SURFACE TREATMENT AGENT

Abstract

A surface-treating agent containing (1) at least one perfluoro(poly)ether group containing silane compound of any of the formulae (A1), (A2), (B1), (B2), (C1), (C2), (D1) and (D2):

##STR00001##

and (2) a fluorine containing oil of the general formula (O):

Rf.sup.1-PFPE-Rf.sup.2(O)

wherein: each of the symbols are as defined herein. A content of the fluorine containing oil having a molecular weight of 2.0 or more times higher than the number average molecular weight of the fluorine-containing oils among the fluorine containing oil of the formula (O) is 10 mol % or less.

Claims

1. A surface-treating agent comprising (1) at least one perfluoro(poly)ether group containing silane compound of any of the formulae (A1), (A2), (B1), (B2), (C1), (C2), (D1) and (D2): ##STR00020## wherein: PFPE is each independently at each occurrence a group of the formula:
(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, b, c and d are each independently an integer of 0-200, the sum of a, b, c and d is at least one, and the occurrence order of the respective repeating units in parentheses with the subscript a, b, c or d is not limited in the formula; 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 hydroxyl group or a hydrolyzable group; R.sup.2 is each independently at each occurrence a hydrogen atom or an alkyl group having 1-22 carbon atoms; 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; n1 is, independently per a unit (SiR.sub.n1R.sup.2.sub.3n1), an integer of 0-3; at least one n1 is an integer of 1-3 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; is each independently an integer of 1-9; is each independently an integer of 1-9; X.sup.5 is each independently a single bond or a 2-10 valent organic group; is each independently an integer of 1-9; is each independently an integer of 1-9; X.sup.7 is each independently a single bond or a 2-10 valent organic group; is each independently an integer of 1-9; is each independently an integer of 1-9; R.sup.a is each independently at each occurrence Z.sup.1SiR.sup.71.sub.p1R.sup.72.sub.q1R.sup.73.sub.r1; Z.sup.1 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.sup.1 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; p1 is each independently at each occurrence an integer of 0-3; q1 is each independently at each occurrence an integer of 0-3; r1 is each independently at each occurrence an integer of 0-3; at least one q1 is an integer of 1-3 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; k1 is each independently at each occurrence an integer of 1-3; l1 is each independently at each occurrence an integer of 0-2; m1 is each independently at each occurrence an integer of 0-2; the sum of k1, l1 and m1 is 3 in each unit in parentheses with the subscript ; X.sup.9 is each independently a single bond or a 2-10 valent organic group; is each independently an integer of 1-9; is each independently an integer of 1-9; R.sup.d is each independently at each occurrence ZCR.sup.81.sub.p2R.sup.82.sub.q2R.sup.83.sub.r2; Z.sup.81 is each independently at each occurrence an oxygen atom or a divalent organic group; R.sup.d is each independently at each occurrence R.sup.d; R.sup.81 has the same definition as that of R.sup.d; in R.sup.d, the number of C atoms which are straightly linked via the Z.sup.2 group is up to five; R.sup.82 is each independently at each occurrence YSiR.sup.85.sub.n2R.sup.86.sub.3n2; Y is each independently at each occurrence a divalent organic group; R.sup.85 is each independently at each occurrence a hydroxyl group or a hydrolyzable group; R.sup.86 is each independently at each occurrence a hydrogen atom or a lower alkyl group; n2 is an integer of 1-3 independently per unit (YSiR.sup.85.sub.n2R.sup.86.sub.3n2); in formulae (D1) and (D2), at least one n2 is an integer of 1-3; R.sup.83 is each independently at each occurrence a hydrogen atom or a lower alkyl group; p2 is each independently at each occurrence an integer of 0-3; q2 is each independently at each occurrence an integer of 0-3; r2 is each independently at each occurrence an integer of 0-3; R.sup.e is each independently at each occurrence YSiR.sup.85.sub.n2R.sup.86.sub.n2; R.sup.f is each independently at each occurrence a hydrogen atom or a lower alkyl group; k2 is each independently at each occurrence an integer of 0-3; l2 is each independently at each occurrence an integer of 0-3; and m2 is each independently at each occurrence an integer of 0-3; in formulae (D1) and (D2), at least one q2 is 2 or 3, or at least one l2 is 2 or 3; and (2) a fluorine containing oil of the general formula (O):
Rf.sup.1-PFPE-Rf.sup.2(O) wherein: Rf.sup.1 is each independently at each occurrence a C.sub.1-16 alkyl group which may be substituted by one or more fluorine atoms; Rf.sup.2 is a C.sub.1-16 alkyl group which may be substituted by one or more fluorine atoms, a fluorine atom or a hydrogen atom; PFPE is (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; a, b, c and d are each independently an integer of 0 or more and 300 or less, the sum of a, b, c and d is at least 1, and the occurrence order of the respective repeating units in parentheses with the subscript a, b, c or d is not limited in the formula, wherein a content of the fluorine containing oil having a molecular weight of 2.0 or more times higher than the number average molecular weight of the fluorine-containing oil among the fluorine containing oil of the formula (O) is 10 mol % or less.

