MODIFIED FLUOROOXYMETHYLENE GROUP-CONTAINING PERFLUOROPOLYETHER

Abstract

The present invention provides compound of formulae (A1), (A2), (B1), (B2), (C1) and (C2) which can form a layer having water-repellency, oil-repellency and antifouling property as well as high friction durability:

##STR00001##

wherein each symbols are as defined in the specification.

Claims

1. A perfluoro(poly)ether group containing silane compound of any of the formulae (A1), (A2), (B1), (B2), (C1) and (C2): ##STR00018## wherein: PFPE is each independently at each occurrence —(OC.sub.4F.sub.8).sub.a—(OC.sub.3F.sub.6).sub.b—(OC.sub.2F.sub.4).sub.c—(OCF.sub.2).sub.d—, 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 an integer of 3 or more, a c/d ratio is 0.2 or more and less than 0.9, 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; Rf is each independently at each occurrence an alkyl group having 1-16 carbon atoms which may be substituted by one or more fluorine atoms; R.sup.1 is each independently at each occurrence a hydrogen atom or an alkyl group having 1-22 carbon atoms; R.sup.2 is each independently at each occurrence a hydroxyl group or a hydrolyzable group; R.sup.11 is each independently at each occurrence a hydrogen atom or a halogen atom; R.sup.12 is each independently at each occurrence a hydrogen atom or a lower alkyl group; n is, independently per a unit (—SiR.sup.1.sub.nR.sup.2.sub.3-n), an integer of 0-3; there is at least one R.sup.2 in the formulae (A1), (A2), (B1) and (B2); X.sup.1 is each independently a single bond or a 2-10 valent organic group; X.sup.2 is each independently at each occurrence a single bond or a divalent organic group; t is each independently at each occurrence an integer of 1-10; α is each independently an integer of 1-9; α′ is each independently an integer of 1-9; X.sup.5 is each independently a single bond or a 2-10 valent organic group; β is each independently an integer of 1-9; β′ is each independently an integer of 1-9; X.sup.7 is each independently a single bond or a 2-10 valent organic group; γ is each independently an integer of 1-9; γ′ is each independently an integer of 1-9; R.sup.a is each independently at each occurrence —Z—SiR.sup.71.sub.pR.sup.72.sub.qR.sup.73.sub.r; Z is each independently at each occurrence an oxygen atom or a divalent organic group; R.sup.71 is each independently at each occurrence R.sup.a′; R.sup.a′ has the same definition as that of R.sup.a; in R.sup.a, the number of Si atoms which are straightly linked via the Z group is up to five; R.sup.72 is each independently at each occurrence a hydroxyl group or a hydrolyzable group; R.sup.73 is each independently at each occurrence a hydrogen atom or a lower alkyl group; p is each independently at each occurrence an integer of 0-3; q is each independently at each occurrence an integer of 0-3; r is each independently at each occurrence an integer of 0-3; in one R.sup.a, the sum of p, q and r is 3, and there is at least one R.sup.72 in the formula (C1) and (C2); R.sup.b is each independently at each occurrence a hydroxyl group or a hydrolyzable group; R.sup.c is each independently at each occurrence a hydrogen atom or a lower alkyl group; k is each independently at each occurrence an integer of 1-3; l is each independently at each occurrence an integer of 0-2; m is each independently at each occurrence an integer of 0-2; and the sum of k, l and m is 3 in each unit in parentheses with the subscript γ.

2. The perfluoro(poly)ether group containing silane compound according to claim 1 wherein the c/d ratio is 0.2 or more and 0.85 or less.

3. The perfluoro(poly)ether group containing silane compound according to claim 1 wherein the c/d ratio 0.3 or more and 0.6 or less.

4. The perfluoro(poly)ether group containing silane compound according to claim 1 wherein in PFPE: —(OC.sub.4F.sub.8).sub.a— is —(OCF.sub.2CF.sub.2CF.sub.2CF.sub.2).sub.a—, —(OC.sub.3F.sub.6).sub.b— is —(OCF.sub.2CF.sub.2CF.sub.2).sub.b—, and —(OC.sub.2F.sub.4).sub.c— is —(OCF.sub.2CF.sub.2).sub.c.

5. The perfluoro(poly)ether group containing silane compound according to claim 1 wherein Rf is a perfluoroalkyl group having 1-16 carbon atoms.

6. The perfluoro(poly)ether group containing silane compound according to claim 1 wherein X.sup.1, X.sup.5 and X.sup.7 are each independently a 2-4 valent organic group, α, β and γ are each independently 1-3, and α′, β′ and γ′ are 1.

7. The perfluoro(poly)ether group containing silane compound according to claim 1 wherein X.sup.1, X.sup.5 and X.sup.7 are a divalent organic group, α, β and γ are 1, and α′, β′ and γ′ are 1.

8. The perfluoro(poly)ether group containing silane compound according to claim 1 wherein X.sup.1, X.sup.5 and X.sup.7 are each independently —(R.sup.31).sub.p′—(X.sup.a).sub.q′— wherein: R.sup.31 is a single bond, —(CH.sub.2).sub.s′— (wherein s′ is an integer of 1-20) or a o-, m- or p-phenylene group; X.sup.a is —(X.sup.b).sub.l′— (wherein l′ is an integer of 1-10); X.sup.b is each independently at each occurrence selected from the group consisting of —O—, —S—, an o-, m- or p-phenylene group, —C(O)O—, —Si(R.sup.33).sub.2—, —(Si(R.sup.33).sub.2O).sub.m′—Si(R.sup.33).sub.2— (wherein m′ is an integer of 1-100), —CONR.sup.34—, —O—CONR.sup.34—, —NR.sup.34— and —(CH.sub.2).sub.n′— (wherein n′ is an integer of 1-20); R.sup.33 is each independently at each occurrence a phenyl group, a C.sub.1-6 alkyl group or a C.sub.1-6 alkoxy group; R.sup.34 is each independently at each occurrence a hydrogen atom, a phenyl group or a C.sub.1-6 alkyl group; p′ is 0 or 1; q′ is 0 or 1; the occurrence order of the respective repeating units in parentheses with the subscript p′ or q′ is not limited in the formula; and R.sup.31 and X.sup.a is may be substituted with one or more substituents selected from a fluorine atom, a C.sub.1-3 alkyl group and a C.sub.1-3 fluoroalkyl group.

