Surface treating agent including perfluoro(poly)ether-group-containing silane compound

1. A surface-treating agent comprising at least one perfluoro(poly)ether group containing silane compound of the formula (1):

wherein:

Rf is an alkyl group having 1 to 10 carbon atoms which may be substituted by one or more fluorine atoms;

PFPE is

—(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 to 90, 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;

Q is an oxygen atom or a divalent organic group;

R 1 is a hydrogen atom or an alkyl group having 1 to 22 carbon atoms;

R 2 is each independently a hydrogen atom or an inert monovalent organic group;

X is a hydroxyl group or OR 4 ;

R 4 is each independently at each occurrence a substituted or unsubstituted C 1-12 alkyl group;

Y is a hydrogen atom or a halogen atom;

Z is a fluorine atom or a fluoroalkyl group having 1 to 5 carbon atoms;

e is an integer from 0 to 3;

f is 0 or 1;

g is an integer from 1 to 10;

h is an integer from 0 to 3; and

n is an integer from 1 to 3,

wherein

a number average molecular weight of the perfluoro(poly)ether group containing silane compound is 3000 or more and 6000 or less,

polydispersity of g is more than 1.0 and less than 2.0, and

80 mol % or more of the perfluoro(poly)ether group containing silane compound contained in the surface-treating agent is a compound wherein g is 2 or more.

2. The surface-treating agent according to claim 1 wherein the number average molecular weight of the perfluoro(poly)ether group containing silane compound is 3000 or more and 5000 or less.

3. The surface-treating agent according to claim 1 wherein 90 mol % or more of the perfluoro(poly)ether group containing silane compound contained in the surface-treating agent is a compound wherein g is 2 or more.

4. The surface-treating agent according to claim 1 wherein 80 mol % or more of the perfluoro(poly)ether group containing silane compound contained in the surface-treating agent is the compound wherein g is 3 or more.

5. The surface-treating agent according to claim 1 wherein Rf is a perfluoroalkyl group having 1 to 10 carbon atoms.

6. The surface-treating agent according to claim 1 wherein PFPE is a group:

—(OCF 2 CF 2 CF 2 ) b —

wherein b is an integer of 1 or more and 40 or less.

7. The surface-treating agent according to claim 1 wherein PFPE is a group

—(OCF 2 CF 2 CF 2 CF 2 ) a —(OCF 2 CF 2 CF 2 ) b —(OCF 2 CF 2 ) c —(OCF 2 ) d —

wherein a and b is each independently an integer of 0 to 30, c and d is each independently an integer of 1 to 90, 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.

8. The surface-treating agent according to claim 1 , further comprising a solvent.

9. The surface-treating agent according to claim 1 , further comprising one or more other components selected from the group consisting of a fluorine-containing oil, a silicone oil and a catalyst.

10. The surface-treating agent according to claim 9 wherein the fluorine-containing oil is one or more compounds of the formula (2):

Rf 1 —(OC 4 F 8 ) n′ —(OC 3 F 6 ) b′ —(OC 2 F 4 ) c′ —(OCF 2 ) d′ —Rf 2   (2)

wherein:

Rf 1 is an alkyl group having 1 to 16 carbon atoms which may be substituted by one or more fluorine atoms;

Rf 2 is an alkyl group having 1 to 16 carbon atoms which may be substituted by one or more fluorine atoms, a fluorine atom or a hydrogen atom; and

a′, b′, c′ and d′ are each independently an integer of 0 to 300, the sum of a′, b′, c′ and d′ is at least one, 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.

