Silane compound containing perfluoro(poly)ether group

1. A perfluoro(poly)ether group containing silane compound of the formula (1a):

A-Rf—X—SiQ k Y 3-k   (1a)

wherein A represents a C 1-16 alkyl which may be substituted by one or more fluorine atoms;

Rf represents —(OC 4 F 8 ) a —(OC 3 F 6 ) b —(OC 2 F 4 ) c —(OCF 2 ) d —

wherein a, b, c and d are each independently an integer of 0 or more and 200 or less, the sum of a, b, c and d is 1 or more and the occurrence order of the respective repeating units in parentheses with the subscript a, b, c or d is not limited in the formula;

X represents a group of the formula:

—(R 6 ) p —(X 1 ) q —R 7 —

wherein:

R 6 represents —(CH 2 ) s — or an o-, m- or p-phenylene group;

R 7 represents —(CH 2 ) t — or an o-, m- or p-phenylene group;

X 1 represents —(X 2 ) r —;

X 2 represents, each independently at each occurrence, a group selected from a group consisting of —O—, —S—, an o-, m- or p-phenylene group, —C(O)O—, —CONR 5 —, —O—CONR 5 —, and —(CH 2 ) v —;

R 5 represents, each independently at each occurrence, a hydrogen atom, a phenyl group or a C 1-6 alkyl group;

v is, each independently at each occurrence, an integer of 1-20;

s is an integer of 1-20;

t is an integer of 1-20;

r is an integer of 1-10;

p is 0 or 1; and

q is 0 or 1;

Y represents, each independently at each occurrence, a hydroxyl group, a hydrolyzable group, or a hydrocarbon group provided that Y does not include a silicon atom;

Q represents, each independently at each occurrence, —Z—SiR 1 n R 2 3-n ;

Z represents, each independently at each occurrence, a divalent organic group that does not include a silicon atom,

R 1 represents, each independently at each occurrence, a hydroxyl group or a hydrolyzable group that does not include a silicon atom;

R 2 represents, each independently at each occurrence, a C 1-22 alkyl group that does not include a silicon atom;

n is, each independently in each Q, an integer selected from 0-3, and the total sum of n in all Q groups is one or more;

k is an integer selected from 2-3.

2. The perfluoro(poly)ether group containing silane compound according to claim 1 to wherein k is 3.

3. The perfluoro(poly)ether group containing silane compound according to claim 1 wherein A is a C 1-16 perfluoroalkyl group.

4. The perfluoro(poly)ether group containing silane compound according to claim 1 wherein Rf is a group of the following formula (a) or (b):

—(OC 3 F 6 ) b —  (a)

wherein b is an integer of from 1 or more and 200 or less; or

—(OC 4 F 8 ) a —(OC 3 F 6 ) b —(OC 2 F 4 ) c —(OCF 2 ) d —  (b)

wherein a and b are each independently an integer of 0 or more and 30 or less, c and d are each independently is an integer of 1 or more and 200 or less, the sum of a, b, c and d is 10 or more and 200 or less, and the occurrence order of the respective repeating units in parentheses with the subscript a, b, c or d is not limited in the formula.

5. The perfluoro(poly)ether group containing silane compound according to claim 1 wherein, in Rf:

—(OC 4 F 8 ) a — is —(OCF 2 CF 2 CF 2 CF 2 ) a —;

—(OC 3 F 6 ) b — is —(OCF 2 CF 2 CF 2 ) b —; and

—(OC 2 F 4 ) c — is —(OCF 2 CF 2 ) c —.

6. The perfluoro(poly)ether group containing silane compound according to claim 1 wherein

X is a C 1-20 alkylene group, —R 6 —X 3 —R 7 —, or —X 4 —R 7 —

wherein X 3 represents —O—, —S—, —C(O)O—, —CONR 5 —, —O—CONR 5 —, or —CONR 5 —(CH 2 ) v —N(R 5 )—;

X 4 represents —S—, —C(O)O—, —CONR 5 —, or

—CONR 5 —(CH 2 ) v —N(R 5 )—.

7. The perfluoro(poly)ether group containing silane compound according to claim 1 wherein R 6 is —(CH 2 ) s —, and R 7 is —(CH 2 ) t —.

