SILANE COMPOUND CONTAINING PERFLUORO(POLY)ETHER GROUP

Abstract

The present invention provides a perfluoro(poly)ether group containing silane compound of

(Rf-PFPE).sub.X(CR.sup.a.sub.kR.sup.b.sub.lR.sup.c.sub.m).sub.(1a)

(R.sup.c.sub.mR.sup.b.sub.lR.sup.a.sub.kC).sub.XPFPE-X(CR.sup.a.sub.kR.sup.b.sub.lR.sup.c.sub.m).sub.(1b)

wherein the symbols are as defined in the description.

Claims

1. A perfluoro(poly)ether group containing silane compound of formula (1a):
(Rf-PFPE).sub.X(CR.sup.a.sub.kR.sup.b.sub.lR.sup.c.sub.m).sub.(1a) wherein: 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; 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 5 or more, and the occurrence order of the respective repeating units in parentheses with the subscript a, b, c or d is not limited in the formula; PFPE binds to Rf via oxygen atom at its left end and binds to X via carbon atom at its right end in formula (1a): X is each independently the following divalent organic group; a C.sub.1-20 alkylene group, R.sup.31X.sup.cR.sup.31, or wherein R.sup.31 is each independently a single bond, or (CH.sub.2).sub.s (wherein s is an integer of 1-20), with the proviso that at least one of R.sup.31 is not a single bond; X.sup.c is O, CONR.sup.34, or OCONR.sup.34, wherein R.sup.34 is each independently at each occurrence a hydrogen atom or a C.sub.1-6 alkyl group: is 1; is 1; R.sup.a is each independently at each occurrence ZCR.sup.1.sub.pR.sup.2.sub.qR.sup.3.sub.r; Rb is each independently at each occurrence YSiR.sup.5.sub.nR.sup.6.sub.3-n; Y is each independently at each occurrence 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); R.sup.5 is each independently at each occurrence a hydroxyl group or OR, OCOR, ONC(R).sub.2, N(R).sub.2, NHR, halogen (wherein R is a substituted or non-substituted alkyl group having 1-4 carbon atoms); R.sup.6 is each independently at each occurrence a hydrogen atom or a lower alkyl group; n is an integer of 1-3 independently per unit YSiR.sup.5.sub.nR.sup.6.sub.3-n; k is 0; l is 3; and m is 0.

2. (canceled)

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

4. The perfluoro(poly)ether group containing silane compound according to claim 1 wherein PFPE is a group of any of the following formulae (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.2CF.sub.2).sub.a(OCF.sub.2CF.sub.2CF.sub.2).sub.b(OCF.sub.2CF.sub.2CF.sub.2).sub.c(OCF.sub.2).sub.d(iii) wherein a and b are each independently an integer of 0-30, c and d are each independently an integer of 1-200, the sum of a, b, c and d is 5 or more, and the occurrence order of the respective repeating units in parentheses with the subscript a, b, c or d is not limited in the formula; or
(OC.sub.2F.sub.4R.sup.8).sub.n(iv) wherein R.sup.8 is a group selected from OC.sub.2F.sub.4, OC.sub.3F.sub.6 and OC.sub.4F.sub.8, or a combination of 2 or 3 groups independently selected from these groups, and the sum of OC.sub.2F.sub.4, OC.sub.3F.sub.6 and OC.sub.4F.sub.8 is 5 or more; and n is an integer of 2-100.

5. (canceled)

6. (canceled)

7. The perfluoro(poly)ether group containing silane compound according to claim 1 wherein X is 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.2).sub.2, (CH.sub.2).sub.3, (CH.sub.2).sub.4, (CH.sub.2).sub.5, (CH.sub.2).sub.6, CONH(CH.sub.2).sub.3, CON(CH.sub.3)(CH.sub.2).sub.3, CONH(CH.sub.2).sub.6, CONH(CH.sub.3)(CH.sub.2).sub.6, CH.sub.2OCONH(CH.sub.2).sub.3, and CH.sub.2OCONH(CH.sub.2).sub.6.

8. (canceled)

9. (canceled)

10. (canceled)

11. The perfluoro(poly)ether group containing silane compound according to claim 1 wherein an average molecular weight of the Rf-PFPE moiety is 500-30,000.

12. The perfluoro(poly)ether group containing silane compound according to claim 1 having an average molecular weight of 2,000-32,000.

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

14. The surface-treating agent according to claim 13 further comprising one or more components selected form a fluorine-containing oil, a silicone oil and a catalyst.