2. The surface-treating agent according to claim 1 wherein the content of the fluorine containing oil having a molecular weight of 2.0 or more times higher than the number average molecular weight of the fluorine-containing oil among the fluorine containing oil of the formula (O) is 5 mol % or less.

3. The surface-treating agent according to claim 1 wherein a content of the fluorine containing oil having a molecular weight of 1.8 or more times higher than the number average molecular weight of the fluorine-containing oil among the fluorine containing oil of the formula (O) is 10 mol % or less.

4. The surface-treating agent according to claim 3 wherein the content of the fluorine containing oil having a molecular weight of 1.8 or more times higher than the number average molecular weight of the fluorine-containing oil among the fluorine containing oil of the formula (O) is 5 mol % or less.

5. The surface-treating agent according to claim 1 wherein a number average molecular weight of the fluorine containing oil is 1,500 or more and 30,000 or less.

6. The surface-treating agent according to claim 5 wherein the number average molecular weight of the fluorine containing oil is 2,000 or more and 10,000 or less.

7. A surface-treating agent comprising (1) at least one perfluoro(poly)ether group containing silane compound of any of the formulae (A1), (A2), (B1), (B2), (C1), (C2), (D1) and (D2): ##STR00021## wherein: PFPE is each independently at each occurrence a group of the formula:
(OC.sub.4F).sub.a(OC.sub.3F.sub.6).sub.b(OC.sub.2F.sub.4).sub.c(OCF.sub.2).sub.d wherein a, b, c and d are each independently an integer of 0-200, the sum of a, b, c and d is at least one, and the occurrence order of the respective repeating units in parentheses with the subscript a, b, c or d is not limited in the formula; 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 hydroxyl group or a hydrolyzable group; R.sup.2 is each independently at each occurrence a hydrogen atom or an alkyl group having 1-22 carbon atoms; 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; n1 is, independently per a unit (SiR.sub.n1R.sup.2.sub.3n1), an integer of 0-3; at least one n1 is an integer of 1-3 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; is each independently an integer of 1-9; is each independently an integer of 1-9; X.sup.5 is each independently a single bond or a 2-10 valent organic group; is each independently an integer of 1-9; is each independently an integer of 1-9; X.sup.7 is each independently a single bond or a 2-10 valent organic group; is each independently an integer of 1-9; is each independently an integer of 1-9; R.sup.a is each independently at each occurrence ZSiR.sup.71.sub.p1R.sup.72.sub.q1R.sup.73.sub.r1; Z.sup.1 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.sup.1 group is up to five; R.sup.72 is each independently at each occurrence a hydroxyl group or a hydrolyzable group; R.sup.n is each independently at each occurrence a hydrogen atom or a lower alkyl group; p1 is each independently at each occurrence an integer of 0-3; q1 is each independently at each occurrence an integer of 0-3; r1 is each independently at each occurrence an integer of 0-3; at least one q1 is an integer of 1-3 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; k1 is each independently at each occurrence an integer of 1-3; l1 is each independently at each occurrence an integer of 0-2; m1 is each independently at each occurrence an integer of 0-2; the sum of k1, l1 and m1 is 3 in each unit in parentheses with the subscript ; X.sup.9 is each independently a single bond or a 2-10 valent organic group; is each independently an integer of 1-9; is each independently an integer of 1-9; R.sup.d is each independently