PERFLUORO(POLY)ETHER GROUP-CONTAINING SILANE COMPOUND

Abstract

A perfluoro(poly)ether group-containing silane compound including a structure represented by -PFPE-XSiR.sup.a.sub.kR.sup.b.sub.lR.sup.c.sub.m. In an exemplary embodiment, PFPE is a perfluoro(poly)ether group, X is a substituted or unsubstituted alkylene group having 2 to 20 carbon atoms, R.sup.a is a functional group comprising a Si, R.sup.c is a hydrogen atom or a lower alkyl group, k is an integer of 1 to 3, l and m are an integer of 0 to 2, respectively, and the sum of k, l and m in each SiR.sup.a.sub.kR.sup.b.sub.lR.sup.c.sub.m is 3. Also disclosed is a surface-treating agent containing the silane compound, a pellet containing the surface-treating agent and an article including a base material and a layer formed from the silane compound or the surface-treating agent on a surface of the base material.

Claims

1-17. (canceled)

18. A perfluoro(poly)ether group-containing silane compound represented by formula (A1) or formula (A2):
Rf-PFPE-XSiR.sup.a.sub.kR.sup.b.sub.lR.sup.c.sub.m(A1)
R.sup.c.sub.mR.sup.b.sub.lR.sup.a.sub.kSiX-PFPE-XSiR.sup.a.sub.kR.sup.b.sub.lR.sup.c.sub.m(A2) wherein: PFPE represents, each independently at each occurrence, a group represented by formula: (OC.sub.6F.sub.12).sub.a(OC.sub.5F.sub.10).sub.b(OC.sub.4F.sub.8).sub.c(OC.sub.3F.sub.6).sub.d(OC.sub.2F.sub.4).sub.e(OCF.sub.2).sub.f wherein a, b, c, d, e and f are each independently an integer of 0 or more and 200 or less, the sum of a, b, c, d, e and f is at least 1, and the occurrence order of respective repeating units in parentheses with a symbol a, b, c, d, e or f is not limited in the formula; Rf represents, each independently at each occurrence, an alkyl group having 1 to 16 carbon atoms, optionally substituted with one or more fluorine atoms; X represents, each independently at each occurrence, a substituted or unsubstituted alkylene group having 2 to 20 carbon atoms; R.sup.a represents, each independently at each occurrence, ZSiR.sup.1.sub.pR.sup.2.sub.qR.sup.3.sub.r; Z represents, each independently at each occurrence, an oxygen atom or a divalent organic group; R.sup.1 represents, each independently at each occurrence, R.sup.a; R.sup.a has the same definition as R.sup.a; the number of Si atoms linearly linked via Z group in R.sup.a is up to 5; R.sup.2 represents, each independently at each occurrence, a hydroxyl group or a hydrolyzable group; R.sup.3 represents, each independently at each occurrence, a hydrogen atom or a lower alkyl group; p is, each independently at each occurrence, an integer of 0 to 3; q is, each independently at each occurrence, an integer of 0 to 3; r is, each independently at each occurrence, an integer of 0 to 3; provided that the sum of p, q and r in each ZSiR.sup.1.sub.pR.sup.2.sub.qR.sup.3.sub.r is 3, and two or more Si atoms having at least one R.sup.2 are present in the formulae (A1) and (A2); R.sup.b represents, each independently at each occurrence, a hydroxyl group or a hydrolyzable group; R.sup.c represents, each independently at each occurrence, a hydrogen atom or a lower alkyl group; k is, each independently at each occurrence, an integer of 1 to 3; l is, each independently at each occurrence, an integer of 0 to 2; and m is, each independently at each occurrence, an integer of 0 to 2; provided that the sum of k, l and m in each SiR.sup.a.sub.kR.sup.b.sub.lR.sup.c.sub.m is 3.

19. The perfluoro(poly)ether group-containing silane compound according to claim 18, wherein X represents an unsubstituted alkylene group having 2 to 10 carbon atoms.

20. The perfluoro(poly)ether group-containing silane compound according to claim 18, wherein k is, each independently at each occurrence, 2 or 3.

21. The perfluoro(poly)ether group-containing silane compound according to claim 18, wherein Z is an alkylene group.

22. The perfluoro(poly)ether group-containing silane compound according to claim 18, wherein the number of Si atoms linearly linked via Z group in R.sup.a is 1 or 2.

23. The perfluoro(poly)ether group-containing silane compound according to claim 18, wherein the number of Si atoms linearly linked via Z group in R.sup.a is 1.

24. The perfluoro(poly)ether group-containing silane compound according to claim 18, wherein Rf is a perfluoroalkyl group having 1 to 16 carbon atoms.

25. The perfluoro(poly)ether group-containing silane compound according to claim 18, wherein PFPE is represented by the following formula (a), (b) or (c):
(OC.sub.3F.sub.6).sub.d(a) wherein d is an integer of 1 or more and 200 or less;
(OC.sub.4F.sub.8).sub.c(OC.sub.3F.sub.6).sub.d(OC.sub.2F.sub.4).sub.e(OCF.sub.2).sub.f(b) wherein c and d are each independently an integer of 0 or more and 30 or less; e and f are each independently an integer of 1 or more and 200 or less; the sum of c, d, e and f is an integer of 10 or more and 200 or less; and the occurrence order of respective repeating units in parentheses with a subscript c, d, e or f is not limited in the formula;
(R.sup.6R.sup.7).sub.j(c) wherein R.sup.6 is OCF.sub.2 or OC.sub.2F.sub.4; R.sup.7 is a group selected from OC.sub.2F.sub.4, OC.sub.3F.sub.6, OC.sub.4F.sub.8, OC.sub.5F.sub.10 and OC.sub.6F.sub.12, or a combination of two or three groups selected therefrom; and j is an integer of 2 to 100.