9. The perfluoro(poly)ether group containing silane compound according to claim 1 wherein X.sup.1, X.sup.5 and X.sup.7 are each independently selected from the group consisting of: —CH.sub.2O(CH.sub.2).sub.2—, —CH.sub.2O(CH.sub.2).sub.3—, —CH.sub.2O(CH.sub.2).sub.6—, —CH.sub.2O(CH.sub.2).sub.3Si(CH.sub.3).sub.2OSi(CH.sub.3).sub.2(CH.sub.2).sub.2—, —CH.sub.2O(CH.sub.2).sub.3Si(CH.sub.3).sub.2OSi(CH.sub.3).sub.2OSi(CH.sub.3).sub.2(CH.sub.2).sub.2—, —CH.sub.2O(CH.sub.2).sub.3Si(CH.sub.3).sub.2O(Si(CH.sub.3).sub.2O).sub.2Si(CH.sub.3).sub.2(CH.sub.2).sub.2—, —CH.sub.2O(CH.sub.2).sub.3Si(CH.sub.3).sub.2O(Si(CH.sub.3).sub.2O).sub.3Si(CH.sub.3).sub.2(CH.sub.2).sub.2—, —CH.sub.2O(CH.sub.2).sub.3Si(CH.sub.3).sub.2O(Si(CH.sub.3).sub.2O).sub.10Si(CH.sub.3).sub.2(CH.sub.2).sub.2—, —CH.sub.2O(CH.sub.2).sub.3Si(CH.sub.3).sub.2O(Si(CH.sub.3).sub.2O).sub.20Si(CH.sub.3).sub.2(CH.sub.2).sub.2—, —CH.sub.2OCH.sub.2(CH.sub.2).sub.7CH.sub.2Si(OCH.sub.3).sub.2OSi(OCH.sub.3).sub.2(CH.sub.2).sub.2Si(OCH.sub.3).sub.2OSi(OCH.sub.3).sub.2(CH.sub.2).sub.2—, —CH.sub.2OCH.sub.2CH.sub.2CH.sub.2Si(OCH.sub.3).sub.2OSi(OCH.sub.3).sub.2(CH.sub.2).sub.3—, —CH.sub.2OCH.sub.2CH.sub.2CH.sub.2Si(OCH.sub.2CH.sub.3).sub.2OSi(OCH.sub.2CH.sub.3).sub.2(CH.sub.2).sub.3—, —CH.sub.2OCH.sub.2CH.sub.2CH.sub.2Si(OCH.sub.3).sub.2OSi(OCH.sub.3).sub.2(CH.sub.2).sub.2—, —CH.sub.2OCH.sub.2CH.sub.2CH.sub.2Si(OCH.sub.2CH.sub.3).sub.2OSi(OCH.sub.2CH.sub.3).sub.2(CH.sub.2).sub.2—, —(CH.sub.2).sub.2—, —(CH.sub.2).sub.3—, —(CH.sub.2).sub.4—, —(CH.sub.2).sub.6—, —CONH—(CH.sub.2).sub.3—, —CON(CH.sub.3)—(CH.sub.2).sub.3—, —CON(Ph)-(CH.sub.2).sub.3— (wherein Ph is a phenyl group), —CONH—(CH.sub.2).sub.6—, —CON(CH.sub.3)—(CH.sub.2).sub.6—, —CON(Ph)-(CH.sub.2).sub.6— (wherein Ph is a phenyl group), —CONH—(CH.sub.2).sub.2NH(CH.sub.2).sub.3—, —CONH—(CH.sub.2).sub.6NH(CH.sub.2).sub.3—, —CH.sub.2O—CONH—(CH.sub.2).sub.3—, —CH.sub.2O—CONH—(CH.sub.2).sub.6—, —S—(CH.sub.2).sub.3—, —(CH.sub.2).sub.2S(CH.sub.2).sub.3—, —CONH—(CH.sub.2).sub.3Si(CH.sub.3).sub.2OSi(CH.sub.3).sub.2(CH.sub.2).sub.2—, —CONH—(CH.sub.2).sub.3Si(CH.sub.3).sub.2OSi(CH.sub.3).sub.2OSi(CH.sub.3).sub.2(CH.sub.2).sub.2—, —CONH—(CH.sub.2).sub.3Si(CH.sub.3).sub.2O(Si(CH.sub.3).sub.2O).sub.2Si(CH.sub.3).sub.2(CH.sub.2).sub.2—, —CONH—(CH.sub.2).sub.3Si(CH.sub.3).sub.2O(Si(CH.sub.3).sub.2).sub.3Si(CH.sub.3).sub.2(CH.sub.2).sub.2—, —CONH—(CH.sub.2).sub.3Si(CH.sub.3).sub.2O(Si(CH.sub.3).sub.2O).sub.10Si(CH.sub.3).sub.2(CH.sub.2).sub.2—, —CONH—(CH.sub.2).sub.3Si(CH.sub.3).sub.2O(Si(CH.sub.3).sub.2O).sub.20Si(CH.sub.3).sub.2(CH.sub.2).sub.2— —C(O)O—(CH.sub.2).sub.3—, —C(O)O—(CH.sub.2).sub.6—, —CH.sub.2—O—(CH.sub.2).sub.3—Si(CH.sub.3).sub.2—(CH.sub.2).sub.2—Si(CH.sub.3).sub.2—(CH.sub.2).sub.2—, —CH.sub.2—O—(CH.sub.2).sub.3—Si(CH.sub.3).sub.2—(CH.sub.2).sub.2—Si(CH.sub.3).sub.2—CH(CH.sub.3)—, —CH.sub.2—O—(CH.sub.2).sub.3—Si(CH.sub.3).sub.2—(CH.sub.2).sub.2—Si(CH.sub.3).sub.2—(CH.sub.2).sub.3—, —CH.sub.2—O—(CH.sub.2).sub.3—Si(CH.sub.3).sub.2—(CH.sub.2).sub.2—Si(CH.sub.3).sub.2—CH(CH.sub.3)—CH.sub.2—, ##STR00019##

10. The perfluoro(poly)ether group containing silane compound according to claim 1 wherein X.sup.1 is —O—CFR.sup.13—(CF.sub.2).sub.e—, R.sup.13 is a fluorine atom or a lower fluoroalkyl group, and e is 0 or 1.

11. The perfluoro(poly)ether group containing silane compound according to claim 1 wherein X.sup.2 is —(CH.sub.2).sub.s—, and s is an integer of 0-2.

12. The perfluoro(poly)ether group containing silane compound according to claim 1 wherein in the formula (C1) and (C2), k is 3, and q is 3 in R.sup.a.

13. The perfluoro(poly)ether group containing silane compound according to claim 1 wherein X.sup.1, X.sup.5 and X.sup.7 are each independently a 3-10 valent organic group.

14. The perfluoro(poly)ether group containing silane compound according to claim 1 wherein X.sup.1, X.sup.5 and X.sup.7 are each independently selected from the group consisting of: ##STR00020## ##STR00021## wherein in each group, at least one of T is the following group attached to PFPE in the formulae (A1), (A2), (B1), (B2), (C1) and (C2): —CH.sub.2O(CH.sub.2).sub.2—, —CH.sub.2O(CH.sub.2).sub.3—, —CF.sub.2O(CH.sub.2).sub.3—, —(CH.sub.2).sub.2—, —(CH.sub.2).sub.3—, —(CH.sub.2).sub.4—, —CONH—(CH.sub.2).sub.3—, —CON(CH.sub.3)—(CH.sub.2).sub.3—, —CON(Ph)-(CH.sub.2).sub.3— (wherein Ph is a phenyl group), and ##STR00022## at least one of the other T is —(CH.sub.2).sub.n— (wherein n is an integer of 2-6) attached to the carbon atom or the Si atom in the formulae (A1), (A2), (B1), (B2), (C1) and (C2) and the others are each independently a methyl group, a phenyl group, or a alkoxy having 1-6 carbon atoms, R.sup.41 is a hydrogen atom, a phenyl group, an alkoxy group having 1 to 6 carbon atoms or an alkyl group having 1 to 6 carbon atoms, and R.sup.42 is a hydrogen atom or a C.sub.1-6 alkyl group.