at each occurrence ZCR.sup.81.sub.p2R.sup.82.sub.q2R.sup.83.sub.r2; Z.sup.2 is each independently at each occurrence an oxygen atom or a divalent organic group; R.sup.81 is each independently at each occurrence R.sup.d; R.sup.d has the same definition as that of R.sup.d; in R.sup.d, the number of C atoms which are straightly linked via the Z.sup.2 group is up to five; R.sup.8 is each independently at each occurrence YSiR.sup.85.sub.n2R.sup.86.sub.3n2; Y is each independently at each occurrence a divalent organic group; R.sup.85 is each independently at each occurrence a hydroxyl group or a hydrolyzable group; R.sup.86 is each independently at each occurrence a hydrogen atom or a lower alkyl group; n2 is an integer of 1-3 independently per unit (YSiR.sup.85.sub.n2R.sup.86.sub.3n2); in formulae (D1) and (D2), at least one n2 is an integer of 1-3; R.sup.83 is each independently at each occurrence a hydrogen atom or a lower alkyl group; p2 is each independently at each occurrence an integer of 0-3; q2 is each independently at each occurrence an integer of 0-3; r2 is each independently at each occurrence an integer of 0-3; R.sup.e is each independently at each occurrence YSiR.sup.85.sub.n2R.sup.86.sub.n2; R.sup.f is each independently at each occurrence a hydrogen atom or a lower alkyl group; k2 is each independently at each occurrence an integer of 0-3; l2 is each independently at each occurrence an integer of 0-3; and m2 is each independently at each occurrence an integer of 0-3; in formulae (D1) and (D2), at least one q2 is 2 or 3, or at least one l2 is 2 or 3; and (2) a fluorine containing oil of the general formula (O):
Rf.sup.1-PFPE-Rf.sup.2(O) wherein: Rf.sup.1 is each independently at each occurrence a C.sub.1-16 alkyl group which may be substituted by one or more fluorine atoms; Rf.sup.2 is a C.sub.1-16 alkyl group which may be substituted by one or more fluorine atoms, a fluorine atom or a hydrogen atom; PFPE is (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; a, b, c and d are each independently an integer of 0 or more and 300 or less, the sum of a, b, c and d is at least 1, and the occurrence order of the respective repeating units in parentheses with the subscript a, b, c or d is not limited in the formula, wherein a content of the fluorine containing oil having a molecular weight of 5,000 or more in the fluorine containing oil of the formula (O) is 10 mol % or less.

8. The surface-treating agent according to claim 7 wherein the content of the fluorine containing oil having a molecular weight of 5,000 or more in the fluorine containing oil of the formula (O) is 5 mol % or less.

9. The surface-treating agent according to claim 1 wherein a dispersity of the fluorine containing oil is 1.00 or more and 1.20 or less.

10. The surface-treating agent according to claim 9 wherein the dispersity of the fluorine containing oil is 1.00 or more and 1.10 or less.

11. The surface-treating agent according to claim 1 wherein the number average molecular weight of the fluorine containing oil is 1,500 or more and 5,500 or less.

12. The surface-treating agent according to claim 1 wherein the fluorine containing oil is one or more compounds of the formula (O1) or (O2):
R.sup.21(OCF.sub.2CF.sub.2CF.sub.2).sub.bR.sup.22(O1)
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.dR.sup.22(O2) 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 (O1), b is an integer of 1 or more and 100 or less; in the formula (O2), 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.

13. The surface-treating agent according to claim 12 wherein the fluorine containing oil is one or more fluorine containing oils of the formula (O2), and the number average molecular weight of the fluorine containing oil is 1,500-5,500.