26. The perfluoro(poly)ether group-containing silane compound according to claim 18, wherein Rf is perfluoroalkyl group having 1 to 16 carbon atoms, PFPE is represented by the following formula (a), (b) or (c):
(OC.sub.3F.sub.6).sub.d(a) wherein d is an integer of 1 or more and 200 or less;
(OC.sub.4F.sub.8).sub.c(OC.sub.3F.sub.6).sub.d(OC.sub.2F.sub.4).sub.e(OCF.sub.2).sub.f(b) wherein c and d are each independently an integer of 0 or more and 30 or less; e and f are each independently an integer of 1 or more and 200 or less; the sum of c, d, e and f is an integer of 10 or more and 200 or less; and the occurrence order of respective repeating units in parentheses with a subscript c, d, e or f is not limited in the formula;
(R.sup.6R.sup.7).sub.j(c) wherein R.sup.6 is OCF.sub.2 or OC.sub.2F.sub.4; R.sup.7 is a group selected from OC.sub.2F.sub.4, OC.sub.3F.sub.6, OC.sub.4F.sub.8, OC.sub.5F.sub.10 and OC.sub.6F.sub.12, or a combination of two or three groups selected therefrom; j is an integer of 2 to 100; X is an unsubstituted linear alkylene group having 2 to 10 carbon atoms; k is 3; and q is 3.

27. A surface-treating agent comprising at least one perfluoro(poly)ether group-containing silane compound represented by formula (A1) and/or formula (A2) according to claim 18.

28. The surface-treating agent according to claim 27, further comprising one or more other components selected from a fluorine-containing oil, a silicone oil, an alcohol, a catalyst, a transition metal, a halide ion, and a compound containing an atom having an unshared electron pair in a molecular structure.

29. The surface-treating agent according to claim 28, further comprising a solvent.

30. The surface-treating agent according to claim 27, which is used as an antifouling coating agent or a water-proof coating agent.

31. A pellet comprising the surface-treating agent according to claim 27.

32. An article comprising a base material, and a layer formed from the compound according to claim 18 on the surface of the base material.

33. The article according to claim 32, wherein the article is an optical member.

34. The article according to claim 32, wherein the article is a display.

35. An article comprising a base material, and a layer formed from the surface-treating agent according to claim 27 on the surface of the base material.

36. The article according to claim 35, wherein the article is an optical member.

37. The article according to claim 35, wherein the article is a display.

Description

EXAMPLES

[0224] The PFPE-containing silane compound of the present invention will be more specifically described with reference to the following Examples, but the present invention is not intended to be limited to these Examples.

Synthesis Example 1

[0225] To a 100-mL four-necked flask equipped with a reflux condenser, a thermometer and a stirrer, 10 g of a perfluoropolyether-modified allyl compound represented by an average compositional formula CF.sub.3CF.sub.2CF.sub.2O(CF.sub.2CF.sub.2CF.sub.2O).sub.20CF.sub.2CF.sub.2CH.sub.2CHCH.sub.2, 10 g of 1,3-bis(trifluoromethyl)benzene, and 0.7 g of trichlorosilane were added and stirred at 5 C. under a nitrogen stream for 30 minutes. Subsequently, 0.05 ml of a solution containing 2% of a Pt complex of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane in xylene was added thereto, and thereafter the resultant was heated to 60 C., and stirred at that temperature for 3 hours. Thereafter, the volatile content was distilled off under reduced pressure, thereby providing 9 g of perfluoropolyether group-containing silane compound (A) having trichlorosilane at a terminal, represented by the following formula.

[0226] Perfluoropolyether Group-Containing Silane Compound (A):

CF.sub.3CF.sub.2CF.sub.2O(CF.sub.2CF.sub.2CF.sub.2O).sub.20CF.sub.2CF.sub.2CH.sub.2CH.sub.2CH.sub.2SiCl.sub.3

Synthesis Example 2

[0227] To a 100-mL four-necked flask equipped with a reflux condenser, a thermometer and a stirrer, 9 g of perfluoropolyether group-containing trichlorosilane compound (A) having trichlorosilane at a terminal, synthesized in Synthesis Example 1, and 15 g of 1,3-bis(trifluoromethyl)benzene were added and stirred at 5 C. under a nitrogen stream for 30 minutes. Subsequently, 14 ml of a solution containing 0.7 mol/L allyl magnesium bromide in diethyl ether was added thereto, and thereafter the resultant was heated to room temperature, and stirred at that temperature for 10 hours. Thereafter, the resultant was cooled to 5 C., 3 ml of methanol was added thereto, thereafter perfluorohexane was added thereto and the mixture was stirred for 30 minutes, and thereafter a perfluorohexane layer was collected by separation with a separating funnel. Subsequently, the volatile content was distilled off under reduced pressure, thereby providing 10 g of the following perfluoropolyether group-containing allyl compound (B) having an allyl group at a terminal.

[0228] Perfluoropolyether Group-Containing Allyl Compound (B):

CF.sub.3CF.sub.2CF.sub.2O(CF.sub.2CF.sub.2CF.sub.2O).sub.20CF.sub.2CF.sub.2CH.sub.2CH.sub.2CH.sub.2Si(CH.sub.2CHCH.sub.2).sub.3

Synthesis Example 3

[0229] To a 100-mL four-necked flask equipped with a reflux condenser, a thermometer and a stirrer, 10 g of perfluoropolyether group-containing allyl compound (B) having an allyl group at a terminal, synthesized in Synthesis Example 2, 15 g of 1,3-bis(trifluoromethyl)benzene, and 3.15 g of trichlorosilane were added and stirred at 5 C. under a nitrogen stream for 30 minutes. Subsequently, 0.1 ml of a solution containing 2% of a Pt complex of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane in xylene was added thereto, and thereafter the resultant was heated to 60 C., and stirred at that temperature for 2 hours. Thereafter, the volatile content was distilled off under reduced pressure, thereby providing 11 g of the following perfluoropolyether group-containing trichlorosilane compound (C) having trichlorosilane at a terminal.