15. A compound of any one of the formulae (B1-4), (B2-4), (C1-4) and (C2-4):
(Rf-PFPE).sub.β′—X.sup.5′—(R.sup.82—CH═CH.sub.2).sub.β  (B1-4)
(CH.sub.2═CH—R.sup.82).sub.β—X.sup.5′-PFPE-X.sup.5′—(R.sup.82—CH═CH.sub.2).sub.β  (B2-4)
(Rf-PFPE).sub.γ′—X.sup.7′—(R.sup.82—CH═CH.sub.2).sub.γ  (C1-4)
(CH.sub.2═CH—R.sup.82).sub.γ—X.sup.7′-PFPE-X.sup.7′—(R.sup.82—CH═CH.sub.2).sub.γ  (C2-4) wherein: PFPE is each independently at each occurrence —(OC.sub.4F.sub.8).sub.a—(OC.sub.3F.sub.6).sub.b—(OC.sub.2F.sub.4).sub.c—(OCF.sub.2).sub.d—, 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 an integer of 3 or more, the c/d ratio is 0.2 or more and less than 0.9, 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; Rf is each independently at each occurrence an alkyl group having 1-16 carbon atoms which may be substituted by one or more fluorine atoms; X.sup.5′ is each independently a single bond or a 2-10 valent organic group; β is each independently an integer of 1-9; β′ is each independently an integer of 1-9; X.sup.7′ is each independently a single bond or a 2-10 valent organic group; γ is each independently an integer of 1-9; γ′ is each independently an integer of 1-9; and R.sup.82 is a single bond or a divalent organic group.

16. A compound of any one of the formulae (C1-5) and (C2-5):
(Rf-PFPE).sub.γ′-X.sup.7′—(R.sup.82—CH.sub.2CH.sub.2—SiR.sup.83.sub.kR.sup.b.sub.lR.sup.c.sub.m).sub.γ  (C1-5)
(R.sup.c.sub.mR.sup.b.sub.lR.sup.83.sub.kSi—CH.sub.2CH.sub.2—R.sup.82).sub.γ—X.sup.7′-PFPE-**X.sup.7′—(R.sup.82—CH.sub.2CH.sub.2—SiR.sup.83.sub.kR.sup.b.sub.lR.sup.c.sub.m).sub.γ  (C2-5) wherein: PFPE is each independently at each occurrence —(OC.sub.4F.sub.8).sub.a—(OC.sub.3F.sub.6).sub.b—(OC.sub.2F.sub.4).sub.c—(OCF.sub.2).sub.d—, 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 an integer of 3 or more, a c/d ratio is 0.2 or more and less than 0.9, 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; Rf is each independently at each occurrence an alkyl group having 1-16 carbon atoms which may be substituted by one or more fluorine atoms; X.sup.7′ is each independently a single bond or a 2-10 valent organic group; γ is each independently an integer of 1-9; γ′ is each independently an integer of 1-9; R.sup.82 is a single bond or a divalent organic group; R.sup.83 is a halogen atom; R.sup.b is each independently at each occurrence a hydroxyl group or a hydrolyzable group; R.sup.c is each independently at each occurrence a hydrogen atom or a lower alkyl group; k is each independently at each occurrence an integer of 1-3; l is each independently at each occurrence an integer of 0-2; m is each independently at each occurrence an integer of 0-2; and the sum of k, l and m is 3 in each unit in parentheses with the subscript γ.

17. A compound of any one of the formulae (C1-6) and (C2-6):
(Rf-PFPE).sub.γ′-X.sup.7′—(R.sup.82—CH.sub.2CH.sub.2—SiR.sup.b.sub.lR.sup.c.sub.m(R.sup.84—CH═CH.sub.2).sub.k).sub.γ  (C1-6)
((CH═CH.sub.2—R.sup.84).sub.kR.sup.c.sub.mR.sup.b.sub.lSi—CH.sub.2CH.sub.2—R.sup.82).sub.γ—X.sup.7′-PFPE-**X.sup.7′—(R.sup.82—CH.sub.2CH.sub.2—SiR.sup.b.sub.lR.sup.c.sub.m(R.sup.84—CH═CH.sub.2).sub.k).sub.γ  (C2-6) wherein: PFPE is each independently at each occurrence —(OC.sub.4F.sub.8).sub.a—(OC.sub.3F.sub.6).sub.b—(OC.sub.2F.sub.4).sub.c—(OCF.sub.2).sub.d—, 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 an integer of 3 or more, a c/d ratio is 0.2 or more and less than 0.9, 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; Rf is each independently at each occurrence an alkyl group having 1-16 carbon atoms which may be substituted by one or more fluorine atoms; X.sup.7′ is each independently a single bond or a 2-10 valent organic group; γ is each independently an integer of 1-9; γ′ is each independently an integer of 1-9; R.sup.82 is a single bond or a divalent organic group; R.sup.84 is a single bond or a divalent organic group; R.sup.b is each independently at each occurrence a hydroxyl group or a hydrolyzable group; R.sup.c is each independently at each occurrence a hydrogen atom or a lower alkyl group; k is each independently at each occurrence an integer of 1-3; l is each independently at each occurrence an integer of 0-2; m is each independently at each occurrence an integer of 0-2; and the sum of k, l and m is 3 in the unit in parentheses with the subscript γ.

18. The compound according to claim 16 wherein k is 3.

19. The compound according to claim 15 wherein X.sup.5′ and X.sup.7′ are a divalent organic group, β and γ are 1, and β′ and γ′ are 1.

20. A mixture comprising the compound of claim 15 and a fluorine-containing oil and/or a solvent.

21. The mixture according to claim 20 wherein the fluorine-containing oil is one or more compounds of the formula (3):
R.sup.21—(OC.sub.4F.sub.8).sub.a′—(OC.sub.3F.sub.6).sub.b′—(OC.sub.2F.sub.4).sub.c′—(OCF.sub.2).sub.d′—R.sup.22  (3) wherein: R.sup.21 is an alkyl group having 1-16 carbon atoms which may be substituted by one or more fluorine atoms; R.sup.22 is an alkyl group having 1-16 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 the repeating number of each of four repeating units of perfluoro(poly)ether which constitute a main backbone of the polymer, and 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.

22. The mixture according to claim 20 wherein the fluorine-containing oil is one or more compounds of the formula (3a) or (3b):
R.sup.21—(OCF.sub.2CF.sub.2CF.sub.2).sub.b″—R.sup.22  (3a)
R.sup.21—(OCF.sub.2CF.sub.2CF.sub.2CF.sub.2).sub.a″—(OCF.sub.2CF.sub.2CF.sub.2).sub.b″—(OCF.sub.2CF.sub.2).sub.c″—(OCF.sub.2).sub.d″—R.sup.22  (3b) wherein: R.sup.21 is an alkyl group having 1-16 carbon atoms which may be substituted by one or more fluorine atoms; R.sup.22 is an alkyl group having 1-16 carbon atoms which may be substituted by one or more fluorine atoms, a fluorine atom or a hydrogen atom; 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.

23. A surface-treating agent comprising the perfluoro(poly)ether group containing silane compound according to claim 1.

24. The surface-treating agent according to claim 23 wherein the perfluoro(poly)ether group containing silane compound is at least one compound of any one of the formulae (A1) and (A2).