14. The surface-treating agent according to a claim 1 wherein Rf is a perfluoroalkyl group having 1-16 carbon atoms.

15. The surface-treating agent according to claim 1 wherein PFPE is a group of any of the following formulas (i) to (iv):
(OCF.sub.2CF.sub.2CF.sub.2).sub.b(i) wherein b is an integer of 1-200;
(OCF(CF.sub.3)CF.sub.2).sub.b(ii) wherein b is an integer of 1-200;
(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(iii) wherein a and b are each independently 0 or an integer of 1-30, c and d are each independently an integer of 1-200, 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; or
(R.sup.7R.sup.8).sub.f(iv) wherein R.sup.7 is OCF.sub.2 or OC.sub.2F.sub.4, R.sup.8 is a group selected from OC.sub.2F.sub.4, OC.sub.3F.sub.6 and OC.sub.4F.sub.8; and f is an integer of 2-100.

16. The surface-treating agent according to claim 1 wherein X.sup.1, X.sup.5, X.sup.7 and X.sup.9 are each independently a 2-4 valent organic group, , , and are each independently 1-3, and , , and are 1.

17. The surface-treating agent according to claim 1 wherein X.sup.1, X.sup.5, X.sup.7 and X.sup.9 are each independently a 2 valent organic group, , , and are 1, and , , and are 1.

18. The surface-treating agent according to claim 17 wherein X.sup.1, X.sup.5, X.sup.7 and X.sup.9 are each independently (R.sup.31).sub.p(X.sup.a).sub.q wherein: R.sup.31 is each independently 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.mSi(R.sup.33).sub.2 (wherein m is an integer of 1-100), CONR.sup.34, OCONR.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, 1 or 2; q is 0 or 1; at least one of p and q is 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.

19. The surface-treating agent according to claim 1 wherein X.sup.1, X.sup.5, X.sup.7 and X.sup.9 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.2OCF.sub.2CHFOCF.sub.2, CH.sub.2OCF.sub.2CHFOCF.sub.2CF.sub.2, CH.sub.2OCF.sub.2CHFOCF.sub.2CF.sub.2CF.sub.2, CH.sub.2OCH.sub.2CF.sub.2CF.sub.2OCF.sub.2, CH.sub.2OCH.sub.2CF.sub.2CF.sub.2OCF.sub.2CF.sub.2, CH.sub.2OCH.sub.2CF.sub.2CF.sub.2OCF.sub.2CF.sub.2CF.sub.2, CH.sub.2OCH.sub.2CF.sub.2CF.sub.2OCF(CF.sub.3)CF.sub.2OCF.sub.2, CH.sub.2OCH.sub.2CF.sub.2CF.sub.2OCF(CF.sub.3)CF.sub.2OCF.sub.2CF.sub.2, CH.sub.2OCH.sub.2CF.sub.2CF.sub.2OCF(CF.sub.3)CF.sub.2OCF.sub.2CF.sub.2CF.sub.2, CH.sub.2OCH.sub.2CHFCF.sub.2OCF.sub.2, CH.sub.2OCH.sub.2CHFCF.sub.2OCF.sub.2CF.sub.2, CH.sub.2OCH.sub.2CHFCF.sub.2OCF.sub.2CF.sub.2CF.sub.2, CH.sub.2OCH.sub.2CHFCF.sub.2OCF(CF.sub.3)CF.sub.2OCF.sub.2, CH.sub.2OCH.sub.2CHFCF.sub.2OCF(CF.sub.3)CF.sub.2OCF.sub.2CF.sub.2, CH.sub.2OCH.sub.2CHFCF.sub.2OCF(CF.sub.3)CF.sub.2OCF.sub.2CF.sub.2CF.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.5, (CH.sub.2).sub.6, (CH.sub.2).sub.2Si(CH.sub.3).sub.2(CH.sub.2).sub.2 CONH(CH.sub.2), CONH(CH.sub.2).sub.2, 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.2OCONH(CH.sub.2).sub.3, CH.sub.2OCONH(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.2O).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.2O(CH.sub.2).sub.3Si(CH.sub.3).sub.2(CH.sub.2).sub.2Si(CH.sub.3).sub.2(CH.sub.2).sub.2, CH.sub.2O(CH.sub.2).sub.3Si(CH.sub.3).sub.2(CH.sub.2).sub.2Si(CH.sub.3).sub.2CH(CH.sub.3), CH.sub.2O(CH.sub.2).sub.3Si(CH.sub.3).sub.2(CH.sub.2).sub.2Si(CH.sub.3).sub.2(CH.sub.2).sub.3, CH.sub.2O(CH.sub.2).sub.3Si(CH.sub.3).sub.2(CH.sub.2).sub.2Si(CH.sub.3).sub.2CH(CH.sub.3)CH.sub.2, OCH.sub.2, O(CH.sub.2).sub.3, OCFHCF.sub.2, ##STR00022##

20. The surface-treating agent according to claim 1 wherein X.sup.1 is OCFR.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.

