PERFLUORO(POLY)ETHER GROUP CONTAINING SILANE COMPOUND

Abstract

The present invention provides a perfluoro(poly)ether group containing silane compound of the formula (1):

XR.sup.a.sub.R.sup.b.sub.R.sup.c.sub.(1)

wherein each symbols are as defined in the description.

Claims

1. A perfluoro(poly)ether group containing silane compound of the formula (1):
XR.sup.a.sub.R.sup.b.sub.R.sup.c.sub.(1) wherein: R.sup.a is each independently at each occurrence Rf-PFPE-; 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 1 or more, and the occurrence order of the respective repeating units in parentheses with the subscript a, b, c or d is not limited in the formula; R.sup.b is each independently at each occurrence ZSiR.sup.1.sub.kR.sup.2.sub.lR.sup.3.sub.m; Z is each independently at each occurrence an oxygen atom or a divalent organic group; R.sup.1 is each independently at each occurrence R.sup.b; R.sup.b has the same definition as that of R.sup.b; in R.sup.b, the number of Si atoms which are straightly linked via the Z group is up to five; R.sup.2 is each independently at each occurrence a hydroxyl group or a hydrolyzable group; R.sup.3 is each independently at each occurrence a hydrogen atom or a lower alkyl group; k is each independently at each occurrence an integer of 0-3; l is each independently at each occurrence an integer of 0-3; m is each independently at each occurrence an integer of 0-3; in one R.sup.b, the sum of k, l and m is 3, and in the formula (1), at least one of l is one or more; R.sup.c is each independently at each occurrence a radical scavenger group or an ultraviolet ray absorbing group; X is a 3-10 valent organic group; is an integer of 1-8; is an integer of 1-8; and is an integer of 1-8.

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

3. 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.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 an integer of 0-30, 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
(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 n is an integer of 2-100.

4. The perfluoro(poly)ether group containing silane compound according to claim 1 wherein R.sup.c is ##STR00012##

5. The perfluoro(poly)ether group containing silane compound according to claim 1 wherein X is each independently selected from the group consisting of: ##STR00013## wherein R.sup.41 is each independently a hydrogen atom, a phenyl group, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms; some of T are a divalent R.sup.43 attached to R.sup.a of the formula (1); R.sup.43 is each independently a divalent organic group; others of T are a divalent R.sup.44 attached to R.sup.b of the formula (1); R.sup.44 is each independently a divalent organic group; further others of T are a divalent R.sup.45 attached to R.sup.c of the formula (1); R.sup.45 is each independently a divalent organic group; the others T are each independently a C.sub.1-6 alkyl group, a phenyl group or a C.sub.1-6 alkoxy group, if present.

6. The perfluoro(poly)ether group containing silane compound according to claim 5 wherein R.sup.43 is a group of the following formula:
(CR.sup.50.sub.2).sub.rR.sup.46.sub.s(CR.sup.47.sub.2).sub.t wherein R.sup.5 is each independently at each occurrence a hydrogen atom, a fluorine atom, an alkyl group having 1-3 carbon atoms or a phenyl group; R.sup.46 is each independently at each occurrence O or CONR.sup.48; R.sup.48 is each independently at each occurrence a hydrogen atom, an alkyl group having 1-3 carbon atoms or a phenyl group; R.sup.47 is each independently at each occurrence a hydrogen atom, a fluorine atom, an alkyl group having 1-3 carbon atoms or a phenyl group; r is an integer of 0-10; s is 0 or 1; t is an integer of 0-10; and the occurrence order of the respective repeating units in parentheses with the subscript r, s or t is not limited in the formula; or a group of the following formula: ##STR00014## wherein R.sup.42 is each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms; R.sup.44 is (CH.sub.2).sub.f wherein f is an integer of 0-6; and R.sup.45 is (CH.sub.2).sub.g wherein g is an integer of 0-6.

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

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

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

10. The surface-treating agent according to claim 9 further comprising one or more components selected form a fluorine-containing oil, a silicone oil and a catalyst.

11. The surface-treating agent according to claim 10 comprising a fluorine-containing oil wherein the fluorine-containing oil is one or more compounds of the formula (3):
R.sup.21(OC.sub.4F).sub.a(OC.sub.3F).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 constitute a main backbone of the polymer, and are each independently an integer of 0 or more and 300 or less, the sum of a, b, c and d is 1 or more, and the occurrence order of the respective repeating units in parentheses with the subscript a, b, c and d is not limited in the formula.

12. The surface-treating agent according to claim 10 comprising a fluorine-containing oil 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.

13. The surface-treating agent according to claim 12 comprising one or more compounds of the formula (3b).

14. The surface-treating agent according to claim 12 wherein a mass ratio of the perfluoro(poly)ether group containing silane compound of the formula (1) according to any one of claims 1-8 and the compound of the formula (3b) is 4:1-1:4.

15. The surface-treating agent according to claim 12 wherein the compound of the formula (3a) has a number average molecular weight of 2,000-8,000.

16. The surface-treating agent according to claim 12 wherein the compound of the formula (3b) has a number average molecular weight of 2,000-30,000.

17. The surface-treating agent according to claim 1 wherein the compound of the formula (3b) has a number average molecular weight of 8,000-30,000.

18. The surface-treating agent according to claim 9 further comprising a solvent.

19. The surface-treating agent according to claim 9 which is used as an antifouling-coating agent or a water-proof coating agent.