25. The surface-treating agent according to claim 23 wherein the perfluoro(poly)ether group containing silane compound is at least one compound of any one of the formulae (B1) and (B2).

26. The surface-treating agent according to claim 23 wherein the perfluoro(poly)ether group containing silane compound is at least one compound of any one of the formulae (C1) and (C2).

27. The surface-treating agent according to claim 23 further comprising one or more components selected form a fluorine-containing oil, a silicone oil, and a catalyst.

28. The surface-treating agent according to claim 27 wherein the fluorine-containing oil is one or more compounds of the formula (3):
R.sup.21—(OC.sub.4F.sub.8).sub.a′—(OC.sub.3F.sub.6).sub.b′—(OC.sub.2F.sub.4).sub.c′—(OCF.sub.2).sub.d′—R.sup.22  (3) wherein: R.sup.21 is an alkyl group having 1-16 carbon atoms which may be substituted by one or more fluorine atoms; R.sup.22 is an alkyl group having 1-16 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 the repeating number of each of four repeating units of perfluoro(poly)ether which constitute a main backbone of the polymer, and 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.

29. The surface-treating agent according to claim 27 wherein the fluorine-containing oil is one or more compounds of the formula (3a) or (3b):
R.sup.21—(OCF.sub.2CF.sub.2CF.sub.2).sub.b″—R.sup.22  (3a)
R.sup.21—(OCF.sub.2CF.sub.2CF.sub.2CF.sub.2).sub.a″—(OCF.sub.2CF.sub.2CF.sub.2).sub.b″—(OCF.sub.2CF.sub.2).sub.c″—(OCF.sub.2).sub.d″—R.sup.22  (3b) wherein: R.sup.21 is an alkyl group having 1-16 carbon atoms which may be substituted by one or more fluorine atoms; R.sup.22 is an alkyl group having 1-16 carbon atoms which may be substituted by one or more fluorine atoms, a fluorine atom or a hydrogen atom; 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.

30. The surface-treating agent according to claim 29 wherein a mass ratio of the perfluoro(poly)ether group containing silane compound and the compound of the formula (3b) is 4:1-1:4.

31. The surface-treating agent according to claim 29 wherein the compound of the formula (3a) has a number average molecular weight of 2,000-8,000.

32. The surface-treating agent according to claim 29 wherein the compound of the formula (3b) has a number average molecular weight of 8,000-30,000.

33. The surface-treating agent according to claim 29 wherein the fluorine-containing oil is one or more compounds of the formula (3b) wherein a c″/d″ ratio is 0.2 or more and less than 0.9.

34. The surface-treating agent according to claim 23 further comprising a solvent.

35. The surface-treating agent according to claim 23 which is used as an antifouling-coating agent or a water-proof coating agent.

36. The surface-treating agent according to claim 23 for vacuum deposition.

37. A pellet comprising the surface-treating agent according to claim 23.

38. An article comprising a base material and a layer which is formed on a surface of the base material from the compound according to claim 1.

39. The article according to claim 38 wherein the base material is a glass or a sapphire glass.

40. The article according to claim 39 wherein the glass is a glass selected from the group consisting of a soda-lime glass, an alkali aluminosilicate glass, a borosilicate glass, a non-alkaline glass, a crystal glass, and a quartz glass.

41. The article according to claim 38 wherein the article is an optical member.

42. The article according to claim 38 wherein the article is a display.

Description

EXAMPLES

[0563] The surface-treating agent of the present invention will be described in detail through Examples, although the present invention is not limited to Examples. It is noted that in Examples, the occurrence order of the repeating units (CF.sub.2O), (CF.sub.2CF.sub.2O), (CF(CF.sub.3)CF.sub.2O), (CF.sub.2CF.sub.2CF.sub.2O), (CF.sub.2CF(CF.sub.3)O) and (CF.sub.2CF.sub.2CF.sub.2CF.sub.2O) constituting the perfluoroether is not limited.

Synthesis of a Perfluoro(Poly)Ether Group Containing Silane Compound Wherein the E/M Ratio is 0.85

Synthesis Example 1 (Synthesis of a Perfluoropolyether Peroxide)

[0564] Perfluorohexane (2200 g) was added to a tubular reactor for a photochemical synthesis provided with a 100 W of high pressure mercury lamp and a circulating cooling jacket, and after cooling to 55° C., chlorodifluoromethane (R22) (1600 g) was added.

[0565] Supplying of oxygen was started at the rate of 12.2 L/h, and the mercury lamp was turned on. Then, chlorotrifluoroethylene and tetrafluoroethylene were supplied at the rate of 0.1 L/h and 10.2 L/h, respectively. The supplying was kept constant for 5 hours-reaction, and the temperature was kept constant at −55° C.

[0566] After the reaction for 5 hours, the lamp was turned off, the supplying of the raw material was stopped, and chlorodifluoromethane was evaporated. As a result of analysis by .sup.19F-NMR, T-(CF.sub.2CF.sub.2O).sub.n(CF.sub.2O).sub.m(CF.sub.2CF.sub.2OO).sub.p(CF.sub.2OO).sub.q-T (wherein T is OCF.sub.2Cl, OCF.sub.2CF.sub.2Cl, OCF.sub.3, OCF.sub.2COF, or OCOF) was obtained and the n/m ratio was 0.72.

Synthesis Example 2 (Heat Treatment of the Perfluoropolyether Peroxide)

[0567] The crude product obtained in Synthesis Example 1 was heat-treated under an UV irradiation, and then materials having low boiling point such as a solvent, etc. was removed to obtain an oil component (91 g).

Synthesis Example 3 (Synthesis of a Modified Perfluoropolyether)

[0568] To a four necked flask of 1 L provided with a stirrer, a dropping funnel, a reflux condenser and a thermometer, methanol (22 ml), acetic acid (20 ml) and sodium iodide (25 g) were added, and stirring was started. A solution of the product of Synthesis Example 2 (80 g) dissolved in Novec (trademark) 7200 (623 g) was added dropwise from a dropping funnel, stirring was performed with heating at 50° C. for 3 hours to obtain an oil component of CH.sub.3OCOCF.sub.2O—(CF.sub.2CF.sub.2O).sub.m′—(CF.sub.2O).sub.n′—CF.sub.2CO.sub.2CH.sub.3 (65 g). As a result of analysis by .sup.19F-NMR, the m′/n′ ratio was 0.82.

Synthesis Example 4 (Adjustment of a Molecular Weight)

[0569] The oil component of CH.sub.3OCOCF.sub.2O—(CF.sub.2CF.sub.2O).sub.m′—(CF.sub.2O).sub.n′—CF.sub.2CO.sub.2CH.sub.3 (65 g) obtained in Synthesis Example 3 was dissolved in perfluorohexane (200 g), and silica gel (30 g) was added and stirred. After celite filtration was performed, the mixture was washed with perfluorohexane to collect fraction (45 g) containing mainly compounds having high molecular weight. By the washing with Novec (trademark) 7200/CF.sub.3CH.sub.2OH (1:1), fraction containing mainly compounds having low molecular weight (18 g) which was adsorbed to silica gel was separated.