15. The surface-treating agent according to claim 14 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.dR.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 constitutes 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.

16. The surface-treating agent according to claim 14 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.bR.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.dR.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.

17. The surface-treating agent according to claim 16 comprising at least one compound of the formula (3b).

18. The surface-treating agent according to claim 16 wherein a mass ratio of the perfluoro(poly)ether group containing silane compound of the formula (1a) and the compound of the formula (3b) is 4:1-1:4.

19. The surface-treating agent according to claim 16 wherein the compound of the formula (3a) has a number average molecular weight of 2,000-8,000.

20. The surface-treating agent according to claim 16 wherein the compound of the formula (3b) has a number average molecular weight of 2,000-30,000.

21. The surface-treating agent according to claim 16 wherein the compound of the formula (3b) has a number average molecular weight of 8,000-30,000.

22. The surface-treating agent according to claim 13 further comprising a solvent.

23. The surface-treating agent according to claim 13 which is used as an antifouling-coating agent or a water-proof coating agent.

24. The surface-treating agent according to claim 13 for vacuum deposition.

25. A pellet containing the surface-treating agent according to claim 13.

26. 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.

27. The article according to claim 26 wherein the article is an optical member.

28. The article according to claim 26 wherein the article is a display.

29. 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 13.

Description

EXAMPLES

[0192] 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 the occurrence order of the four repeating units (CF.sub.2O), (CF.sub.2CF.sub.2O), (CF(CF.sub.3)CF.sub.2O), (CF.sub.2CF.sub.2CF.sub.2O) and (CF.sub.2CF.sub.2CF.sub.2CF.sub.2O) constituting the perfluoropolyether of is not limited in Examples.

Synthesizing Example 1

[0193] To a four necked flask of 100 mL provided with a reflux condenser, a thermometer and a stirrer, NaH (4.62 g), and tetrabutylammonium bromide (0.41 g) were added. Then, 1,3-bis(trifluoromethyl)benzene (23 g), 1,4-dibromobutane (42 g), and pentaerythritol triallyl ether (10 g) were added and stirred at 65 C., and then separated and purified to obtain pentaerythritol triallyl ether bromo adduct (A) (5.23 g).

[0194] Pentaerythritol triallyl ether bromo adduct (A):

BrCH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2OCH.sub.2C(CH.sub.2CH.sub.2CHCH.sub.2).sub.3

Synthesizing Example 2

[0195] To a four necked flask of 100 mL provided with a reflux condenser, a thermometer and a stirrer, a perfluoropolyether modified alcohol compound of the average composition: CF.sub.3O(CF.sub.2CF.sub.2O).sub.20(CF.sub.2O).sub.16CF.sub.2CH.sub.2OH (with proviso that although the compound comprising a small amount of the repeating units (CF.sub.2CF.sub.2CF.sub.2CF.sub.2O) and/or (CF.sub.2CF.sub.2CF.sub.2O) in the mixture, it was not taken into consideration since it was a very small amount) (8.96 g), 1,3-bis(trifluoromethyl)benzene (51 g), and KOH (0.39 g) were added and stirred at 70 C. Then, pentaerythritol triallyl ether bromo adduct (A) (3.60 g) obtained in Synthesizing Example 1, and tetrabutylammonium bromide (0.14 g) were added and stirred at 70 C., and then separated and purified to obtain perfluoropolyether group containing allyloxy compound (B) having an allyl group at the terminal (4.86 g).

[0196] Perfluoropolyether group containing allyloxy compound (B):

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

Synthesizing Example 3

[0197] To a four necked flask of 50 mL provided with a reflux condenser, a thermometer and a stirrer, perfluoropolyether group containing allyloxy compound (B) (3.33 g) obtained in Synthesizing Example 2, 1,3-bis(trifluoromethyl)benzene (7.24 g), and triacetoxysilane (0.01 g) were added and stirred for 30 minutes. Then, trichlorosilane (1.16 g) and a xylene solution (0.03 ml) containing Pt complex of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane at 2% were added and stirred at 60 C. for 3 hours. Then, volatile content was distilled off under a reduced pressure to obtain, and a mixture of methanol (0.13 g) and trimethyl orthoformate (5.25 g) was added, and then, stirred at 50 C. and separate and purified to obtain perfluoropolyether group containing silane compound (C) having trimethoxysilyl group at the terminal (3.12 g).