20. The surface-treating agent according to claim 9 for vacuum deposition.

21. A pellet comprising the surface-treating agent according to claim 9.

22. An article comprising a base material and a layer which is formed on a surface of the base material from the perfluoro(poly)ether group containing silane compound according to claim 1.

23. The article according to claim 22 wherein the article is an optical member.

24. The article according to claim 22 wherein the article is a display.

25. 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 9.

Description

EXAMPLES

[0165] 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

[0166] To a four necked flask of 100 mL provided with a reflux condenser, a thermometer and a stirrer, 4-hydroxy-1,2,2,6,6-pentamethylpiperidine (10 g), sodium hydride (4.6 g), and tetrabutylammonium bromide (0.1 g) were added, and then allyl chloride (14.7 g) was added and the mixture were stirred at 50 C. Then, the mixture was purified and separated to obtain Compound (A) (9.6 g).

##STR00008##

Synthesizing Example 2

[0167] To a four necked flask of 100 mL provided with a reflux condenser, a thermometer and a stirrer, a perfluoropolyallylether of the average composition: CF.sub.3O(CF.sub.2CF.sub.2O).sub.20(CF.sub.2O).sub.16CF.sub.2CH.sub.2OCH.sub.2CHCH.sub.2 (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) (5 g) and 1,3-bis(trifluoromethyl)benzene (6 g) were added, and stirred for 30 minutes. Then, 2,4,6,8-tetramethylcyclotetrasiloxane (0.35 g) and a xylene solution (0.02 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, and 1,3-bis(trifluoromethyl)benzene (6 g) and Compound (A) (0.3 g) obtained in Synthesizing Example 1 were added, and stirred at 60 C. for 3 hours. Then, vinyltrimethoxysilane (0.5 g) was added, and stirred at 60 C. for 3 hours. Then, the mixture was purified and separated to obtain perfluoropolyether group containing silane compound (B) (3.4 g).

[0168] Perfluoropolyether group containing silane compound (B):

##STR00009##

wherein PFPE is CF.sub.3O(CF.sub.2CF.sub.2O).sub.20(CF.sub.2O).sub.16CF.sub.2.

Example 1

[0169] Compound (B) obtained in Synthesizing Example 2 was dissolved in hydrofluoroether (Novec HFE7200 manufactured by Sumitomo 3M Ltd.)) such that the concentration was 20 wt % to prepare Surface-treating agent 1.

Synthesizing Example 3

[0170] To a four necked flask of 100 mL provided with a reflux condenser, a thermometer and a stirrer, a perfluoropolyallylether of the average composition: CF.sub.3CF.sub.2CF.sub.2O(CF.sub.2CF.sub.2CF.sub.2O).sub.2OCF.sub.2CF.sub.2CH.sub.2OCH.sub.2CHCH.sub.2 (5 g) and 1,3-bis(trifluoromethyl)benzene (6 g) were added and stirred for 30 minutes. Then, 2,4,6,8-tetramethylcyclotetrasiloxane (0.36 g) and a xylene solution (0.02 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, and 1,3-bis(trifluoromethyl)benzene (6 g) and Compound (A) (0.25 g) obtained in Synthesizing Example 1 were added, and stirred at 60 C. for 3 hours. Then, vinyltrimethoxysilane (0.5 g) was added, and stirred at 60 C. for 3 hours. Then, the mixture was purified and separated to obtain perfluoropolyether group containing silane compound (C) (3.5 g).

[0171] Perfluoropolyether group containing silane compound (C):

##STR00010##

wherein PFPE is CF.sub.3CF.sub.2CF.sub.2 (CF.sub.2CF.sub.2CF.sub.2O).sub.20CF.sub.2CF.sub.2.

Example 2

[0172] 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 2.

[0173] Surface-treating agents 1 and 2 prepared in the above were 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.

Comparative Example 1

[0174] The surface-treating agent was prepared and the surface-treating layer was formed similarly to Example 1 except that Control compound 1 shown below was used in place of Compound (C).

##STR00011##

wherein PFPE is CF.sub.3O(CF.sub.2CF.sub.2O).sub.20 (CF.sub.2O).sub.16CF.sub.2.

[0175] Evaluation of UV Resistance

[0176] A static water contact angle after the UV irradiation of the surface-treating layers formed on the surface of the base material in the above Examples 1 and 2 and Comparative Example 1 respectively was measured. The UV irradiation was performed by using UVB-UV lamp (G15T8E, manufactured by Sankyo Denki Co., Ltd., the irradiance is 2.74 mW/cm.sup.2 at 306 nm). 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.).

[0177] 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 UV irradiation time is zero). Then, the static water contact angle (degree) was measured for each defined elapsed time. The evaluation was performed until the cumulative irradiation time of 286 hours. The results are shown in Table 1.

TABLE-US-00001 TABLE 1 Irradiation Contact angle (degree) time Comparative (hours) Example 1 Example 2 Example 1 0 114.1 115.1 113.7 73 114.4 115.0 112.2 98 114.8 114.8 111.9 124 113.3 112.9 110.8 161 111.4 110.0 107.1 238 107.8 106.1 104.5 259 106.5 105.8 103.9 286 106.3 105.1 102.5

[0178] As understood from the above results, it was confirmed that the perfluoropolyether group containing silane compound of the present invention having a radical scavenger group and/or an ultraviolet ray absorbing group had increased UV resistance in comparison with Comparative Example I which did not have such structure.

INDUSTRIAL APPLICABILITY

[0179] 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.