11. The surface-treating agent according to claim 9 wherein the fluorine-containing oil is one or more compounds of the formula (2a) or (2b):

Rf 1 —(OCF 2 CF 2 CF 2 ) b′ —Rf 2   (2a)

Rf 1 —(OCF 2 CF 2 CF 2 CF 2 ) a′ —(OCF 2 CF 2 CF 2 ) b′ —(OCF 2 CF 2 ) c′ —(OCF 2 ) d′ —Rf 2   (2b)

wherein:

Rf 1 is an alkyl group having 1 to 16 carbon atoms which may be substituted by one or more fluorine atoms;

Rf 2 is an alkyl group having 1 to 16 carbon atoms which may be substituted by one or more fluorine atoms, a fluorine atom or a hydrogen atom;

in the formula (2a), b′ is an integer of 1 or more and 300 or less;

in the formula (2b), a′ and b′ is each independently an integer of 0 to 30, c′ and d′ is each independently an integer of 1 to 300, 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.

12. The surface-treating agent according to claim 1 which is used as an antifouling-coating agent or a waterproof-coating agent.

13. A pellet comprising the surface-treating agent according to claim 1 .

14. An article comprising a base material and a layer which is formed on a surface of the base material from the surface-treating agent according to claim 1 .

15. The article according to claim 14 wherein the base material is a glass.

16. The article according to claim 14 wherein the article is an optical member.

17. The article according to claim 14 wherein the article is a display.

18. A process for preparing a surface-treating agent comprising a perfluoro(poly)ether group containing silane compound of the formula (1):

wherein:

Rf is an alkyl group having 1 to 10 carbon atoms which may be substituted by one or more fluorine atoms;

PFPE is

—(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 to 90, the sum of a, b, c and d is at least 1, 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;

Q is an oxygen atom or a divalent organic group;

R 1 is a hydrogen atom or an alkyl group having 1 to 22 carbon atoms;

R 2 is each independently a hydrogen atom or an inert monovalent organic group;

X is a hydroxyl group or OR 4 ;

R 4 is each independently at each occurrence a substituted or unsubstituted C 1-12 alkyl group;

Y is a hydrogen atom or a halogen atom;

Z is a fluorine atom or a fluoroalkyl group having 1 to 5 carbon atoms;

e is an integer from 0 to 3;

f is 0 or 1;

g is an integer from 1 to 10;

h is an integer from 0 to 3; and

n is an integer from 1 to 3,

wherein a number average molecular weight of the perfluoro(poly)ether group containing silane compound is 3000 or more and 6000 or less,

polydispersity of g is more than 1.0 and less than 2.0, and

80 mol % or more of the perfluoro(poly)ether group containing silane compound contained in the surface-treating agent is a compound wherein g is 2 or more,

comprising the steps of:

reacting a perfluoro(poly)ether compound of the formula (1a):

wherein Rf, PFPE, Q, Z, e and f are as defined for the formula (1) and Y 1 is a chlorine, an iodine or a bromine, with a reactive double bond containing silane compound of the formula (1b):

wherein R 1 , R 2 , h and n are as defined for the formula (1), and X 1 is a hydroxyl group, a hydrolyzable group or a halogen atom in a fluorine containing aromatic compound,

and then, optionally following steps (a) and/or (b):

(a) when Y and Y 1 are different, converting Y 1 to Y; and

(b) when X and X 1 are different, converting X 1 to X.

19. A process for preparing a surface-treating agent comprising a perfluoro(poly)ether group containing silane compound of the formula (1′):

wherein:

Rf is an alkyl group having 1 to 10 carbon atoms which may be substituted by one or more fluorine atoms;

PFPE is

—(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 to 90, the sum of a, b, c and d is at least 1, 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;

Q is an oxygen atom or a divalent organic group;

R 1 is a hydrogen atom or an alkyl group having 1 to 22 carbon atoms;

X is a hydroxyl group or OR 4 ;

R 4 is each independently at each occurrence a substituted or unsubstituted C 1-12 alkyl group;