[0570] Then, the oil component (45 g) collected in the above operation was dissolved in perfluorohexane (150 g), silica gel (30 g) was added, and the mixture was stirred. After celite filtration was performed, the mixture was washed with perfluorohexane to collect fraction (30 g) containing mainly compounds having high molecular weight. By the washing with Novec (trademark) 7200/CF.sub.3CH.sub.2OH (1:1), fraction containing mainly compounds having low molecular weight (15 g) which was adsorbed to silica gel was obtained. As a result of analysis by .sup.19F-NMR, the m′/n′ ratio was 0.85.

Synthesis Example 5 (Hydrolysis Reaction)

[0571] To a glass reactor (300 ml) provided with a stirrer and a thermal sensor, the oil component (15 g) of CH.sub.3OCOCF.sub.2O—(CF.sub.2CF.sub.2O).sub.m′—(CF.sub.2O).sub.n′—CF.sub.2CO.sub.2CH.sub.3 obtained in Synthesis Example 4, perfluorohexane (30 ml), tetrahydrofuran (30 ml), and 1 mol/l of an aqueous potassium hydroxide solution (33 ml) were added, and the mixture was stirred for 3 hours. Then, 1N of hydrochloric acid (30 ml) was added, and stirred for 30 minutes. Then, the lower phase was separated, and the solvent was evaporated to obtain HOOCCF.sub.2O—(CF.sub.2CF.sub.2O).sub.m′—(CF.sub.2O).sub.n′—CF.sub.2COOH (13.5 g).

Synthesis Example 6 (Fluorination Reaction)

[0572] To a glass reactor (100 ml) provided with a stirrer, a reflux condenser and a thermal sensor, the oil component (13.5 g) of HOOCCF.sub.2O—(CF.sub.2CF.sub.2O).sub.m′—(CF.sub.2O).sub.n′—CF.sub.2COOH obtained in Synthesis Example 5 was added.

[0573] Heating was performed such that the temperature in the reactor reached 60° C., and a F.sub.2/N.sub.2 gas mixture which was adjusted such that a F.sub.2 gas concentration was 7.3 vol % was flowed at the rate of 30 ml/min for 200 minutes to obtain a mixture of (A) CF.sub.3O(CF.sub.2CF.sub.2O).sub.22(CF.sub.2O).sub.26CF.sub.2COOH, (B)CF.sub.3O(CF.sub.2CF.sub.2O).sub.22(CF.sub.2O).sub.26CF.sub.3 and (C)HCOOCCF.sub.2O(CF.sub.2CF.sub.2O).sub.22(CF.sub.2O).sub.26CF.sub.2COOH.

Synthesis Example 7 (One Terminal Type of Carboxylic Acid)

[0574] The mixture (13.4 g) obtained in Synthesis Example 6 was dissolved in perfluorohexane (50 g), and silica gel (50 g) was added and stirred for 30 minutes. Silica gel was filtered, and washed with perfluorohexane (200 ml) to obtain product (B) CF.sub.3O(CF.sub.2CF.sub.2O).sub.22(CF.sub.2O).sub.26CF.sub.3 (1.92 g) of Synthesis Example 6. Then, silica gel was washed with a mixed solution (300 ml) of Novec (trademark) 7200/CF.sub.3CH.sub.2OH (5:1) to obtain one terminal type of carboxylic acid (A) CF.sub.3O(CF.sub.2CF.sub.2O).sub.22(CF.sub.2O).sub.26CF.sub.2COOH (7.35 g).

Synthesis Example 8 (Alcohol Compound)

[0575] To a four necked flask of 50 mL provided with a reflux condenser, a thermometer and a stirrer, perfluoropolyether modified carboxylic acid compound (7 g) of an average composition: CF.sub.3O(CF.sub.2CF.sub.2O).sub.22(CF.sub.2O).sub.26CF.sub.2COOH (a mixture contained a compound comprising a slight amount of repeating units (CF.sub.2CF.sub.2CF.sub.2CF.sub.2O) and/or (CF.sub.2CF.sub.2CF.sub.2O)), bis(2-methoxyethyl)ether (7 g), and NaBH.sub.4 (0.186 g) were added, and stirred at 110° C. for 48 hours. Then, the mixture was cooled to 5° C., and perfluorohexane (9 g) was added, and then 3N of hydrochloric acid (9 g) was added dropwise. Then, insoluble materials were filtered, perfluorohexane phase which was a lower phase was separated with a separating funnel. Then, a volatile component was evaporated to obtain the following perfluoropolyether group containing alcohol compound having alcohol at its terminal (A) (6.44 g).

[0576] Perfluoropolyether group containing alcohol compound (A): [0577] CF.sub.3O(CF.sub.2CF.sub.2O).sub.22(CF.sub.2O).sub.26CF.sub.2CH.sub.2OH

Synthesis Example 9 (Allylether Compound)

[0578] To a four necked flask of 50 mL provided with a reflux condenser, a thermometer and a stirrer, perfluoropolyether modified alcohol compound (A) (6 g) prepared in Synthesis Example 8, 1,3-bis(trifluoromethyl)benzene (4 g) and NaOH (0.16 g) were added, and stirred at 65° C. for 4 hours. Then, allyl bromide (0.048 g) was added, and stirred at 65° C. for 6 hours. Then, the mixture was cooled to a room temperature, perfluorohexane (4 g) was added and insoluble materials were filtered. Washing with 3N of hydrochloric acid using a separating funnel was performed. Then, volatile components were evaporated to obtain the following perfluoropolyether group containing allyloxy compound (B) (5.7 g) having an allyl group at its terminal.

[0579] Perfluoropolyether group containing allyloxy compound (B): [0580] CF.sub.3O(CF.sub.2CF.sub.2O).sub.22(CF.sub.2O).sub.26CF.sub.2CH.sub.2CH.sub.2CH═CH.sub.2

Synthesis Example 10 (Trichloro Compound)

[0581] To a four necked flask of 30 mL provided with a reflux condenser, a thermometer and a stirrer, perfluoropolyether modified allyloxy compound (B) (5 g) prepared in Synthesis Example 9, 1,3-bis(trifluoromethyl)benzene (5 g), triacetoxymethylsilane (0-015 g), and trichlorosilane (0.343 g) were added and stirred under a nitrogen streaming at 5° C. for 30 minutes. Subsequently, after adding a xylene solution (0.025 ml) containing Pt complex of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane at 2%, the solution was warmed to 60° C. and stirred at this temperature for 5 hours. Then, a volatile content was evaporated to obtain the following perfluoropolyether group containing trichloro compound (C) (4.75 g).

[0582] Perfluoropolyether group containing trichloro compound (C): [0583] CF.sub.3O(CF.sub.2CF.sub.2O).sub.22(CF.sub.2O).sub.26CF.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2SiCl.sub.3

Synthesis Example 11 (Triallylsilane Compound)

[0584] To a four necked flask of 30 mL provided with a reflux condenser, a thermometer and a stirrer, perfluoropolyether group containing trichloro compound having trichlorosilane at its terminal (C) (4.5 g) prepared in Synthesis Example 10 and 1,3-bis(trifluoromethyl)benzene (5 g) were added and stirred under a nitrogen streaming at 5° C. for 30 minutes. Subsequently, diethyl ether solution (6.22 ml) containing allyl magnesium bromide (0.9 mol/L) was added, and the solution was warmed to room temperature and stirred at this temperature for 10 hours. Then, after cooling the solution to 5° C. and adding methanol (1.78 ml), the solution was warmed to a room temperature and insoluble materials were filtered. Then, after a volatile content was evaporated, a nonvolatile fraction was diluted with perfluorohexane, and washing operation with methanol in a separatory funnel was performed. Then, a volatile content was evaporated to obtain the following perfluoropolyether group containing triallylsilane compound (D) having an allyl group at its terminal (4.74 g).

