Fluorine-containing surface treating agent and an article surface-treated therewith
The purpose of the present invention is to provide a surface treating agent which provides a surface where stain does not easily adhere, does not stand out and is easily wiped off. The present invention is a perfluoropolyether group-containing polyorganosiloxane represented by the following formula (1) and a surface treating agent comprising the same, A k (R) n Z-Q-Rf-Q-Z(R) n A k (1) wherein Rf is a divalent perfluoropolyether group; Q is a divalent group linking Rf with Z; Z is a polyorganosiloxane group having at least three siloxane bonds with its valency being trivalent to undecavalent; R is a monovalent organic group having 8 to 40 carbon atoms, n is an integer of from 1 to 8; A is a group represented by the following formula (2); and k is an integer of from 1 to 9, provided that a total of n+k=the valency of Z−1 wherein R′ is an alkyl group having 1 to 4 carbon atoms or a phenyl group; X is a hydrolysable group, a is 2 or 3; and b is an integer of from 2 to 10.
1. A perfluoropolyether group-containing polyorganosiloxane represented by the following formula (1),
A k (R) n Z-Q-Rf-Q-Z(R) n A k (1)
wherein Rf is a divalent perfluoropolyether group; Q is a divalent group linking Rf with Z; Z is a polyorganosiloxane group having at least three siloxane bonds with its valency being trivalent to undecavalent; R is a monovalent organic group having 8 to 40 carbon atoms, n is an integer of from 1 to 8; A is a group represented by the following formula (2); and k is an integer of from 1 to 9, provided that n+k=(the valency of Z−1),
wherein R′ is an alkyl group having 1 to 4 carbon atoms or a phenyl group; X is a hydrolysable group, a is 2 or 3; and b is an integer of from 2 to 10.
2. The polyorganosiloxane according to claim 1 , wherein R is a tetradecyl group or a hexadecyl group and n is from 1 to 3.
3. The polyorganosiloxane according to claim 1 or 2 , wherein Rf in formula (1) is a group represented by the following formula,
—(C c F 2c O) d —
wherein c is an integer of from 1 to 6and d is an integer of from 1 to 100.
4. The polyorganosiloxane according to claim 3 , wherein Rf is a group represented by the following general formula (3), (4), or (5),
wherein Y is, independently of each other, F or a CF 3 group; e is an integer of from 1 to 3; g is an integer of from 2 to 6, f and i each are an integer of from 0 to 100, provided that a total of f and i is from 2 to 100; and h is an integer of from 0 to 6; and wherein these repeating units may be sequenced at random,
—C e F 2e (OCF 2 CF 2 CF 2 ) j OC e F 2e — (4)
wherein j is an integer of from 1 to 100; and e is an integer of from 1 to 3,
wherein Y is F or a CF 3 group; e is an integer of from 1 to 3; and k and l each are an integer of from 0 to 100, provided that a total of k and l is from 2 to 100; and wherein these repeating units may be sequenced at random.
5. The polyorganosiloxane according to claim 3 , wherein Rf in formula (1) is a group represented by the following formula (6),
—CF 2 (OCF 2 CF 2 ) m (OCF 2 ) n OCF 2 — (6)
wherein m=0-50, n=1-50, and m+n=2-60.
6. The polyorganosiloxane according to any one of claims 1 to 5 , wherein Q in formula (1) is a group having an amide bond, an ether bond, an ester bond or a vinyl bond.
7. The polyorganosiloxane according to any one of claims 1 to 6 , wherein Z in formula (1) is a group represented by either one of the following formulas
8. The polyorganosiloxane according to any one of claims 1 to 7 , wherein X is a methoxy group or an ethoxy group.
9. A surface treating agent composition comprising:
a perfluoropolyether group-containing polyorganosiloxane represented by the following formula (1) and/or
a partial hydrolysis condensate thereof,
A k (R) n Z-Q-Rf-Q-Z(R) n A k (1)
wherein Rf is a divalent perfluoropolyether group; Q is a divalent group linking Rf with Z; Z is a polyorganosiloxane group having at least three siloxane bonds with its valency being trivalent to undecavalent; R is a monovalent organic group having 8 to 40 carbon atoms, n is an integer of from 1 to 8; A is a group represented by the following formula (2); and k is an integer of from 1 to 9, provided that n+k=(the valency of Z−1),
wherein R′ is an alkyl group having 1 to 4 carbon atoms or a phenyl group; X is a hydrolysable group, a is 2 or 3; and b is an integer of from 2 to 10.