Z is a fluorine atom or a fluoroalkyl group having 1 to 5 carbon atoms;

e is an integer from 0 to 3;

f is 0 or 1;

g is an integer from 1 to 10; and

his an integer from 0 to 3;

wherein a number average molecular weight of the perfluoro(poly)ether group containing silane compound is 3000 or more and 6000 or less,

polydispersity of g is more than 1.0 and less than 2.0, and

80 mol % or more of the perfluoro(poly)ether group containing silane compound contained in the surface-treating agent is a compound wherein g is 2 or more,

comprising the steps of:

reacting a perfluoro(poly)ether compound of the formula (1a):

wherein Rf, PFPE, Q, Z, e and f are as defined above, and Y 1 is a chlorine, an iodine or a bromine,

with a compound of the formula (1c):

wherein R 1 and h are as defined above, in a fluorine containing aromatic compound to obtain a compound of the formula (1d):

wherein Rf, PFPE, Q, Y 1 , Z, R 1 , e, f, g and h are as defined above, and then

reacting the obtained compound with a compound of HX wherein X is as defined above.

20. The process according to claim 18 wherein the fluorine containing aromatic compound is selected from the group consisting of perfluorobenzene, pentafluorobenzene, 1,2,3,4-tetrafluorobenzene, 1,2,3,5-tetrafluorobenzene, 1,2,4,5-tetrafluorobenzene, 1,2,3-trifluorobenzene, 1,2,4-trifluorobenzene, 1,3,5-trifluorobenzene, benzotrifluoride, fluorobenzene, 1-chloro-2-fluorobenzene, 1-chloro-3-fluorobenzene, 1-chloro-4-fluorobenzene, 2,6-dichlorofluorobenzene, 1-fluoro-3-(trifluoromethoxy)benzene, 1-fluoro-2,4-dinitrobenzene, 2,4-dimethoxy-1-fluorobenzene, 1-fluoro-4-nitrobenzene, 2-fluorotoluene, 3-fluorotoluene, 4-fluorotoluene, 3-fluorobenzotrifluoride, 1-chloro-2,4-difluorobenzene, 1-chloro-3,4-difluorobenzene, 1-chloro-3,5-difluorobenzene, 2-chloro-1,3-difluorobenzene, chloropentafluorobenzene, 2,4-dichlorofluorobenzene, 2,5-dichlorofluorobenzene, 2,6-dichlorofluorobenzene, 1,2-dichloro-4-fluorobenzene, 1,3-dichloro-5-fluorobenzene, 1,3-dichloro-2,4,6-trifluorobenzene, 3,4-difluorobenzonitrile, 3,5-difluorobenzonitrile, 3,4-difluoronitrobenzene, 1-ethoxy-2,3-difluorobenzene, 1,2-dicyano-4,5-difluorobenzene, 1-acetoxy-3-fluorobenzene, 1-acetoxy-4-fluorobenzene, 1-acetonyl-4-fluorobenzene, 2-fluoro-m-xylene, 3-fluoro-o-xylene, 4-fluoro-o-xylene, pentafluoroanisole, tetrafluorophthalonitrile, 2-trifluoromethylbenzal chloride, 3-trifluoromethylbenzal chloride, 4-trifluoromethylbenzal chloride, methyl 3-(trifluoromethyl)benzoate, difluorobenzonitrile, bistrifluoromethyl benzonitrile, 4-trifluoromethyl benzonitrile, aminobenzotrifluoride, and trifluoromethylaniline.

21. The process according to claim 18 wherein the fluorine containing aromatic compound is a fluorine containing aromatic compound having 0 to 3 debyes of polarizability.

22. The process according to claim 18 wherein the fluorine containing aromatic compound is selected from the group consisting of benzotrifluoride, difluorobenzonitrile, and bistrifluoromethyl benzonitrile.