[0585] Perfluoropolyether group containing triallylsilane compound (D): [0586] CF.sub.3O(CF.sub.2CF.sub.2O).sub.22(CF.sub.2O).sub.26CF.sub.2CH.sub.2OCH.sub.2CH.sub.2CH.sub.2Si(CH.sub.2CH═CH.sub.2).sub.3

Synthesis Example 12 (Trichlorosilane Compound)

[0587] To a four necked flask of 500 mL provided with a reflux condenser, a thermometer and a stirrer, perfluoropolyether group containing triallylsilane compound having an allyl group at its terminal (D) (4.5 g) prepared in Synthesis Example 11, 1,3-bis(trifluoromethyl)benzene (4.5 g), triacetoxymethylsilane (0.015 g), and trichlorosilane (1.13 g) were added and stirred under a nitrogen streaming at 5° C. for 30 minutes. Subsequently, after adding a xylene solution (0.045 ml) containing Pt complex of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane at 2%, the solution was warmed to 60° C. and stirred at this temperature for 5 hours. Then, a volatile content was evaporated under a reduced pressure to obtain the perfluoropolyether group containing trichlorosilane compound having trichlorosilane at its terminal (E) (4.87 g)

[0588] Perfluoropolyether group containing trichlorosilane compound (E): [0589] CF.sub.3O(CF.sub.2CF.sub.2O).sub.22(CF.sub.2O).sub.26CF.sub.2CH.sub.2OCH.sub.2CH.sub.2CH.sub.2Si(CH.sub.2CH.sub.2CH.sub.2SiCl).sub.3

Synthesis Example 13 (Trimethoxysilane Compound)

[0590] To a four necked flask of 30 mL provided with a reflux condenser, a thermometer and a stirrer, perfluoropolyether group containing trichlorosilane compound having trichlorosilane at its terminal (E) (4.5 g) prepared in Synthesis Example 12 and 1,3-bis(trifluoromethyl)benzene (5 g) were added and stirred under a nitrogen streaming at 50° C. for 30 minutes. Subsequently, after a mixed solution of methanol (0.21 g) and trimethyl orthoformate (9.96 g) was added, the solution was warmed to 65° C. and stirred at this temperature for 3 hours. Then, a volatile content was evaporated under a reduced pressure to obtain the following perfluoropolyether group containing trimethoxysilane compound (F) (4.49 g).

[0591] Perfluoropolyether group containing trimethoxysilane compound (F): [0592] CF.sub.3O(CF.sub.2CF.sub.2O).sub.22(CF.sub.2O).sub.26CF.sub.2CH.sub.2OCH.sub.2CH.sub.2CH.sub.2Si(CH.sub.2C.sub.2CH.sub.2Si(OCH.sub.3).sub.3).sub.3

Synthesis of Perfluoro(Poly)Ether Group Containing Silane Compound Having an E/M Ratio of 0.6

Synthesis Example 14 (Synthesis of Perfluoropolyether Peroxide)

[0593] Similarly to Synthesis Example 1 except that oxygen, chlorotrifluoroethylene, and tetrafluoroethylene were supplied at the rate of 8.6 L/h, 0.084 L/h and 7.2 L/h, respectively, to a tubular reactor for a photochemical synthesis provided with 400 W of high pressure mercury lamp and a circulating cooling jacket, perfluorohexane (1100 g) was added, and cooled to −40° C., and then chlorodifluoromethane (R22) (2500 g) was added.

[0594] Supplying of oxygen was started at the rate of 24.5 L/h, and the mercury lamp was turned on. Then, chlorotrifluoroethylene and tetrafluoroethylene were supplied at the rate of 0.2 L/h and 20.4 L/h, respectively. The supplying was kept constant for 5 hours-reaction, and the temperature was kept constant at −40° C.

[0595] After the reaction for 4 hours, the lamp was turned off, the supplying of the raw material was stopped, and chlorodifluoromethane was evaporated. As a result of analysis by .sup.19F-NMR, T-(CF.sub.2CF.sub.2O).sub.n(CF.sub.2O).sub.m(CF.sub.2CF.sub.2OO).sub.p(CF.sub.2OO).sub.q-T (wherein T was OCF.sub.2Cl,OCF.sub.2CF.sub.2Cl,OCF.sub.3,OCF.sub.2COF,OCOF) was obtained, and the n/m ratio was 0.57.

Synthesis Example 15 (Heat-Treatment of Perfluoropolyether Peroxide)

[0596] An oil component (90 g) can be obtained similarly to Synthesis Example 2 except that the compound prepared in Synthesis Example 14 was used.

Synthesis Example 16 (Synthesis of Modified Perfluoropolyether Compound)

[0597] Similarly to Synthesis Example 3 except that the compound (80 g) prepared in Synthesis Example 15, an oil component of CH.sub.3OCOCF.sub.2—(CF.sub.2CF.sub.2O).sub.m′—(CF.sub.2O).sub.n′—CF.sub.2OCO.sub.2CH.sub.3 (60 g) was obtained. As a result of analysis by .sup.19F-NMR, the m′/n′ ratio was 0.60.

Synthesis Example 17 (Adjustment of a Molecular Weight)

[0598] The oil component of CH.sub.3OCOCF.sub.2O—(CF.sub.2CF.sub.2O).sub.m′—(CF.sub.2O).sub.n′—CF.sub.2CO.sub.2CH.sub.3 (55 g) prepared in Synthesis Example 16 was dissolved in perfluorohexane (200 g), and silica gel (27 g) was added and stirred. After celite filtration was performed, the mixture was washed with perfluorohexane to collect fraction (38 g) containing mainly compounds having high molecular weight. By the washing with Novec (trademark) 7200/CF.sub.3CH.sub.2OH (1:1), fraction (15 g) containing mainly compounds having low molecular weight adsorbed to silica gel were separated.

[0599] Then, the oil component (38 g) collected in the above operation was dissolved in perfluorohexane (150 g), and silica gel (20 g) was added and the mixture was stirred. After celite filtration was performed, the mixture was washed with perfluorohexane to separate fraction (22 g) containing mainly compounds having high molecular weight. By the washing with Novec (trademark) 7200/CF.sub.3CH.sub.2OH (1:1), fraction containing mainly compounds having low molecular weight (14 g) which was adsorbed to silica gel was obtained. As a result of analysis by .sup.19F-NMR, the m′/n′ ratio was 0.60.

Synthesis Example 18 (Hydrolysis Reaction)

[0600] Similarly to Synthesis Example 5 except that the compound (14 g) prepared in Synthesis Example 17 was used, an oil component of HOOCOCF.sub.2O—(CF.sub.2CF.sub.2O).sub.m′—(CF.sub.2O).sub.n′—CF.sub.2COOH (12.7 g) was obtained.

