 6 to 18 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), a —CH 2 CH(OZ 1 )CH 2 — group (wherein Z 1 is a hydrogen atom or an acetyl group), a —(CH 2 ) m —SO 2 —(CH 2 ) n — group, or a —(CH 2 ) m —S—(CH 2 ) n — group (wherein m is from 1 to 10 and n is from 0 to 10); and RF is a linear or branched fluoroalkyl group having 1 to 20 carbon atoms.

3. The fluorine-containing polymer according to claim 1 , wherein the (meth) acrylate monomer (A2) is a monomer having a saturated cyclic hydrocarbon group.

4. The fluorine-containing polymer according to claim 1 , wherein the (meth)acrylate monomer (A2) has 4 to 20 carbon atoms.

5. The fluorine-containing polymer according to claim 1 , wherein, in the (meth)acrylate monomer (A2), a carbon atom in a ring in the cyclic hydrocarbon group directly bonds to an ester group in the (meth)acrylate monomer.

6. The fluorine-containing polymer according to claim 1 , wherein, in the (meth)acrylate monomer (A2), the cyclic hydrocarbon group is at least one selected from the group consisting of a cyclohexyl group, a t-butyl cyclohexyl group, an isobornyl group, a dicyclopentanyl group and a dicyclopentanyl group.

7. The fluorine-containing polymer according to claim 1 , wherein the (meth)acrylate monomer (A2) is at least one selected from the group consisting of t-butylcyclohexyl methacrylate, benzyl methacrylate, isobornyl methacrylate, isobornyl acrylate, dicyclopentanyl methacrylate, dicyclopentanyl acrylate, and dicyclopentenyl acrylate.

8. The fluorine-containing polymer according to claim 1 , which contains also repeating units derived from a monomer other than the monomers (A1), (A2), (A3-1) and (A3).

9. The fluorine-containing polymer according to claim 8 , wherein the monomer (A3) is free from a fluorine atom.

10. A method of producing a fluorine-containing polymer for a water- and oil-repellent agent comprising polymerizing repeating units derived from:

component (A) which comprises;

(A1) a fluorine-containing monomer of the formula:

CH2=C(—X)—C(═O)—Y—Z—Rf

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

Y is —O— or —NH—,

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

Rf is a fluoroalkyl group having 1 to 20 carbon atoms,

(A2) a (meth) acrylate monomer having a cyclic hydrocarbon group,

and

(A3-1) a non-crosslinkable monomer of the formula: CH2=CA1COOA2,

wherein A1 is a hydrogen atom, a methyl group, a chlorine atom, a bromine atom, or an iodine atom, and A2 is an alkyl group represented by CnH2n+1, where n is from 1 to 30,

(A3) at least one monomer selected from the group consisting of vinyl halide and vinylidene halide, and

in the presence of

(B) an amino-mercapto-functional organopolysiloxane having 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 and wherein Me is a methyl group;

wherein the amino-mercapto-functional organopolysiloxane (B) functions as a chain transfer agent; and

wherein, upon polymerization, the amino-mercapto-functional organopolysiloxane (B) bonds to the fluorine-containing monomer through the mercapto group of the amino-mercapto-functional organopolysiloxane.

11. A water- and oil-repellent agent comprising the fluorine-containing polymer according to claim 1 .

12. The water and oil-repellent agent according to claim 11 , which contains also an aqueous medium.

13. The water and oil-repellent agent according to claim 11 , which is an aqueous dispersion.

14. A method of treating a substrate, comprising applying the water- and oil-repellent agent according to claim 11 to the substrate.

15. A textile treated with the water- and oil-repellent agent according to claim 11 .

16. The fluorine-containing polymer according to claim 1 wherein, in the (meth) acrylate monomer (A2), the cyclic hydrocarbon group is a saturated or unsaturated monocyclic group, polycyclic group, or bridged ring group.

17. The fluorine-containing polymer according to claim 1 , wherein n is from 10 to 30 in the A 2 group of the non-crosslinkable monomer (A3-1).

18. The fluorine-containing polymer according to claim 1 , wherein, in the (meth)acrylate monomer (A2), the cyclic hydrocarbon group is a bridged ring group.