[0198] Perfluoropolyether group containing silane compound (C):

CF.sub.3O(CF.sub.2CF.sub.2O).sub.20(CF.sub.2O).sub.16CF.sub.2CH.sub.2OCH.sub.2CH.sub.2CH.sub.2CH.sub.2OCH.sub.2C(CH.sub.2OCH.sub.2CH.sub.2CH.sub.2Si(OMe).sub.3).sub.3

Synthesizing Example 4

[0199] To a four necked flask of 100 mL provided with a reflux condenser, a thermometer and a stirrer, perfluoropolyether modified alcohol compound (8.5 g) of the average composition: CF.sub.3CF.sub.2CF.sub.2O(CF.sub.2CF.sub.2CF.sub.2O).sub.20CF.sub.2CF.sub.2CH.sub.2OH, 1,3-bis(trifluoromethyl)benzene (45 g) and KOH (0.33 g) were added and stirred at 70 C. Then, pentaerythritol triallyl ether bromo adduct (A) (3.10 g) obtained in Synthesizing Example 1 and tetrabutylammonium bromide (0.12 g) were added and stirred at 70 C., and then separated and purified to obtain perfluoropolyether group containing allyloxy compound (D) having allyl group at the terminal (4.81 g).

[0200] Perfluoropolyether group containing allyloxy compound (D):

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.2CH.sub.2OCH.sub.2C(CH.sub.2OCH.sub.2CHCH.sub.2).sub.3

Synthesizing Example 5

[0201] To a four necked flask of 50 mL provided with a reflux condenser, a thermometer and a stirrer, perfluoropolyether group containing allyloxy compound (D) (4.5 g) obtained in Synthesizing Example 4, 1,3-bis(trifluoromethyl)benzene (8.87 g), and triacetoxysilane (0.01 g) were added and stirred for 30 minutes. Then, trichlorosilane (1.42 g) and a xylene solution (0.04 ml) containing Pt complex of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane at 2% were added and stirred at 60 C. for 3 hours. Then, volatile content was distilled off under a reduced pressure to obtain, and a mixture of methanol (0.16 g) and trimethyl orthoformate (6.44 g) was added, and then, stirred at 50 C. and separate and purified to obtain perfluoropolyether group containing silane compound (E) having trimethoxysilyl group at the terminal (4.36 g).

[0202] perfluoropolyether group containing silane compound (E):

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.2CH.sub.2OCH.sub.2C(CH.sub.2OCH.sub.2CH.sub.2CH.sub.2Si(OMe).sub.3).sub.3

Synthesizing Example 6

[0203] To a four necked flask of 50 mL provided with a reflux condenser, a thermometer and a stirrer, perfluoropolyether group containing allyloxy compound of CF.sub.3O(CF.sub.2CF.sub.2O).sub.20(CF.sub.2O).sub.16CF.sub.2C(OCH.sub.2CHCH.sub.2)(CH.sub.2CHCH.sub.2).sub.2 (5.0 g) (with proviso that although the compound comprising a small amount of the repeating units (CF.sub.2CF.sub.2CF.sub.2CF.sub.2O) and/or (CF.sub.2CF.sub.2CF.sub.2O) in the mixture, it was not taken into consideration since it was a very small amount), 1,3-bis(trifluoromethyl)benzene (9.0 g), and triacetoxysilane (0.01 g) were added and stirred for 30 minutes. Then, trichlorosilane (1.50 g) and a xylene solution (0.05 ml) containing Pt complex of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane at 2% were added and stirred at 60 C. for 3 hours. Then, volatile content was distilled off under a reduced pressure to obtain, and a mixture of methanol (0.20 g) and trimethyl orthoformate (7.0 g) was added, and then, stirred at 50 C. and separate and purified to obtain perfluoropolyether group containing silane compound (F) having trimethoxysilyl group at the terminal (5.32 g).

[0204] Perfluoropolyether group containing silane compound (F):

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

Synthesizing Example 7

[0205] To a four necked flask of 50 mL provided with a reflux condenser, a thermometer and a stirrer, perfluoropolyether group containing allyloxy compound of CF.sub.3CF.sub.2CF.sub.2O(CF.sub.2CF.sub.2CF.sub.2O).sub.20CF.sub.2CF.sub.2C(OCH.sub.2CHCH.sub.2)(CH.sub.2CHCH.sub.2).sub.2 (4.0 g), 1,3-bis(trifluoromethyl)benzene (7.2 g), and triacetoxysilane (0.01 g) were added and stirred for 30 minutes. Then, trichlorosilane (1.20 g) and a xylene solution (0.04 ml) containing Pt complex of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane at 2% were added and stirred at 60 C. for 3 hours. Then, volatile content was distilled off under a reduced pressure to obtain, and a mixture of methanol (0.16 g) and trimethyl orthoformate (5.6 g) was added, and then, stirred at 50 C. and separate and purified to obtain perfluoropolyether group containing silane compound (G) having trimethoxysilyl group at the terminal (4.4 g).