10. An article having, on the surface thereof, a cured coating made from a perfluoropolyether group-containing polyorganosiloxane represented by the following formula (1) and/or a partial hydrolysis condensate thereof,
A k (R) n Z-Q-Rf-Q-Z(R) n A k (1)
wherein Rf is a divalent perfluoropolyether group; Q is a divalent group linking Rf with Z; Z is a polyorganosiloxane group having at least three siloxane bonds with its valency being trivalent to undecavalent; R is a monovalent organic group having 8 to 40 carbon atoms, n is an integer of from 1 to 8; A is a group represented by the following formula (2); and k is an integer of from 1 to 9, provided that n+k=(the valency of Z−1),
wherein R′ is an alkyl group having 1 to 4 carbon atoms or a phenyl group; X is a hydrolysable group, a is 2 or 3; and b is an integer of from 2 to 10.
11. The surface treating agent composition according to claim 9 , wherein R is a tetradecyl group or a hexadecyl group and n is from 1 to 3.
12. The surface treating agent composition according to claim 9 or 11 , wherein Rf in formula (1) is a group represented by the following formula,
—(C c F 2c O) d —
wherein c is an integer of from 1 to 6 and d is an integer of from 1 to 100.
13. The surface treating agent composition according to claim 12 , wherein Rf is a group represented by the following general formula (3), (4), or (5),
wherein Y is, independently of each other, F or a CF 3 group; e is an integer of from 1 to 3; g is an integer of from 2 to 6, f and i each are an integer of from 0 to 100, provided that a total of f and i is from 2 to 100; and h is an integer of from 0 to 6; and wherein these repeating units may be sequenced at random,
—C e F 2e (OCF 2 CF 2 CF 2 ) j OC e F 2e — (4)
wherein j is an integer of from 1 to 100; and e is an integer of from 1 to 3,
wherein Y is F or a CF 3 group; e is an integer of from 1 to 3; and k and l each are an integer of from 0 to 100, provided that a total of k and l is from 2 to 100; and wherein these repeating units may be sequenced at random.
14. The surface treating agent composition according to claim 12 , wherein Rf in formula (1) is a group represented by the following formula (6),
—CF 2 (OCF 2 CF 2 ) m (OCF 2 ) n OCF 2 — (6)
wherein m=0-50,n=1-50, and m+n=2-60.
15. The surface treating agent composition according to claim 9 , wherein Q in formula (1) is a group having an amide bond, an ether bond, an ester bond or a vinyl bond.
16. The surface treating agent composition according to claim 9 , wherein Z in formula (1) is a group represented by either one of the following formulas.
17. The surface treating agent composition according to claim 9 , wherein X is a methoxy group or an ethoxy group.
18. The article according to claim 10 , wherein R is a tetradecyl group or a hexadecyl group and n is from 1 to 3.
19. The article according to claim 10 or 18 , wherein Rf in formula (1) is a group represented by the following formula,
—(C c F 2c O) d —
wherein c is an integer of from 1 to 6 and d is an integer of from 1 to 100.
20. The article according to claim 19 , wherein Rf is a group represented by the following general formula (3), (4), or (5),
wherein Y is, independently of each other, F or a CF 3 group; e is an integer of from 1 to 3; g is an integer of from 2 to 6, f and i each are an integer of from 0 to 100, provided that a total of f and i is from 2 to 100; and h is an integer of from 0 to 6; and wherein these repeating units may be sequenced at random,
—C e F 2e (OCF 2 CF 2 CF 2 ) j OC e F 2e — (4)
wherein j is an integer of from 1 to 100; and e is an integer of from 1 to 3,
wherein Y is F or a CF 3 group; e is an integer of from 1 to 3; and k and l each are an integer of from 0 to 100, provided that a total of k and l is from 2 to 100; and wherein these repeating units may be sequenced at random.
21. The article according to claim 19 , wherein Rf in formula (1) is a group represented by the following formula (6),
—CF 2 (OCF 2 CF 2 ) m (OCF 2 ) n OCF 2 — (6)
wherein m=0-50, n=1-50, and m+n=2-60.
22. The article according to claim 10 , wherein Q in formula (1) is a group having an amide bond, an ether bond, an ester bond or a vinyl bond.
23. The article according to claim 10 , wherein Z in formula (1) is a group represented by either one of the following formulas.
24. The article according to claim 10 , wherein X is a methoxy group or an ethoxy group.