[0230] Perfluoropolyether Group-Containing Trichlorosilane Compound (C):

CF.sub.3CF.sub.2CF.sub.2O(CF.sub.2CF.sub.2CF.sub.2O).sub.20CF.sub.2CF.sub.2CH.sub.2CH.sub.2CH.sub.2Si(CH.sub.2CH.sub.2CH.sub.2SiCl.sub.3).sub.3

Synthesis Example 4

[0231] To a 100-mL four-necked flask equipped with a reflux condenser, a thermometer and a stirrer, 11 g of perfluoropolyether group-containing trichlorosilane compound (C) having trichlorosilane at a terminal, synthesized in Synthesis Example 3, and 15 g of 1,3-bis(trifluoromethyl)benzene were added and stirred at 50 C. under a nitrogen stream for 30 minutes. Subsequently, a mixed solution of 0.30 g of methanol and 5.4 g of trimethyl orthoformate was added, and thereafter the resultant was heated to 55 C., and stirred at that temperature for 2 hours. Thereafter, the volatile content was distilled off under reduced pressure, thereby providing 11 g of the following perfluoropolyether group-containing silane compound (D) having a trimethoxysilyl group at a terminal.

[0232] Perfluoropolyether Group-Containing Silane Compound (D):

CF.sub.3CF.sub.2CF.sub.2O(CF.sub.2CF.sub.2CF.sub.2O).sub.20CF.sub.2CF.sub.2CH.sub.2CH.sub.2CH.sub.2Si[CH.sub.2CH.sub.2CH.sub.2Si(OCH.sub.3).sub.3].sub.3

Synthesis Example 5

[0233] To a 100-mL four-necked flask equipped with a reflux condenser, a thermometer and a stirrer, 10 g of a perfluoropolyether-modified allyl compound represented by an average compositional formula CF.sub.3O(CF.sub.2CF.sub.2O).sub.20(CF.sub.2O).sub.16CF.sub.2CH.sub.2CHCH.sub.2, 14 g of 1,3-bis(trifluoromethyl)benzene, and 1.1 g of trichlorosilane were added and stirred at 5 C. under a nitrogen stream for 30 minutes. Subsequently, 0.08 ml of a solution containing 2% of a Pt complex of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane in xylene was added thereto, and thereafter the resultant was heated to 60 C., stirred at that temperature for 4 hours. Thereafter, the volatile content was distilled off under reduced pressure, thereby providing 10.1 g of perfluoropolyether group-containing trichlorosilane compound (E) having trichlorosilane at a terminal, represented by the following formula.

[0234] Perfluoropolyether Group-Containing Trichlorosilane Compound (E):

CF.sub.3O(CF.sub.2CF.sub.2O).sub.20(CF.sub.2O).sub.16CF.sub.2CH.sub.2CH.sub.2CH.sub.2SiCl.sub.3

Synthesis Example 6

[0235] To a 100-mL four-necked flask equipped with a reflux condenser, a thermometer and a stirrer, 10.1 g of perfluoropolyether group-containing trichlorosilane compound (E) having trichlorosilane at a terminal, synthesized in Synthesis Example 5, and 14 g of 1,3-bis(trifluoromethyl)benzene were added and stirred at 5 C. under a nitrogen stream for 30 minutes. Subsequently, 15.7 ml of a solution containing 1 mol/L allyl magnesium chloride in tetrahydrofuran was added thereto, and thereafter the resultant was heated to room temperature, and stirred at that temperature for 12 hours. Thereafter, the resultant was cooled to 5 C., 4.6 ml of methanol was added thereto, thereafter 20 g of perfluorohexane was added and the mixture was stirred for 30 minutes, and thereafter a perfluorohexane layer was collected by separation with a separating funnel. Subsequently, the volatile content was distilled off under reduced pressure, thereby providing 10.3 g of the following perfluoropolyether group-containing allyl compound (F) having an allyl group at a terminal.

[0236] Perfluoropolyether Group-Containing Allyl Compound (F):

CF.sub.3O(CF.sub.2CF.sub.2O).sub.20(CF.sub.2O).sub.16CF.sub.2CH.sub.2CH.sub.2CH.sub.2Si(CH.sub.2CHCH.sub.2).sub.3

Synthesis Example 7

[0237] To a 100-mL four-necked flask equipped with a reflux condenser, a thermometer and a stirrer, 5.5 g of perfluoropolyether group-containing allyl compound (F) having an allyl group at a terminal, synthesized in Synthesis Example 6, 8 g of 1,3-bis(trifluoromethyl)benzene, and 1.2 g of trichlorosilane were added and stirred at 5 C. under a nitrogen stream for 30 minutes. Subsequently, 0.06 ml of a solution containing 2% of a Pt complex of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane in xylene was added thereto, and thereafter the resultant was heated to 60 C., and stirred at that temperature for 2 hours. Thereafter, the volatile content was distilled off under reduced pressure, thereby providing 5.6 g of the following perfluoropolyether group-containing trichlorosilane compound (G) having trichlorosilane at a terminal.