Synthesis Example 19 (Fluorination Reaction)

[0601] Similarly to Synthesis Ex ample except that the compound (12 g) prepared in Synthesis Example 18, a mixture of (A) CF.sub.3O(CF.sub.2CF.sub.2O).sub.19(CF.sub.2O).sub.31CF.sub.2COOH, (B) CF.sub.3O(CF.sub.2CF.sub.2O).sub.19(CF.sub.2O).sub.31CF.sub.3, and (C) HCOOCCF.sub.2O(CF.sub.2CF.sub.2O).sub.19(CF.sub.2O).sub.31CF.sub.2COOH was obtained.

Synthesis Example 20 (Separation of One Terminal Type of Carboxylic Acid)

[0602] The mixture (12 g) obtained in Synthesis Example 19 was dissolved in perfluorohexane (50 g), and silica gel (50 g) was added and stirred for 30 minutes. Then, celite filtration was performed, the washing with perfluorohexane (200 ml) was performed to obtain product (B) CF.sub.3O(CF.sub.2CF.sub.2O).sub.19(CF.sub.2O).sub.31CF.sub.3 (2.1 g). Then, the washing with a mixed solution (250 ml) of Novec (trademark) 7200/CF.sub.3CH.sub.2OH (5:1) was performed to obtain one terminal type of carboxylic acid (A) CF.sub.3O(CF.sub.2CF.sub.2O).sub.19(CF.sub.2O).sub.31CF.sub.2COOH (7.1 g).

Synthesis Example 21 (Alcohol Compound)

[0603] To a four necked flask of 50 mL provided with a reflux condenser, a thermometer and a stirrer, perfluoropolyether modified carboxylic acid compound (7 g) of an average composition: CF.sub.3O(CF.sub.2CF.sub.2O).sub.18(CF.sub.2O).sub.30CF.sub.2COOH (a mixture contained a compound comprising a slight amount of repeating units (CF.sub.2CF.sub.2CF.sub.2CF.sub.2O) and/or (CF.sub.2CF.sub.2CF.sub.2O)), bis(2-methoxyethyl)ether (7 g), and NaBH.sub.4 (0.186 g) were added, and stirred at 110° C. for 48 hours. Then, the mixture was cooled to 5° C., and perfluorohexane (9.5 g) was added, and then 3N of hydrochloric acid (9.5 g) was added dropwise. Then, insoluble materials were filtered, perfluorohexane phase which was a lower phase was separated with a separating funnel. Then, a volatile component was evaporated to obtain the following perfluoropolyether group containing alcohol compound having alcohol at its terminal (A) (6.52 g).

[0604] Perfluoropolyether group containing alcohol compound (G): [0605] CF.sub.3O(CF.sub.2CF.sub.2O).sub.18(CF.sub.2O).sub.30CF.sub.2CH.sub.2OH

Synthesis Example 22 (Allylether Compound)

[0606] To a four necked flask of 50 mL provided with a reflux condenser, a thermometer and a stirrer, perfluoropolyether modified alcohol compound (G) (6.5 g) prepared in Synthesis Example 21, 1,3-bis(trifluoromethyl)benzene (7 g) and NaOH (0.173 g) were added, and stirred at 65° C. for 4 hours. Then, allyl bromide (0.52 g) was added, and stirred at 65° C. for 6 hours. Then, the mixture was cooled to a room temperature, perfluorohexane (7 g) was added and insoluble materials were filtered. Washing with 3N of hydrochloric acid using a separating funnel was performed. Then, volatile components were evaporated to obtain the following perfluoropolyether group containing allyloxy compound (H) (6.17 g) having an allyl group at its terminal.

[0607] Perfluoropolyether group containing allyloxy compound (H): [0608] CF.sub.3O(CF.sub.2CF.sub.2O).sub.18(CF.sub.2O).sub.30CF.sub.2CH.sub.2OCH.sub.2CH═CH.sub.2

Synthesis Example 23 (Trichloro Compound)

[0609] To a four necked flask of 30 mL provided with a reflux condenser, a thermometer and a stirrer, perfluoropolyether modified allyloxy compound (H) (6 g) prepared in Synthesis Example 22, 1,3-bis(trifluoromethyl)benzene (6 g), triacetoxymethylsilane (0.018 g), and trichlorosilane (0.41 g) were added and stirred under a nitrogen streaming at 5° C. for 30 minutes. Subsequently, after adding a xylene solution (0.028 ml) containing Pt complex of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane at 2%, the solution was warmed to 60° C. and stirred at this temperature for 5 hours. Then, a volatile content was evaporated to obtain the following perfluoropolyether group containing trichloro compound (I) (5.7 g).

[0610] Perfluoropolyether group containing trichloro compound (I): [0611] CF.sub.3O(CF.sub.2CF.sub.2O).sub.18(CF.sub.2O).sub.30CF.sub.2CH.sub.2OCH.sub.2CH.sub.2CH.sub.2SiCl.sub.3

Synthesis Example 24 (Triallylsilane Compound)

[0612] To a four necked flask of 30 mL provided with a reflux condenser, a thermometer and a stirrer, perfluoropolyether group containing trichloro compound having trichlorosilane at its terminal (I) (5 g) prepared in Synthesis Example 23 and 1,3-bis(trifluoromethyl)benzene (5 g) were added and stirred under a nitrogen streaming at 5° C. for 30 minutes. Subsequently, diethyl ether solution containing allyl magnesium bromide (0.9 mol/L) (6.91 ml) was added, and the solution was warmed to room temperature and stirred at this temperature for 10 hours. Then, after cooling the solution to 5° C. and adding methanol (2 ml), the solution was warmed to a room temperature and insoluble materials were filtered. Then, after a volatile content was evaporated, a nonvolatile fraction was diluted with perfluorohexane, and washing operation with methanol in a separatory funnel was conducted. Then, a volatile content was evaporated to obtain the following perfluoropolyether group containing triallylsilane compound (J) having an allyl group at its terminal (5.26 g).

[0613] Perfluoropolyether group containing triallylsilane compound (J): [0614] CF.sub.3O(CF.sub.2CF.sub.2O).sub.18(CF.sub.2O).sub.30CF.sub.2CH.sub.2OCH.sub.2CH.sub.2CH.sub.2Si(CH.sub.2CH═CH.sub.2).sub.3

Synthesis Example 25 (Chlorosilane Compound)

[0615] To a four necked flask of 30 mL provided with a reflux condenser, a thermometer and a stirrer the perfluoropolyether group containing allyl compound (J) having an allyl group at its terminal (J) (5 g) prepared in Synthesis Example 24, 1,3-bis(trifluoromethyl)benzene (5 g), triacetoxymethylsilane (0.016 g), and trichlorosilane (1.25 g) were added and stirred under a nitrogen streaming at 5° C. for 30 minutes. Subsequently, after adding a xylene solution (0.05 ml) containing Pt complex of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane at 2%, the solution was warmed to 60° C. and stirred at this temperature for 5 hours. Then, a volatile content was evaporated under a reduced pressure to obtain the perfluoropolyether group containing trichlorosilane compound having trichlorosilane at its terminal (K) (5.4 g)

[0616] Perfluoropolyether group containing chlorosilane compound (K): [0617] CF.sub.3O(CF.sub.2CF.sub.2O).sub.18(CF.sub.2O).sub.30CF.sub.2CH.sub.2OCH.sub.2CH.sub.2CH.sub.2Si(CH.sub.2CH.sub.2CH.sub.2SiCl.sub.3).sub.3

Synthesis Example 26 (Trimethoxysilane Compound)

[0618] To a four necked flask of 30 mL provided with a reflux condenser, a thermometer and a stirrer, perfluoropolyether group containing trichlorosilane compound having trichlorosilane at its terminal (K) (5 g) prepared in Synthesis Example 25 and 1,3-bis(trifluoromethyl)benzene (5 g) were added and stirred under a nitrogen streaming at 50° C. for 30 minutes. Subsequently, after a mixed solution of methanol (0.23 g) and trimethyl orthoformate (11.1 g) was added, the solution was warmed to 65° C. and stirred at this temperature for 3 hours. Then, a volatile content was evaporated under a reduced pressure to obtain the following perfluoropolyether group containing trimethoxysilane compound (L) (5 g).