23. A surface-treating agent comprising at least one perfluoro(poly)ether group containing silane compound of the formula (1):

wherein:

Rf is an alkyl group having 1 to 10 carbon atoms which may be substituted by one or more fluorine atoms;

PFPE is

—(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 to 90, the sum of a, b, c and d is at least 1, 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;

Q is an oxygen atom or a divalent organic group;

R 1 is a hydrogen atom or an alkyl group having 1 to 22 carbon atoms;

R 2 is each independently a hydrogen atom or an inert monovalent organic group;

X is a hydroxyl group or OR 4 ;

R 4 is each independently at each occurrence a substituted or unsubstituted C 1-12 alkyl group;

Y is a hydrogen atom or a halogen atom;

Z is a fluorine atom or a fluoroalkyl group having 1 to 5 carbon atoms;

e is an integer from 0 to 3;

f is 0 or 1;

g is an integer from 1 to 10;

h is an integer from 0 to 3; and

n is an integer from 1 to 3,

wherein a number average molecular weight of the perfluoro(poly)ether group containing silane compound is 3000 or more and 6000 or less,

polydispersity of g is more than 1.0 and less than 2.0, and

80 mol % or more of the perfluoro(poly)ether group containing silane compound contained in the surface-treating agent is a compound wherein g is 2 or more,

wherein the perfluoro(poly)ether group containing silane compound of the formula (1) is prepared by reacting a perfluoro(poly)ether compound of the formula (1a):

wherein Rf, PFPE, Q, Z, e and f are as defined for the formula (1) and Y 1 is a chlorine, an iodine or a bromine,

with a reactive double bond containing silane compound of the formula (1b):

wherein R 1 , R 2 , h and n are as defined for the formula (1), and X 1 is a hydroxyl group, a hydrolyzable group or a halogen atom

in a fluorine containing aromatic compound,

and then, optionally following steps (a) and/or (b):

(a) when Y and Y 1 are different, converting Y 1 to Y; and

(b) when X and X 1 are different, converting X 1 to X.

24. A surface-treating agent comprising at least one perfluoro(poly)ether group containing silane compound of the formula (1′):

wherein:

Rf is an alkyl group having 1 to 10 carbon atoms which may be substituted by one or more fluorine atoms;

PFPE is

—(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 to 90, the sum of a, b, c and d is at least 1, 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;

Q is an oxygen atom or a divalent organic group;

R 1 is a hydrogen atom or an alkyl group having 1 to 22 carbon atoms;

X is a hydroxyl group or OR 4 ;

R 4 is each independently at each occurrence a substituted or unsubstituted C 1-12 alkyl group;

Z is a fluorine atom or a fluoroalkyl group having 1 to 5 carbon atoms;

e is an integer from 0 to 3;

f is 0 or 1;

g is an integer from 1 to 10; and

his an integer from 0 to 3;

wherein a number average molecular weight of the perfluoro(poly)ether group containing silane compound is 3000 or more and 6000 or less,

polydispersity of g is more than 1.0 and less than 2.0, and

80 mol % or more of the perfluoro(poly)ether group containing silane compound contained in the surface-treating agent is a compound wherein g is 2 or more,

wherein the perfluoro(poly)ether group containing silane compound of the formula (1′) is prepared by reacting a perfluoro(poly)ether compound of the formula (1a):

wherein Rf, PFPE, Q, Z, e and f are as defined above, and Y 1 is a chlorine, an iodine or a bromine,

with a compound of the formula (1c):

wherein R 1 and h are as defined above, in a fluorine containing aromatic compound to obtain a compound of the formula (1d):

wherein Rf, PFPE, Q, Y 1 , Z, R 1 , e, f, g and h are as defined above, and then reacting the obtained compound with a compound of HX wherein X is as defined above.