[0238] Perfluoropolyether Group-Containing Trichlorosilane Compound (G):

CF.sub.3O(CF.sub.2CF.sub.2O).sub.20(CF.sub.2O).sub.16CF.sub.2CH.sub.2CH.sub.2CH.sub.2Si(CH.sub.2CH.sub.2CH.sub.2SiCl.sub.3).sub.3

Synthesis Example 8

[0239] To a 100-mL four-necked flask equipped with a reflux condenser, a thermometer and a stirrer, 5.6 g of perfluoropolyether group-containing trichlorosilane compound (G) having trichlorosilane at a terminal, synthesized in Synthesis Example 7, and 9 g of 1,3-bis(trifluoromethyl)benzene were added and stirred at 50 C. under a nitrogen stream for 30 minutes. Subsequently, a mixed solution of 0.2 g of methanol and 5.8 g of trimethyl orthoformate was added, and thereafter the resultant was heated to 55 C., and stirred at that temperature for 3 hours. Thereafter, the volatile content was distilled off under reduced pressure, thereby providing 5.7 g of the following perfluoropolyether group-containing silane compound (H) having a trimethoxysilyl group at a terminal.

[0240] Perfluoropolyether Group-Containing Silane Compound (H):

CF.sub.3O(CF.sub.2CF.sub.2O).sub.20(CF.sub.2O).sub.16CF.sub.2CH.sub.2CH.sub.2CH.sub.2Si[CH.sub.2CH.sub.2CH.sub.2Si(OCH.sub.3).sub.3].sub.3

Synthesis Example 9

[0241] To a 100-mL four-necked flask equipped with a reflux condenser, a thermometer and a stirrer, 9 g of perfluoropolyether group-containing silane compound (A) having trichlorosilane at a terminal, synthesized in Synthesis Example 1, and 15 g of 1,3-bis(trifluoromethyl)benzene were added and stirred at 5 C. under a nitrogen stream for 30 minutes. Subsequently, 10 ml of a solution containing 1.6 mol/L vinyl magnesium chloride in tetrahydrofuran was added thereto, and thereafter the resultant was heated to room temperature, and stirred at that temperature for 10 hours. Thereafter, the resultant was cooled to 5 C., 5 ml of methanol was added thereto, thereafter perfluorohexane was added thereto and the mixture was stirred for 30 minutes, and thereafter a perfluorohexane layer was collected by separation with a separating funnel. Subsequently, the volatile content was distilled off under reduced pressure, thereby providing 9.1 g of the following perfluoropolyether group-containing vinyl compound (I) having a vinyl group at a terminal.

[0242] Perfluoropolyether Group-Containing Vinyl Compound (I):

CF.sub.3CF.sub.2CF.sub.2O(CF.sub.2CF.sub.2CF.sub.2O).sub.20CF.sub.2CF.sub.2CH.sub.2CH.sub.2CH.sub.2Si(CHCH.sub.2).sub.3

Synthesis Example 10

[0243] To a 100-mL four-necked flask equipped with a reflux condenser, a thermometer and a stirrer, 9.1 g of perfluoropolyether group-containing vinyl compound (I) having a vinyl group at a terminal, synthesized in Synthesis Example 9, 12 g of 1,3-bis(trifluoromethyl)benzene, and 3.0 g of trichlorosilane were added and stirred at 5 C. under a nitrogen stream for 30 minutes. Subsequently, 0.1 ml of a solution containing 2% of a Pt complex of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane in xylene was added thereto, and thereafter the resultant was heated to 60 C., and stirred at that temperature for 3 hours. Thereafter, the volatile content was distilled off under reduced pressure, thereby providing 9.2 g of the following perfluoropolyether group-containing trichlorosilane compound (J) having trichlorosilane at a terminal.

[0244] Perfluoropolyether Group-Containing Trichlorosilane Compound (J):

CF.sub.3CF.sub.2CF.sub.2O(CF.sub.2CF.sub.2CF.sub.2O).sub.20CF.sub.2CF.sub.2CH.sub.2CH.sub.2CH.sub.2Si(CH.sub.2CH.sub.2SiCl.sub.3).sub.3

Synthesis Example 11

[0245] To a 100-mL four-necked flask equipped with a reflux condenser, a thermometer and a stirrer, 9.2 g of perfluoropolyether group-containing trichlorosilane compound (J) having trichlorosilane at a terminal, synthesized in Synthesis Example 10, and 12 g of 1,3-bis(trifluoromethyl)benzene were added and stirred at 50 C. under a nitrogen stream for 30 minutes. Subsequently, a mixed solution of 0.40 g of methanol and 13.2 g of trimethyl orthoformate was added, and thereafter the resultant was heated to 55 C., and stirred at that temperature for 3 hours. Thereafter, the volatile content was distilled off under reduced pressure, thereby providing 9.3 g of the following perfluoropolyether group-containing silane compound (K) having a trimethoxysilyl group at a terminal.

[0246] Perfluoropolyether Group-Containing Silane Compound (K):

CF.sub.3CF.sub.2CF.sub.2O(CF.sub.2CF.sub.2CF.sub.2O).sub.20CF.sub.2CF.sub.2CH.sub.2CH.sub.2CH.sub.2Si[CH.sub.2CH.sub.2Si(OCH.sub.3).sub.3].sub.3

Synthesis Example 12

[0247] To a 100-mL four-necked flask equipped with a reflux condenser, a thermometer and a stirrer, 10.1 g of perfluoropolyether group-containing trichlorosilane compound (E) having trichlorosilane at a terminal, synthesized in Synthesis Example 5, and 12 g of 1,3-bis(trifluoromethyl)benzene were added and stirred at 5 C. under a nitrogen stream for 30 minutes. Subsequently, 9.5 ml of a solution containing 1.6 mol/L vinyl magnesium chloride in tetrahydrofuran was added thereto, and thereafter the resultant was heated to room temperature, and stirred at that temperature for 12 hours. Thereafter, the resultant was cooled to 5 C., 6 ml of methanol was added thereto, thereafter 20 g of perfluorohexane was added thereto and the mixture was stirred for 30 minutes, and thereafter a perfluorohexane layer was collected by separation with a separating funnel. Subsequently, the volatile content was distilled off under reduced pressure, thereby providing 10.2 g of the following perfluoropolyether group-containing vinyl compound (L) having a vinyl group at a terminal.