8. The perfluoro(poly)ether group containing silane compound according to claim 1 wherein

X is a C 1-20 alkylene group or —(CH 2 ) s —O—(CH 2 ) t —.

9. The perfluoro(poly)ether group containing silane compound according to claim 1 wherein

X is a group selected from a group consisting of:

—CH 2 O(CH 2 ) 2 —,

—CH 2 O(CH 2 ) 3 —,

—CH 2 O(CH 2 ) 6 —,

—(CH 2 ) 2 —,

—(CH 2 ) 3 —,

—(CH 2 ) 4 —,

—(CH 2 ) 6 —,

—CONH—(CH 2 ) 3 —,

—CON(CH 3 )—(CH 2 ) 3 —,

—CON(Ph)-(CH 2 ) 3 — wherein Ph represents a phenyl group,

—CONH—(CH 2 ) 6 —,

—CON(CH 3 )—(CH 2 ) 6 —,

—CON(Ph)-(CH 2 ) 6 — wherein Ph represents a phenyl group,

—CONH—(CH 2 ) 2 NH(CH 2 ) 3 —,

—CONH—(CH 2 ) 6 NH(CH 2 ) 3 —,

—CH 2 O—CONH—(CH 2 ) 3 —,

—CH 2 O—CONH—(CH 2 ) 6 —,

—S—(CH 2 ) 3 —,

—(CH 2 ) 2 S(CH 2 ) 3 —,

—C(O)O—(CH 2 ) 3 —,

—C(O)O—(CH 2 ) 6 —,

and

10. The perfluoro(poly)ether group containing silane compound according to claim 1 wherein Y is, each independently at each occurrence, a group selected from a group consisting of a hydroxyl group, —OR(R′) wherein R′ represents a C 1-12 alkyl group, a C 1-12 alkyl group, a C 2-12 alkenyl group, a C 2-12 alkynyl group and a phenyl group.

11. The perfluoro(poly)ether group containing silane compound according to claim 1 wherein Y is, each independently at each occurrence, a hydroxyl group or an —O(R′) wherein represents a C 1-12 alkyl group.

12. The perfluoro(poly)ether group containing silane compound according to claim 1 wherein n is 3 in Q.

13. The perfluoro(poly)ether group containing silane compound according to claim 1 wherein

A is a C 1-16 perfluoroalkyl group;

Rf is a group of the following formula (a) or (b):

—(OC 3 F 6 ) b —  (a)

wherein b is an integer of 1 or more and 200 or less; or

—(OC 4 F 8 ) a —(OC 3 F 6 ) b —(OC 2 F 4 ) c —(OCF 2 ) d —  (b)

wherein a and b are each independently an integer of 0 or more and 30 or less, c and d are each independently an integer of 1 or more and 200 or less, the sum of a, b, c and d is 10 or more and 200 or less, and the occurrence order of the respective repeating units in parentheses with the subscript a, b, c or d is not limited in the formula;

and

n is 3.

14. The perfluoro(poly)ether group containing silane compound according to claim 1 wherein a number average molecular weight of the A-Rf— moiety is 500-30,000.

15. The perfluoro(poly)ether group containing silane compound according to claim 1 which has a number average molecular weight of 2,000-32,000.

16. The perfluoro(poly)ether group containing silane compound according to claim 6 wherein R 6 is —(CH 2 ) s —, and R 7 is —(CH 2 ) t —.

17. A process for producing the perfluoro(poly)ether group containing silane compound of the formula (1a) according to claim 1 , which comprises the following steps:

Step (1): reacting a compound of the formula (1a-1):

A-Rf—X′—CH ═CH 2   (1a-1)

wherein A and Rf are as defined in claim 1 , and X′ represents a divalent organic group;

with HSiM 3 wherein M is each independently a halogen atom or a C 1-6 alkoxy group, to obtain a compound of the formula (1a-2):

A-Rf—X′CH 2 —CH 2 —SiM 3   (1a-2)

wherein A, Rf, X′ and M are as defined above;

Step (2′): reacting a compound of the formula (1a-2) with a compound of

Formula: G-Z′—CH═CH 2 wherein Z′ represents a bond or a divalent organic group, G represents Li, Na or K, and optionally,

a compound of

Formula: Y h L wherein Y is as defined in claim 1 , L represents a group which is able to bind to Y, and h is an integer of 1-3

to obtain a compound of the formula (1a-3):