21. The surface-treating agent according to claim 1 wherein X.sup.2 is (CH.sub.2).sub.s, and s is an integer of 0-2.

22. The surface-treating agent according to claim 1 wherein k1 is 3, and q1 is 3 in R.sup.a.

23. The surface-treating agent according to claim 1 wherein l2 is 3, and n2 is 3.

24. The surface-treating agent according to claim 1 wherein Y is a C.sub.1-6 alkylene group, (CH.sub.2).sub.gO(CH.sub.2).sub.h (wherein g is an integer of 0-6, and h is an integer of 0-6), or -phenylene-(CH.sub.2).sub.i (wherein i is an integer of 0-6).

25. The surface-treating agent according to claim 1 wherein X.sup.1, X.sup.5, X.sup.7 and X.sup.9 are each independently a 3-10 valent organic group.

26. The surface-treating agent according to claim 25 wherein X.sup.1, X.sup.5, X.sup.7 and X.sup.9 are each independently selected from the group consisting of: ##STR00023## wherein in each group, at least one of T is the following group attached to PFPE in the formulae (A1), (A2), (B1), (B2), (C1), (C2), (D1) and (D2): 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), CONH(CH.sub.2).sub.2, 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 ##STR00024## 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), (C2), (D1) and (D2), and if present, the others T are each independently a methyl group, a phenyl group, a alkoxy having 1-6 carbon atoms, or a radical scavenger group or an ultraviolet ray absorbing group, R.sup.41 is each independently 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 each independently a hydrogen atom, a C.sub.1-6 alkyl group or a C.sub.1-6 alkoxy group.

27. The surface-treating agent according to claim 1 wherein the perfluoro(poly)ether group containing silane compound is at least one compound of any of the formulae (A1) and (A2).

28. The surface-treating agent according to claim 1 wherein the perfluoro(poly)ether group containing silane compound is at least one compound of any of the formulae (B1) and (B2).

29. The surface-treating agent according to claim 1 wherein the perfluoro(poly)ether group containing silane compound is at least one compound of any of the formulae (C1) and (C2).

30. The surface-treating agent according to claim 1 wherein the perfluoro(poly)ether group containing silane compound is at least one compound of any of the formulae (D1) and (D2).

31. The surface-treating agent according to claim 1 containing the fluorine containing oil at 5-95% by weight with respect to the total of the perfluoro(poly)ether group containing silane compound and the fluorine containing oil.

32. The surface-treating agent according to claim 1 further comprising one or more other components selected form a silicone oil and a catalyst.

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

34. The surface-treating agent according to claim 1 which is used as an antifouling-coating agent or a water-proof coating agent.

35. The surface-treating agent according to claim 1 for vacuum deposition.

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

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

38. The article having a haze value of 0.3 or less.

39. The article according to claim 37 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 37 wherein the article is an optical member.

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

43. The surface-treating agent according to claim 6 wherein the content of the fluorine containing oil in the surface treating agent is 5-90% by mass with respect to the total of the perfluoro(poly)ether group containing silane compound and the fluorine containing oil.

Description

EXAMPLES

[0448] 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, all chemical formulae described below mean an average composition.

[0449] Compound (A) and Compound (B) were used as a perfluoro(poly)ether group containing silane compound.

##STR00019##

wherein m is an integer of 1-6.

[0450] Each of three perfluoropolyether compounds (Compounds (C)-(E)) having different molecular weight distribution were used as a the fluorine containing oil.

Structure:

[0451]
CF.sub.3O(CF.sub.2O).sub.p(CF.sub.2CF.sub.2O).sub.qCF.sub.3

wherein p and q is given values.

[0452] Compound (C)

[0453] Compound (C) is obtained as a fraction at 194 C.-320 C. by molecular-distilling FOMBLIN M03 (manufactured by Solvay Specialty Polymers Japan K.K.) under 60-70 Pa.