[0248] Perfluoropolyether Group-Containing Vinyl Compound (L):

CF.sub.3O(CF.sub.2CF.sub.2O).sub.20(CF.sub.2O).sub.16CF.sub.2CH.sub.2CH.sub.2CH.sub.2Si(CHCH.sub.2).sub.3

Synthesis Example 13

[0249] To a 100-mL four-necked flask equipped with a reflux condenser, a thermometer and a stirrer, 6.0 g of perfluoropolyether group-containing vinyl compound (L) having a vinyl group at a terminal, synthesized in Synthesis Example 12, 9 g of 1,3-bis(trifluoromethyl)benzene, and 1.5 g of trichlorosilane were added and stirred at 5 C. under a nitrogen stream for 30 minutes. Subsequently, 0.06 ml of a solution containing 2% of a Pt complex of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane in xylene was added thereto, and thereafter the resultant was heated to 60 C., and stirred at that temperature for 2 hours. Thereafter, the volatile content was distilled off under reduced pressure, thereby providing 6.1 g of the following perfluoropolyether group-containing trichlorosilane compound (M) having trichlorosilane at a terminal.

[0250] Perfluoropolyether Group-Containing Trichlorosilane Compound (M):

CF.sub.3O(CF.sub.2CF.sub.2O).sub.20(CF.sub.2).sub.16CF.sub.2CH.sub.2CH.sub.2CH.sub.2Si(CH.sub.2CH.sub.2SiCl.sub.3).sub.3

Synthesis Example 14

[0251] To a 100-mL four-necked flask equipped with a reflux condenser, a thermometer and a stirrer, 6.1 g of perfluoropolyether group-containing trichlorosilane compound (M) having trichlorosilane at a terminal, synthesized in Synthesis Example 13, and 9 g of 1,3-bis(trifluoromethyl)benzene were added and stirred at 50 C. under a nitrogen stream for 30 minutes.

[0252] Subsequently, a mixed solution of 0.25 g of methanol and 8.3 g of trimethyl orthoformate was added, and thereafter the resultant was heated to 55 C., and stirred at that temperature for 3 hours. Thereafter, the volatile content was distilled off under reduced pressure, thereby providing 6.2 g of the following perfluoropolyether group-containing silane compound (N) having a trimethoxysilyl group at a terminal.

[0253] Perfluoropolyether group-containing silane compound (N):

CF.sub.3(CF.sub.2CF.sub.2O).sub.20(CF.sub.2O).sub.16CF.sub.2CH.sub.2CH.sub.2CH.sub.2Si[CH.sub.2CH.sub.2Si(OCH.sub.3).sub.3].sub.3

Synthesis Example 15

[0254] To a 100-mL four-necked flask equipped with a reflux condenser, a thermometer and a stirrer, 10.0 g of perfluoropolyether group-containing trichlorosilane compound (E) having trichlorosilane at a terminal, synthesized in Synthesis Example 5, and 12 g of 1,3-bis(trifluoromethyl)benzene were added and stirred at 5 C. under a nitrogen stream for 30 minutes. Subsequently, 16.5 ml of a solution containing 1.0 mol/L butenyl magnesium bromide in tetrahydrofuran was added thereto, and thereafter the resultant was heated to room temperature, and stirred at that temperature for 12 hours. Thereafter, the resultant was cooled to 5 C., 6 ml of methanol was added thereto, thereafter 20 g of perfluorohexane was added thereto and the mixture was stirred for 30 minutes, and thereafter a perfluorohexane layer was collected by separation with a separating funnel. Subsequently, the volatile content was distilled off under reduced pressure, thereby providing 10.1 g of the following perfluoropolyether group-containing butenyl compound (O) having a butenyl group at a terminal.

[0255] Perfluoropolyether Group-Containing Butenyl Compound (O):

CF.sub.3O(CF.sub.2CF.sub.2O).sub.20(CF.sub.2O).sub.16CF.sub.2CH.sub.2CH.sub.2CH.sub.2Si(CH.sub.2CH.sub.2CHCH.sub.2).sub.3

Synthesis Example 16

[0256] To a 100-mL four-necked flask equipped with a reflux condenser, a thermometer and a stirrer, 6.0 g of perfluoropolyether group-containing butenyl compound (O) having a butenyl group at a terminal, synthesized in Synthesis Example 15, 9 g of 1,3-bis(trifluoromethyl)benzene, and 1.5 g of trichlorosilane were added and stirred at 5 C. under a nitrogen stream for 30 minutes. Subsequently, 0.06 ml of a solution containing 2% of a Pt complex of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane in xylene was added thereto, and thereafter the resultant was heated to 60 C., and stirred at that temperature for 2 hours. Thereafter, the volatile content was distilled off under reduced pressure, thereby providing 6.1 g of the following perfluoropolyether group-containing trichlorosilane compound (P) having trichlorosilane at a terminal.

[0257] Perfluoropolyether Group-Containing Trichlorosilane Compound (P):

CF.sub.3O(CF.sub.2CF.sub.2O).sub.20(CF.sub.2O).sub.16CF.sub.2CH.sub.2CH.sub.2CH.sub.2Si(CH.sub.2CH.sub.2CH.sub.2CH.sub.2SiCl.sub.3).sub.3

Synthesis Example 17

[0258] To a 100-mL four-necked flask equipped with a reflux condenser, a thermometer and a stirrer, 6.1 g of perfluoropolyether group-containing trichlorosilane compound (P) having trichlorosilane at a terminal, synthesized in Synthesis Example 16, and 9 g of 1,3-bis(trifluoromethyl)benzene were added and stirred at 50 C. under a nitrogen stream for 30 minutes. Subsequently, a mixed solution of 0.25 g of methanol and 8.3 g of trimethyl orthoformate was added, and thereafter the resultant was heated to 55 C., and stirred at that temperature for 3 hours. Thereafter, the volatile content was distilled off under reduced pressure, thereby providing 6.2 g of the following perfluoropolyether group-containing silane compound (Q) having a trimethoxysilyl group at a terminal.