A-Rf—X′—CH 2 —CH 2 —Si(Y 3-k′ )(—Z′—CH═CH 2 ) k′   (1a-3)

wherein A, Rf, X′, Y and Z′ is as defined above, and k′ is an integer of 2-3; and

Step (3): reacting a compound of the formula (1a-3) with HSiM 3 wherein M is as defined above, and optionally

a compound of

Formula: R 1 i L′ wherein R 1 is as defined in claim 1 , L′ represents a group which is able to bind to R 1 , and i is an integer of 1-3, and/or

a compound of

Formula: R 2 j L″ wherein R 2′ represents a C 1-22 alkyl group, L″ represents a group which is able to bind to R 2′ , and j is an integer of 1-3.

18. A surface-treating agent comprising at least one the perfluoro(poly)ether group containing silane compound of the formula (1a) according to claim 1 .

19. The surface-treating agent according to claim 18 which further comprises one or more component selected form a fluorine-containing oil, a silicone oil and a catalyst.

20. The surface-treating agent according to claim 19 , comprising a fluorine-containing oil selected from one or more compounds of the formula (3):

R 21 —(OC 4 F 8 ) a′ —(OC 3 F 6 ) b′ —(OC 2 F 4 ) c′ —(OCF 2 ) d′ —R 22   (3)

wherein:

R 21 represents an alkyl group having 1 to 16 carbon atoms which may be substituted by one or more fluorine atoms;

R 22 represents an alkyl group having 1 to 16 carbon atoms which may be substituted by one or more fluorine atoms, a hydrogen atom or a fluorine atom; and

a′, b′, c′ and d′ are each independently an integer of 0 or more and 300 or less, the sum of a′, b′, c′ and d′ is 1 or more, and the occurrence order of the respective repeating units in parentheses with the subscript a′, b′, c′ and d′ is not limited in the formula.

21. The surface-treating agent according to claim 19 , comprising a fluorine-containing oil selected from one or more compounds of the formula (3a) or (3b):

R 21 —(OCF 2 CF 2 CF 2 ) b″ —R 22   (3a)

R 21 —(OCF 2 CF 2 CF 2 CF 2 ) a″ —(OCF 2 CF 2 CF 2 ) b″ —(OCF 2 CF 2 ) c″ —(OCF 2 ) d″ —R 22   (3b)

wherein:

R 21 represents an alkyl group having 1 to 16 carbon atoms which may be substituted by one or more fluorine atoms;

R 22 represents an alkyl group having 1 to 16 carbon atoms which may be substituted by one or more fluorine atoms, a hydrogen atom or a fluorine atom; and

in the formula (3a), b″ is an integer of 1 or more and 100 or less;

in the formula (3b), a″ and b″ are each independently an integer of 0 or more and 30 or less, and c″ and d″ are each independently an integer of 1 or more and 300 or less; and

the occurrence order of the respective repeating units in parentheses with the subscript a″, b″, c″ or d″ is not limited in the formula.

22. The surface-treating agent according to claim 21 which comprises one or more compounds of the formula (3b).

23. The surface-treating agent according to claim 21 which comprises the compound of the formula (3a) and the compound of the formula (3b) at a mass ratio of 1:1-1:30.

24. The surface-treating agent according to claim 21 which comprises the compound of the formula (3a) and the compound of the formula (3b) at a mass ratio of 1:1-1:10.

25. The surface-treating agent according to claim 22 wherein a mass ratio of the perfluoro(poly)ether group containing silane compound of the formula (1a) and the compound of the formula (3b) is 4:1-1:4.

26. The surface-treating agent according to claim 21 wherein the compound of the formula (3a) has a number average molecular weight of 2,000-8,000.

27. The surface-treating agent according to claim 21 wherein the compound of the formula (3b) has a number average molecular weight of 2,000-30,000.

28. The surface-treating agent according to claim 21 wherein the compound of the formula (3b) has a number average molecular weight of 8,000-30,000.

29. The surface-treating agent according to claim 18 which further comprises a solvent.

30. The surface-treating agent according to claim 18 which is used as an antifouling-coating agent.

31. The surface-treating agent according to claim 18 for vacuum deposition.

32. A pellet comprising the surface-treating agent according to claim 18 .