[0454] Compound (D)

[0455] FOMBLIN M03 (manufactured by Solvay Specialty Polymers Japan K.K.)

[0456] Compound (E)

[0457] FOMBLIN Z03 (manufactured by Solvay Specialty Polymers Japan K.K.)

[0458] Compound (F)

[0459] 4:1 mixture of Compound (C) and Compound (D)

[0460] Compound (G) 1:1 mixture of Compound (C) and Compound (D)

[0461] Compound (H)

[0462] 3:7 mixture of Compound (C) and Compound (D)

[0463] With respect to Compounds (C)-(H), the weight average molecular weight (Mw), number average molecular weight (Mn) and dispersity (Mw/Mn) were measured by gel permeation chromatography (GPC). The measurement of GPC were performed under the following conditions. Mw, Mn, Mw/Mn and the contents of the fluorine containing oil having x times Mn are shown in Table 1.

[0464] Equipment: GPCmax (manufactured by HPLC system: Malvern Instruments)

[0465] Mobile phase: Mixed solvent of AK-225 (manufactured by Asahi Glass Co., Ltd, ASAHIKLIN AK-225) and hexafluoroisopropanol (HFIP)

(AK-225/HFIP=90/10 (volume ratio))

[0466] Analytical column: Two Shodex KF-806L were connected in series.

[0467] Standard sample for measurement of molecular weight: Three perfluoropolyether compounds having Mn of 1000-10000 Detector:

[0468] Mobile phase flow rate: 0.7 mL/min

[0469] Column temperature: 30 C.

TABLE-US-00001 TABLE 1 Content of compounds Content of compounds having a molecular having a molecular weight more than x weight of 5000 or times Mn (mol %) Mw Mn Mw/Mn more (mol %) x = 3.0 x = 2.0 x = 1.8 Compound 3,087 2,904 1.063 2.7 0.8 1.1 2.0 (C) Compound 4,400 3,026 1.432 12.7 7.5 10.5 11.5 (D) Compound 4,411 3,275 1.347 17.1 7.4 11.3 12.8 (E) Compound 3,075 3,506 1.140 8.8 0.9 2.4 6.6 (F) Compound 3,098 3,665 1.183 10.3 2.1 4.2 7.1 (G) Compound 3,123 3,839 1.230 12.6 3.6 6.1 8.2 (H)

[0470] Preparation of the Surface Treating Agent:

Example 1

[0471] Compound (A) and Compound (C) were dissolved in hydrofluoroether (manufactured by 3M Company, Novec HFE7200) at the mass ratio of 2:1 such that concentration (the total of Compound (A) and Compound (C)) was 0.1 wt % to prepare the surface treating agent 1.

Example 2

[0472] Compound (A) and Compound (C) were dissolved in hydrofluoroether (manufactured by 3M Company, Novec HFE7200) at the mass ratio of 1:1 such that concentration (the total of Compound (A) and Compound (C)) was 0.1 wt % to prepare the surface treating agent 2.

Example 3

[0473] Compound (B) and Compound (C) were dissolved in hydrofluoroether (manufactured by 3M Company, Novec HFE7200) at the mass ratio of 1:1 such that concentration (the total of Compound (B) and Compound (C)) was 0.1 wt % to prepare the surface treating agent 3.

Example 4

[0474] Compound (A) and Compound (F) were dissolved in hydrofluoroether (manufactured by 3M Company, Novec HFE7200) at the mass ratio of 1:1 such that concentration (the total of Compound (A) and Compound (F)) was 0.1 wt % to prepare the surface treating agent 4.

Example 5

[0475] Compound (A) and Compound (G) were dissolved in hydrofluoroether (manufactured by 3M Company, Novec HFE7200) at the mass ratio of 1:1 such that concentration (the total of Compound (A) and Compound (G)) was 0.1 wt % to prepare the surface treating agent 5.

Example 6

[0476] Compound (A) and Compound (H) were dissolved in hydrofluoroether (manufactured by 3M Company, Novec HFE7200) at the mass ratio of 1:1 such that concentration (the total of Compound (A) and Compound (H)) was 0.1 wt % to prepare the surface treating agent 6.