[0259] Perfluoropolyether Group-Containing Silane Compound (Q):

CF.sub.3O(CF.sub.2CF.sub.2O).sub.20(CF.sub.2O).sub.16CF.sub.2CH.sub.2CH.sub.2CH.sub.2Si[CH.sub.2CH.sub.2CH.sub.2CH.sub.2Si(OCH.sub.3).sub.3].sub.3

Synthesis Example 18

[0260] To a 100-mL four-necked flask equipped with a reflux condenser, a thermometer and a stirrer, 10.0 g of perfluoropolyether group-containing trichlorosilane compound (E) having trichlorosilane at a terminal, synthesized in Synthesis Example 5, and 12 g of 1,3-bis(trifluoromethyl)benzene were added and stirred at 5 C. under a nitrogen stream for 30 minutes. Subsequently, 16.5 ml of a solution containing 1.0 mol/L hexenyl magnesium bromide in tetrahydrofuran was added thereto, and thereafter the resultant was heated to room temperature, and stirred at that temperature for 12 hours. Thereafter, the resultant was cooled to 5 C., 6 ml of methanol was added thereto, thereafter 20 g of perfluorohexane was added thereto and the mixture was stirred for 30 minutes, and thereafter a perfluorohexane layer was collected by separation with a separating funnel. Subsequently, the volatile content was distilled off under reduced pressure, thereby providing 10.1 g of the following perfluoropolyether group-containing hexenyl compound (R) having a hexenyl group at a terminal.

[0261] Perfluoropolyether Group-Containing Hexenyl Compound (R):

CF.sub.3O(CF.sub.2CF.sub.2O).sub.20(CF.sub.2O).sub.16CF.sub.2CH.sub.2CH.sub.2CH.sub.2Si(CH.sub.2CH.sub.2CH.sub.2CH.sub.2CHCH.sub.2).sub.3

Synthesis Example 19

[0262] To a 100-mL four-necked flask equipped with a reflux condenser, a thermometer and a stirrer, 6.0 g of perfluoropolyether group-containing hexenyl compound (R) having a hexenyl group at a terminal, synthesized in Synthesis Example 18, 9 g of 1,3-bis(trifluoromethyl)benzene, and 1.5 g of trichlorosilane were added and stirred at 5 C. under a nitrogen stream for 30 minutes. Subsequently, 0.06 ml of a solution containing 2% of a Pt complex of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane in xylene was added thereto, and thereafter the resultant was heated to 60 C., and stirred at that temperature for 2 hours. Thereafter, the volatile content was distilled off under reduced pressure, thereby providing 6.1 g of the following perfluoropolyether group-containing trichlorosilane compound (S) having trichlorosilane at a terminal.

[0263] Perfluoropolyether Group-Containing Trichlorosilane Compound (S):

CF.sub.3O(CF.sub.2CF.sub.2O).sub.20(CF.sub.2).sub.16CF.sub.2CH.sub.2CH.sub.2CH.sub.2Si(CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2SiCl.sub.3).sub.3

Synthesis Example 20

[0264] To a 100-mL four-necked flask equipped with a reflux condenser, a thermometer and a stirrer, 6.1 g of perfluoropolyether group-containing trichlorosilane compound (S) having trichlorosilane at a terminal, synthesized in Synthesis Example 19, and 9 g of 1,3-bis(trifluoromethyl)benzene were added and stirred at 50 C. under a nitrogen stream for 30 minutes. Subsequently, a mixed solution of 0.25 g of methanol and 8.3 g of trimethyl orthoformate was added, and thereafter the resultant was heated to 55 C., and stirred at that temperature for 3 hours. Thereafter, the volatile content was distilled off under reduced pressure, thereby providing 6.2 g of the following perfluoropolyether group-containing silane compound (T) having a trimethoxysilyl group at a terminal.

[0265] Perfluoropolyether Group-Containing Silane Compound (T):

CF.sub.3O(CF.sub.2CF.sub.2O).sub.20(CF.sub.2O).sub.16CF.sub.2CH.sub.2CH.sub.2CH.sub.2Si[CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2Si(OCH.sub.3).sub.3].sub.3

Synthesis Example 21

[0266] To a 100-mL four-necked flask equipped with a reflux condenser, a thermometer and a stirrer, 13 g of a perfluoropolyether-modified allyl compound represented by an average compositional formula CF.sub.3O(CF.sub.2CF.sub.2O).sub.21(CF.sub.2O).sub.29CF.sub.2CH.sub.2CHCH.sub.2, 15.6 g of 1,3-bis(trifluoromethyl)benzene, and 1.3 g of trichlorosilane were added and stirred at 5 C. under a nitrogen stream for 30 minutes. Subsequently, 0.10 ml of a solution containing 2% of a Pt complex of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane in xylene was added thereto, and thereafter the resultant was heated to 60 C., and stirred at that temperature for 4 hours. Thereafter, the volatile content was distilled off under reduced pressure, thereby providing 13.2 g of perfluoropolyether group-containing trichlorosilane compound (U) having trichlorosilane at a terminal, represented by the following formula.