[0206] Perfluoropolyether group containing silane compound (G):

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

Example 1

[0207] Compound (C) obtained in Synthesizing Example 3 was dissolved in hydrofluoroether (Novec HFE7200 manufactured by Sumitomo 3M Ltd.)) such that the concentration was 20 wt % to prepare Surface-treating agent 1.

[0208] 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 3.010.sup.3 Pa. Firstly, silicon dioxide was deposited on the surface of this chemical strengthening glass 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 (C)) was vacuum-deposited per one plate of the chemical strengthening glass (55 mm100 mm). Then, the chemical strengthening glass having the deposited layer was stood under a temperature of 20 C. and a humidity of 65% for 24 hours.

Example 2

[0209] The surface-treating agent was prepared and the surface-treating layer was formed similarly to Example 1 except that Compound (E) obtained in Synthesis Example 5 was used in place of Compound (C).

Example 3

[0210] The surface-treating agent was prepared and the surface-treating layer was formed similarly to Example 1 except that Compound (F) obtained in Synthesis Example 6 was used in place of Compound (C).

Example 4

[0211] The surface-treating agent was prepared and the surface-treating layer was formed similarly to Example 1 except that Compound (G) obtained in Synthesis Example 7 was used in place of Compound (C).

Example 5

[0212] The surface-treating agent was prepared and the surface-treating layer was formed similarly to Example 1 except that perfluoropolyether group containing silane compound (H) shown below was used in place of Compound (C).

[0213] Perfluoropolyether group containing silane compound (H):

CF.sub.3O(CF.sub.2CF.sub.2O).sub.20(CF.sub.2O).sub.16CF.sub.2C[OC(O)NHCH.sub.2CH.sub.2CH.sub.2Si(OMe).sub.3][CH.sub.2CH.sub.2CH.sub.2Si(OMe).sub.3].sub.2

Comparative Examples 1-3

[0214] The surface-treating agent was prepared and the surface-treating layer was formed similarly to Example 1 except that Control compounds 1-3 shown below were used in place of Compound (C).

##STR00008##

wherein g is an integer of 1-6.

##STR00009##

wherein g is an integer of 1-6.

[0215] Evaluation of Friction Durability

[0216] A static water contact angle of the surface-treating layers formed on the surface of the base material in the above Examples and Comparative Examples respectively 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.).

[0217] 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). 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, 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 at a rate of 140 mm/second while applying the load. The static water contact angle (degree) was measured per 2,500 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 1 (in the table, the symbol - represents no measurement).

TABLE-US-00001 TABLE 1 Number of rubbing Contact Angle (degree) (times) Example 1 Example 2 Example 3 Example 4 Example 5 0 113.1 113.8 113.4 113.0 113.2 2500 112.7 112.5 112.1 111.9 111.7 5000 112.3 111.4 112.0 109.5 108.8 7500 112.0 111.2 110.6 109.2 108.4 10000 112.3 108.2 107.1 107.5 107.4 12500 112.2 106.4 105.9 106.2 104.2 15000 111.1 106.1 104.7 104.0 103.8 17500 110.9 104.9 104.8 103.7 103.5 20000 109.6 104.5 103.9 102.6 102.4 22500 108.3 102.7 102.4 102.2 101.9 Number of Contact Angle (degree) rubbing Comparative Comparative Comparative (times) Example 1 Example 2 Example 3 0 113.0 112.8 113.6 2500 104.0 110.9 108.2 5000 74.3 110.4 92.5 7500 107.2 10000 105.5 12500 104.2 15000 95.0 17500 20000 22500

[0218] As understood from the above results, it was confirmed that Examples 1-5 using the perfluoropolyether group containing silane compound of the present invention having some Si(OMe).sub.3 branching from a carbon atom of the main chain showed improved friction durability in comparison with Comparative Examples 1-3 using the compounds having no such structure.

INDUSTRIAL APPLICABILITY

[0219] 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.