Comparative Example 1

[0477] Compound (A) and Compound (D) were dissolved in hydrofluoroether (manufactured by 3M Company, Novec HFE7200) at the mass ratio of 1:1 such that concentration (the total of Compound (A) and Compound (D)) was 0.1 wt % to prepare the surface treating agent 7.

Comparative Example 2

[0478] Compound (A) and Compound (E) were dissolved in hydrofluoroether (manufactured by 3M Company, Novec HFE7200) at the mass ratio of 1:1 such that concentration (the total of Compound (A) and Compound (E)) was 0.1 wt % to prepare the surface treating agent 8.

[0479] Formation of the surface treating layer (spray treatment):

[0480] Next, Surface treating agents 1-5 above prepared was uniformly spray-coated on a chemical strengthening glass (Gorilla glass manufactured by Corning Incorporated; thickness: 0.7 mm) by using the commercial spray coating equipment equipped with a two-fluid nozzle. The surface of the chemical strengthening glass was subjected to a plasma treatment using an atmospheric pressure plasma generator just prior to spray coating. A coating amount of the surface-treating agent was 0.2 m1 per one plate of chemical strengthening glass (55 mm100 mm). Then, the chemical strengthening glass having the spray treated layer was stood under an atmosphere where temperature is 20 C. and humidity is 65% for 48 hours. Thus, the spray treated layer was cured and the surface-treating layer was formed.

[0481] Evaluation

[0482] Evaluation of Friction Durability

[0483] A static water contact angle of the surface-treating layers formed on the surface of the base material from the surface treating agents 1-8 was measured. The static water contact angle was measured for 1 L of water by using a contact angle measuring instrument (manufactured by KYOWA INTERFACE SCIENCE Co., Ltd.).

[0484] Firstly, as an initial evaluation, the static water contact angle of the surface-treating layer of which the surface had not still contacted with anything after formation thereof was measured (the number of rubbing is zero).

[0485] Then, as an evaluation of the friction durability, a steel wool friction durability evaluation was performed. Specifically, the base material on which the surface-treating layer was formed was horizontally arranged, and then, a steel wool (grade No. 0000, dimensions: 5 mm10 mm10 mm) was contacted with the exposed surface of the surface-treating layer and a load of 1000 gf was applied thereon. Then, the steel wool was shuttled while applying the load at the rate 140 mm/sec. The static water contact angle was measured per 1,000 times. The evaluation was stopped when the measured value of the contact angle became to be less than 100 degree. The number of reciprocation is shown in the following table at the time of becoming the contact angle less than 100 degree.

[0486] Evaluation of Haze value

[0487] With respect to the surface treating layers formed on the surface of the base material from the surface treating agents 1-8, haze values were measured by Haze meter (Manufactured by NIPPON DENSHOKU INDUSTRIES CO., LTD NDH-7000). The results are shown in Table 2.

TABLE-US-00002 TABLE 2 Friction Haze Mixture durability value ratio (times) (%) Example 1 Compound (A)/ 2:1 20,000 0.18 Compound (C) Example 2 Compound (A)/ 1:1 16,000 0.17 Compound (C) Example 3 Compound (B)/ 1:1 9,000 0.20 Compound (C) Example 4 Compound (A)/ 1:1 16,000 0.19 Compound (F) Example 5 Compound (A)/ 1:1 15,000 0.20 Compound (G) Example 6 Compound (A)/ 1:1 14,000 0.26 Compound (H) Comparative Compound (A)/ 1:1 7,000 0.40 Example 1 Compound (D) Comparative Compound (A)/ 1:1 8,000 0.30 Example 2 Compound (E)

[0488] From table 2, in Examples 1-3 using the surface treating agent containing substantively no the fluorine containing oil having higher molecular weight, it was confirmed that haze value was lower than that in Comparative Examples 1-2. In Examples 1-3 using the surface treating agent containing substantively no the fluorine containing oil having higher molecular weight, it was confirmed that friction durability was higher than that in Comparative Examples 1-2. In particular, it was confirmed that the surface treating layer in Example 1 has lower haze value and higher friction durability.

INDUSTRIAL APPLICABILITY

[0489] 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.