[0267] Perfluoropolyether Group-Containing Trichlorosilane Compound (U):

CF.sub.3O(CF.sub.2CF.sub.2O).sub.21(CF.sub.2O).sub.29CF.sub.2CH.sub.2CH.sub.2CH.sub.2SiCl.sub.3

Synthesis Example 22

[0268] To a 100-mL four-necked flask equipped with a reflux condenser, a thermometer and a stirrer, 13.2 g of perfluoropolyether group-containing trichlorosilane compound (U) having trichlorosilane at a terminal, synthesized in Synthesis Example 21, and 15.6 g of 1,3-bis(trifluoromethyl)benzene were added and stirred at 5 C. under a nitrogen stream for 30 minutes. Subsequently, 17.8 ml of a solution containing 1 mol/L allyl magnesium chloride in tetrahydrofuran was added thereto, and thereafter the resultant was heated to room temperature, and stirred at that temperature for 12 hours. Thereafter, the resultant was cooled to 5 C., 7.1 ml of methanol was added thereto, thereafter 30 g of perfluorohexane was added thereto and the mixture was stirred for 30 minutes, and thereafter a perfluorohexane layer was collected by separation with a separating funnel. Subsequently, the volatile content was distilled off under reduced pressure, thereby providing 13.0 g of the following perfluoropolyether group-containing allyl compound (V) having an allyl group at a terminal.

[0269] Perfluoropolyether Group-Containing Allyl Compound (V):

CF.sub.3O(CF.sub.2CF.sub.2O).sub.21(CF.sub.2O).sub.29CF.sub.2CH.sub.2CH.sub.2CH.sub.2Si(CH.sub.2CHCH.sub.2).sub.3

Synthesis Example 23

[0270] To a 100-mL four-necked flask equipped with a reflux condenser, a thermometer and a stirrer, 12.5 g of perfluoropolyether group-containing allyl compound (V) having an allyl group at a terminal, synthesized in Synthesis Example 22, 17.3 g of 1,3-bis(trifluoromethyl)benzene, and 2.5 g of trichlorosilane were added and stirred at 5 C. under a nitrogen stream for 30 minutes. Subsequently, 0.17 ml of a solution containing 2% of a Pt complex of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane in xylene was added thereto, and thereafter the resultant was heated to 60 C., and stirred at that temperature for 2 hours. Thereafter, the volatile content was distilled off under reduced pressure, thereby providing 12.6 g of the following perfluoropolyether group-containing trichlorosilane compound (W) having trichlorosilane at a terminal.

[0271] Perfluoropolyether Group-Containing Trichlorosilane Compound (W):

CF.sub.3O(CF.sub.2CF.sub.2O).sub.21(CF.sub.2O).sub.29CF.sub.2CH.sub.2CH.sub.2CH.sub.2Si(CH.sub.2CH.sub.2CH.sub.2SiCl.sub.3).sub.3

Synthesis Example 24

[0272] To a 100-mL four-necked flask equipped with a reflux condenser, a thermometer and a stirrer, 12.6 g of perfluoropolyether group-containing trichlorosilane compound (W) having trichlorosilane at a terminal, synthesized in Synthesis Example 23, and 17 g of 1,3-bis(trifluoromethyl)benzene were added and stirred at 50 C. under a nitrogen stream for 30 minutes. Subsequently, a mixed solution of 0.4 g of methanol and 13.3 g of trimethyl orthoformate was added, and thereafter the resultant was heated to 55 C., and stirred at that temperature for 3 hours. Thereafter, the volatile content was distilled off under reduced pressure, thereby providing 12.7 g of the following perfluoropolyether group-containing silane compound (X) having a trimethoxysilyl group at a terminal.

[0273] Perfluoropolyether Group-Containing Silane Compound (X):

CF.sub.3O(CF.sub.2CF.sub.2O).sub.21(CF.sub.2O).sub.29CF.sub.2CH.sub.2CH.sub.2CH.sub.2Si[CH.sub.2CH.sub.2CH.sub.2Si(OCH.sub.3).sub.3].sub.3

Example 1

[0274] Compound (D) obtained in Synthesis Example 4 was dissolved in hydrofluoroether (NOVEC HFE 7200 manufactured by 3M) so that the concentration was 20% by weight, thereby preparing surface-treating agent 1.

[0275] Surface-treating agent 1 prepared above was vapor-deposited on chemically reinforced glass (Gorilla glass having a thickness of 0.7 mm, manufactured by Corning Incorporated). Such a vacuum deposition treatment was at a pressure of 3.010.sup.3 Pa. First, silicon dioxide at a thickness of 7 nm was deposited on the surface of the chemically reinforced glass to form a silicon dioxide film, and subsequently 2 mg of a surface-treating agent (namely, containing 0.4 mg of compound (D)) per the chemically reinforced glass (55 mm100 mm) was deposited. Thereafter, the chemically reinforced glass with a deposited film was left to still stand under an atmosphere of a temperature of 20 C. and a humidity of 65% for 24 hours. Thus, the deposited film was cured, thereby forming a surface-treating layer.

Example 2

[0276] A surface-treating agent was prepared and a surface-treating layer was formed in the same manner as in Example 1 except that compound (H) was used instead of compound (D).

Examples 3 to 4

[0277] Each surface-treating agent was prepared and each surface-treating layer was formed in the same manner as in Example 1 except that compound (K) or compound (N) was used instead of compound (D).

Examples 5 to 6

[0278] Each surface-treating agent was prepared and each surface-treating layer was formed in the same manner as in Example 1 except that compound (Q) or compound (T) was used instead of compound (D).

Example 7

[0279] A surface-treating agent was prepared and a surface-treating layer was formed in the same manner as in Example 1 except that compound (X) was used instead of compound (D).

Comparative Example 1

[0280] A surface-treating agent was prepared and a surface-treating layer was formed in the same manner as in Example 1 except that the following control compound 1 was used instead of compound (D).