25. The surface-treating agent according to claim 23 wherein the fluorine containing aromatic compound is selected from the group consisting of perfluorobenzene, pentafluorobenzene, 1,2,3,4-tetrafluorobenzene, 1,2,3,5-tetrafluorobenzene, 1,2,4,5-tetrafluorobenzene, 1,2,3-trifluorobenzene, 1,2,4-trifluorobenzene, 1,3,5-trifluorobenzene, benzotrifluoride, fluorobenzene, 1-chloro-2-fluorobenzene, 1-chloro-3-fluorobenzene, 1-chloro-4-fluorobenzene, 2,6-dichlorofluorobenzene, 1-fluoro-3-(trifluoromethoxy)benzene, 1-fluoro-2,4-dinitrobenzene, 2,4-dimethoxy-1-fluorobenzene, 1-fluoro-4-nitrobenzene, 2-fluorotoluene, 3-fluorotoluene, 4-fluorotoluene, 3-fluorobenzotrifluoride, 1-chloro-2,4-difluorobenzene, 1-chloro-3,4-difluorobenzene, 1-chloro-3,5-difluorobenzene, 2-chloro-1,3-difluorobenzene, chloropentafluorobenzene, 2,4-dichlorofluorobenzene, 2,5-dichlorofluorobenzene, 2,6-dichlorofluorobenzene, 1,2-dichloro-4-fluorobenzene, 1,3-dichloro-5-fluorobenzene, 1,3-dichloro-2,4,6-trifluorobenzene, 3,4-difluorobenzonitrile, 3,5-difluorobenzonitrile, 3,4-difluoronitrobenzene, 1-ethoxy-2,3-difluorobenzene, 1,2-dicyano-4,5-difluorobenzene, 1-acetoxy-3-fluorobenzene, 1-acetoxy-4-fluorobenzene, 1-acetonyl-4-fluorobenzene, 2-fluoro-m-xylene, 3-fluoro-o-xylene, 4-fluoro-o-xylene, pentafluoroanisole, tetrafluorophthalonitrile, 2-trifluoromethylbenzal chloride, 3-trifluoromethylbenzal chloride, 4-trifluoromethylbenzal chloride, methyl 3-(trifluoromethyl)benzoate, difluorobenzonitrile, bistrifluoromethyl benzonitrile, 4-trifluoromethyl benzonitrile, aminobenzotrifluoride, and trifluoromethyl aniline.

26. The surface-treating agent according to claim 23 wherein the fluorine containing aromatic compound is a fluorine containing aromatic compound having 0 to 3 debyes of polarizability.

27. The surface-treating agent according to claim 23 wherein the fluorine containing aromatic compound is selected from the group consisting of benzotrifluoride, difluorobenzonitrile, and bistrifluoromethyl benzonitrile.

28. The process according to claim 19 wherein the fluorine containing aromatic compound is selected from the group consisting of perfluorobenzene, pentafluorobenzene, 1,2,3,4-tetrafluorobenzene, 1,2,3,5-tetrafluorobenzene, 1,2,4,5-tetrafluorobenzene, 1,2,3-trifluorobenzene, 1,2,4-trifluorobenzene, 1,3,5-trifluorobenzene, benzotrifluoride, fluorobenzene, 1-chloro-2-fluorobenzene, 1-chloro-3-fluorobenzene, 1-chloro-4-fluorobenzene, 2,6-dichlorofluorobenzene, 1-fluoro-3-(trifluoromethoxy)benzene, 1-fluoro-2,4-dinitrobenzene, 2,4-dimethoxy-1-fluorobenzene, 1-fluoro-4-nitrobenzene, 2-fluorotoluene, 3-fluorotoluene, 4-fluorotoluene, 3-fluorobenzotrifluoride, 1-chloro-2,4-difluorobenzene, 1-chloro-3,4-difluorobenzene, 1-chloro-3,5-difluorobenzene, 2-chloro-1,3-difluorobenzene, chloropentafluorobenzene, 2,4-dichlorofluorobenzene, 2,5-dichlorofluorobenzene, 2,6-dichlorofluorobenzene, 1,2-dichloro-4-fluorobenzene, 1,3-dichloro-5-fluorobenzene, 1,3-dichloro-2,4,6-trifluorobenzene, 3,4-difluorobenzonitrile, 3,5-difluorobenzonitrile, 3,4-difluoronitrobenzene, 1-ethoxy-2,3-difluorobenzene, 1,2-dicyano-4,5-difluorobenzene, 1-acetoxy-3-fluorobenzene, 1-acetoxy-4-fluorobenzene, 1-acetonyl-4-fluorobenzene, 2-fluoro-m-xylene, 3-fluoro-o-xylene, 4-fluoro-o-xylene, pentafluoroanisole, tetrafluorophthalonitrile, 2-trifluoromethylbenzal chloride, 3-trifluoromethylbenzal chloride, 4-trifluoromethylbenzal chloride, methyl 3-(trifluoromethyl)benzoate, difluorobenzonitrile, bistrifluoromethyl benzonitrile, 4-trifluoromethyl benzonitrile, aminobenzotrifluoride, and trifluoromethylaniline.