[0619] Perfluoropolyether group containing trimethoxysilane compound (L): [0620] CF.sub.3O(CF.sub.2CF.sub.2O).sub.18(CF.sub.2O).sub.30CF.sub.2CH.sub.2OCH.sub.2CH.sub.2CH.sub.2Si(CH.sub.2CH.sub.2CH.sub.2Si(OCH.sub.3).sub.3).sub.3

Example 1

[0621] Compound (F) was obtained in Synthesis Example 13 was dissolved in hydrofluoroether (Novec HFE7200 manufactured by Sumitomo 3M Ltd.)) such that the concentration was 20 wt % to prepare Surface-treating agent 1.

[0622] Surface-treating agent 1 prepared in the above was vacuum deposited on a chemical strengthening glass (Gorilla glass manufactured by Corning Incorporated; thickness: 0.7 mm). Processing condition of the vacuum deposition was a pressure of 3.0×10.sup.−3 Pa. Firstly, silicon dioxide was deposited on the surface of this chemical strengthening glass in a thickness of 7 nm in a manner of an electron-beam deposition. Subsequently, the surface-treating agent of 2 mg (that is, it contained of 0.4 mg of Compound (D)) was vacuum-deposited per one plate of the chemical strengthening glass (55 mm×100 mm). Then, the chemical strengthening glass having the deposited layer was heated to form the surface-treating layer.

Example 2

[0623] The surface-treating agent was prepared and the surface-treating layer was formed similarly to Example 1 except that Compound (L) obtained in Synthesis Example 26 was used in place of Compound (F), respectively.

Comparative Examples 1 and 2

[0624] The surface-treating agent was prepared and the surface-treating layer was formed similarly to Example 1 except that Control compounds 1 and 2 were used in place of Compound (F), respectively.

[0625] Control Compound 1 [0626] CF.sub.3O(CF.sub.2CF.sub.2O).sub.20(CF.sub.2O).sub.15CF.sub.2CH.sub.2OCH.sub.2CH.sub.2CH.sub.2Si((CH.sub.2CH.sub.2CH.sub.2Si(OCH.sub.3).sub.3).sub.3

[0627] Control Compound 2 [0628] CF.sub.3O(CF.sub.2CF.sub.2O).sub.15(CF.sub.2O).sub.16CF.sub.2CH.sub.2OCH.sub.2CH.sub.2CH.sub.2Si((CH.sub.2CH.sub.2CH.sub.2Si(OCH.sub.3).sub.3).sub.3

[0629] Experiment 1

[0630] Evaluation of Surface Slip Property (Measurement of Coefficient of Dynamic Friction)

[0631] Coefficient of dynamic friction of the surface-treating layers formed on the surface of the base material in the above Examples 1 and 2 and Comparative Examples 1 and 2 was measured. Specifically, the coefficient of dynamic friction (−) was measured by using a surface texture measurement instrument (FPT-1 manufactured by Labthink Co., Ltd.) using a paper as a friction probe according to ASTM D4917. Specifically, the base material on which the surface-treating layer was formed was horizontally arranged, and then, a friction paper (2 cm×2 cm) was contacted to an exposed surface of the surface-treating layer and a load of 200 gf was applied thereon. Then, the friction paper was parallely moved at a speed of 500 mm/second while applying the load and the coefficient of dynamic friction was measured. Four samples for each of Examples and Comparative Examples were measured. The results are shown in Table 1.

[0632] Experiment 2

[0633] Evaluation of Friction Durability

[0634] Friction durability of the surface-treating layers formed on the surface of the base material in the above Examples 1 and 2 and Comparative Examples 1 and 2 was measured by using eraser-friction durability test. Specifically, a sample member on which the surface-treating layer was formed was horizontally arranged, and then, an eraser (manufactured by Kokuyo Co., Ltd., KESHI-70, horizontal dimensions: 1 cm×1.6 cm) was contacted to the surface of the surface-treating layer and a load of 500 gf was applied thereon. Then, the eraser was shuttled at a rate of 20 mm/second while applying the load. The static water contact angle (degree) was measured per 1,000 shuttling. The evaluation was stopped when the measured value of the contact angle became to be less than 100 degree. The results are shown in Table 2.

TABLE-US-00001 TABLE 1 EM Coefficient of dynamic friction (—) ratio Average n = 1 n = 2 n = 3 n = 4 Example 1 0.85 0.024 0.024 0.023 0.024 0.023 Example 2 0.60 0.022 0.021 0.023 0.021 0.023 Comparative 1.33 0.034 0.033 0.035 0.032 0.036 Example 1 Comparative 0.94 0.033 0.033 0.035 0.032 0.033 Example 2

TABLE-US-00002 TABLE 2 The number of Contact Angle (degree) rubbing Comparative Comparative (time) Example 1 Example 2 Example 1 Example 2 0 115.8 115.0 114.6 115.2 1000 114.4 115.7 114.7 114.0 2000 113.4 114.5 113.4 113.5 3000 113.8 115.2 110.5 110.6 4000 112.9 114.8 107.3 109.6 5000 113.4 112.9 102.7 105.9 6000 113.0 112.8 100.5 104.2 7000 113.6 113.0 93.2 103.9 8000 113.4 111.8 — 98.3 9000 113.1 111.4 — — 10000 109.6 111.6 — — 11000 105.1 108.2 — — 12000 102.8 109.1 — — 13000 98.4 106.2 — — 14000 — 106.3 — — 15000 — 105.2 — — 16000 — 103.3 — — 17000 — 99.0 — —

[0635] As understood from Tables 1 and 2, it was confirmed that the surface-treating agent containing the perfluoropolyether group containing silane compound of the present invention having the EM ratio within the range of the present invention (Examples 1 and 2) can provide excellent friction durability in addition to excellent surface slip property (low coefficient of dynamic friction). On the other hand, the surface-treating agent containing the conventional perfluoropolyether group containing silane compound having the EM ratio of more than 9.0 (Comparative Example 1) has less surface slip property and friction durability in comparison with the surface-treating agent of the present invention. A reason for this is presumed as follows: the present invention has higher proportion of methyloxy in the perfluoropolyether chain than the conventional surface-treating agent, thereby being able to increase surface slip property, as a result of which, friction durability is improved.

INDUSTRIAL APPLICABILITY

[0636] The present invention is suitably applied for forming a surface-treating layer on a surface of various base materials, in particular, an optical member in which transparency is required.