[0281] Control Compound 1

CF.sub.3CF.sub.2CF.sub.2O(CF.sub.2CF.sub.2CF.sub.2O).sub.20CF.sub.2CF.sub.2CH.sub.2OCH.sub.2CH.sub.2CH.sub.2Si[CH.sub.2CH.sub.2CH.sub.2Si(OCH.sub.3).sub.3].sub.3

Comparative Example 2

[0282] A surface-treating agent was prepared and a surface-treating layer was formed in the same manner as in Example 1 except that the following control compound 2 was used instead of compound (D).

[0283] Control Compound 2

CF.sub.3O(CF.sub.2CF.sub.2O).sub.20(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

(Evaluation of UV Resistance)

[0284] The static contact angle of water with each of the surface-treating layers formed in Examples and Comparative Examples was measured before and after UV irradiation. UV irradiation was conducted by using a UVB-313 lamp (manufactured by Q-Lab Corporation, irradiance at 310 nm: 0.63 W/m.sup.2) at a distance of 5 cm between the lamp and the surface-treating layer. The static contact angle of water was measured with respect to 1 L of water by using a contact angle measurement apparatus (manufactured by Kyowa Interface Science, Inc.)

[0285] First, the static contact angle of water with each of the formed surface-treating layers before UV irradiation (UV irradiation time: 0 hours) was measured as the initial evaluation. Thereafter, the static contact angle of water with each of the formed surface-treating layers after UV irradiation for a predetermined time was measured. The evaluation of UV resistance was performed for a cumulative irradiation time of 96 hours. The results are shown in Table 1.

TABLE-US-00001 TABLE 1 Cumulative UV Contact angle (degrees) irradiation Comparative Comparative time (hours) Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 1 Example 2 0 116 116 116 116 116 115 116 116 116 24 116 115 116 116 115 115 115 115 116 48 115 115 115 115 115 115 115 104 108 72 115 115 115 115 114 114 115 94 97 96 115 115 115 115 114 114 114 86 84

(Evaluation of Friction Durability)

[0286] Each of the surface-treating layers formed in Examples 1 to 7 and Comparative Examples 1 to 2 was subjected to the following friction durability test as the evaluation of durability in practical use.

[0287] The static contact angle of water of the surface of the surface-treating layer of which the surface had not still contacted with anything after formation thereof (number of times of friction: zero), was measured as the initial evaluation.

[0288] Thereafter, a sample article on which each of the surface-treating layers was formed was horizontally disposed, the following friction block was brought into contact with the surface of each of the surface-treating layers (the contact surface had a circular shape having a diameter of 1 cm), a load of 5 N was applied thereonto, and thereafter the friction block was allowed to reciprocate at a rate of 40 mm/sec with the load being applied. The friction block was allowed to reciprocate at most 4000 times, and the static contact angle of water (degrees) was measured every a number of times of reciprocation (number of times of friction) of 1000. The test was stopped when the measurement value of the static contact angle of water was decreased to less than 60 degrees. The static contact angle of water was measured in the same manner as in the evaluation of UV resistance. The results are shown in Table 2 (the sign - in the Table means no measurement).

[0289] Friction Block

[0290] A silicone rubber product shown below, the surface (diameter: 1 cm) of which was covered with a cotton impregnated with artificial sweat having the following composition, was used as a friction block.

[0291] Composition of Artificial Sweat

[0292] Anhydrous disodium hydrogen phosphate: 2 g

[0293] Sodium chloride: 20 g

[0294] 85% Lactic acid: 2 g

[0295] Histidine hydrochloride: 5 g

[0296] Distilled water: 1 kg

[0297] Silicone Rubber Product

[0298] Silicone rubber plug SR-51 manufactured by Tigers Polymer Corporation, processed into a cylinder shape having a diameter of 1 cm and a thickness of 1 cm.

TABLE-US-00002 TABLE 2 Number of times of Contact angle (degrees) friction Comparative Comparative (times) Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 1 Example 2 0 116 116 116 116 115 115 116 116 116 1000 109 112 111 113 110 109 113 89 105 2000 104 108 107 111 106 102 110 80 89 3000 96 102 101 107 101 96 105 58 62 4000 92 99 95 103 94 86 101 54

[0299] It was found from the results in Table 1 that the surface-treating layers of Examples 1 to 7 were suppressed in a decrease in the contact angle due to UV irradiation as compared with the surface-treating layers of Comparative Examples 1 and 2. The reason for this was considered because the surface-treating layers formed in Examples 1 to 7 were suppressed in decomposition of the surface-treating layers due to UV irradiation. In other words, it has been confirmed that the surface-treating layer formed by use of the perfluoropolyether group-containing silane compound of the present invention, having a linker made of only an alkylene group, is enhanced in UV resistance.

[0300] It was found from the results in Table 2 that the surface-treating layers of Examples 1 to 7 were suppressed in a decrease in the contact angle and had excellent friction durability. The reason for this was considered because the surface-treating layers of Examples 1 to 7 were suppressed in degradation due to chemicals and furthermore the surface-treating layers were enhanced in friction resistance due to PFPE chains closely oriented owing to a surface-treating agent having an alkylene group as a linker (namely, X). In other words, it has been confirmed that the surface-treating layer formed by use of the perfluoropolyether group-containing silane compound of the present invention, having a linker made of only an alkylene group, is enhanced in chemical resistance and abrasion resistance.

[0301] The e/f ratio of compound (H) contained in the surface-treating agent in Example 2 was 1.25, and the e/f ratio of compound (X) contained in the surface-treating agent of Example 7 was 0.72. It was considered that compound (X) contained in the surface-treating agent in Example 7 was lower in the content of a (CF.sub.2CF.sub.2O) unit than the content of a (CF.sub.2O) unit and therefore the surface-treating layer formed was easily slid to result in a further enhancement in friction durability.

INDUSTRIAL APPLICABILITY

[0302] The present invention can be suitably utilized for forming a surface-treating layer on surfaces of various base materials, in particular, on a surface of an optical member required to have permeability.