29. The process according to claim 19 wherein the fluorine containing aromatic compound is a fluorine containing aromatic compound having 0 to 3 debyes of polarizability.

30. The process according to claim 19 wherein the fluorine containing aromatic compound is selected from the group consisting of benzotrifluoride, difluorobenzonitrile, and bistrifluoromethyl benzonitrile.

31. The surface-treating agent according to claim 24 wherein the fluorine containing aromatic compound is selected from the group consisting of perfluorobenzene, pentafluorobenzene, 1,2,3,4-tetrafluorobenzene, 1,2,3,5-tetrafluorobenzene, 1,2,4,5-tetrafluorobenzene, 1,2,3-trifluorobenzene, 1,2,4-trifluorobenzene, 1,3,5-trifluorobenzene, benzotrifluoride, fluorobenzene, 1-chloro-2-fluorobenzene, 1-chloro-3-fluorobenzene, 1-chloro-4-fluorobenzene, 2,6-dichlorofluorobenzene, 1-fluoro-3-(trifluoromethoxy)benzene, 1-fluoro-2,4-dinitrobenzene, 2,4-dimethoxy-1-fluorobenzene, 1-fluoro-4-nitrobenzene, 2-fluorotoluene, 3-fluorotoluene, 4-fluorotoluene, 3-fluorobenzotrifluoride, 1-chloro-2,4-difluorobenzene, 1-chloro-3,4-difluorobenzene, 1-chloro-3,5-difluorobenzene, 2-chloro-1,3-difluorobenzene, chloropentafluorobenzene, 2,4-dichlorofluorobenzene, 2,5-dichlorofluorobenzene, 2,6-dichlorofluorobenzene, 1,2-dichloro-4-fluorobenzene, 1,3-dichloro-5-fluorobenzene, 1,3-dichloro-2,4,6-trifluorobenzene, 3,4-difluorobenzonitrile, 3,5-difluorobenzonitrile, 3,4-difluoronitrobenzene, 1-ethoxy-2,3-difluorobenzene, 1,2-dicyano-4,5-difluorobenzene, 1-acetoxy-3-fluorobenzene, 1-acetoxy-4-fluorobenzene, 1-acetonyl-4-fluorobenzene, 2-fluoro-m-xylene, 3-fluoro-o-xylene, 4-fluoro-o-xylene, pentafluoroanisole, tetrafluorophthalonitrile, 2-trifluoromethylbenzal chloride, 3-trifluoromethylbenzal chloride, 4-trifluoromethylbenzal chloride, methyl 3-(trifluoromethyl)benzoate, difluorobenzonitrile, bistrifluoromethyl benzonitrile, 4-trifluoromethyl benzonitrile, aminobenzotrifluoride, and trifluoromethylaniline.

32. The surface-treating agent according to claim 24 wherein the fluorine containing aromatic compound is a fluorine containing aromatic compound having 0 to 3 debyes of polarizability.

33. The surface-treating agent according to claim 24 wherein the fluorine containing aromatic compound is selected from the group consisting of benzotrifluoride, difluorobenzonitrile, and bistrifluoromethyl benzonitrile.