Coating composition, surface treatment agent containing said composition, and article which is surface-treated with said surface treatment agent

Abstract

According to the present invention, a surface treatment agent which contains a coating composition that contains (A) one or more compounds selected from among organosilane or siloxane compounds represented by formula (1) and partial (hydrolysis) condensation products of the compounds and (B) one or more compounds selected from among silane or siloxane compounds represented by formula (2) and partial (hydrolysis) condensation products of the compounds at a mass ratio of from 50:50 to 90:10 is able to form a cured coating film that has excellently low fingerprint visibility. ##STR00001##
(In formula (1), A represents —C(═O)OR.sup.1, —C(═O)NR.sup.1.sub.2, —C(═O)SR.sup.1 or —P(═O)(OR.sup.1).sub.2; R.sup.1 represents H, an alkyl group, an aryl group or an aralkyl group; Y represents a divalent organic group; R represents an alkyl group or a phenyl group; X represents a hydroxyl group or a hydrolyzable group; and n is 1-3.) ##STR00002##
(In formula (2), Rf represents a perfluoroalkylene group or a divalent perfluoropolyether group.)

Claims

1. A coating composition comprising (A) one or more compounds selected from among compounds having general formula (1) and partial condensates or partial hydrolytic condensates thereof and (B) one or more compounds selected from among compounds having general formula (2) and partial condensates or partial hydrolytic condensates thereof in a weight ratio of from 50:50 to 90:10, total of components (A) and (B) being 100, ##STR00064## wherein A is —C(═O)OR.sup.1, —C(═O)NR.sup.1.sub.2, or —C(═O)SR.sup.1, R.sup.1 is hydrogen, a C.sub.1-C.sub.30 alkyl group, C.sub.6-C.sub.30 aryl group or C.sub.7-C.sub.30 aralkyl group, Y is independently a divalent organic group which may contain an organopolysiloxane residue, R is independently a C.sub.1-C.sub.4 alkyl group or phenyl group, X is independently a hydroxyl group or hydrolyzable group, and n is an integer of 1 to 3, ##STR00065## wherein Rf is a perfluoroalkylene group or divalent perfluoropolyether group, Y is independently a divalent organic group which may contain an organopolysiloxane residue, R is independently a C.sub.1-C.sub.4 alkyl group or phenyl group, X is independently a hydroxyl group or hydrolyzable group, and n is an integer of 1 to 3.

2. The coating composition of claim 1 wherein in formulae (1) and (2), the divalent organic group of Y is independently a C.sub.2-C.sub.30 alkylene group optionally comprising a divalent group selected from among —O—, —S—, —NR—, —C(═O)—, —C(═O)O—, —C(═O)NR—, —OC(═O)NR—, a C.sub.6-C.sub.20 arylene group, silalkylene group, silarylene group, and straight, branched or cyclic divalent organopolysiloxane residues of 2 to 10 silicon atoms, wherein R is C.sub.1-C.sub.4 alkyl or phenyl.

3. The coating composition of claim 1 wherein in formulae (1) and (2), the hydroxyl group or hydrolyzable group of X is independently selected from the group consisting of hydroxyl, C.sub.1—C.sub.10 alkoxy, C.sub.2-C.sub.10 alkoxy-substituted alkoxy, C.sub.2-C.sub.10 acyloxy, C.sub.2-C.sub.10 alkenyloxy, halogen, oxime, isocyanate, and cyanate.

4. The coating composition of claim 1 wherein in formula (2), Rf is a C.sub.3-C.sub.12 perfluoroalkylene group or a divalent perfluoropolyether group having a formula (3): ##STR00066## wherein J is at least one group selected from perfluoroalkylene groups having a structural formulae (a) to (e): ##STR00067## and all J groups may have the same structure or plural structures that may be arrayed randomly or blockwise, and b indicative of a number of repeating units is from 3 to 6.

5. The coating composition of claim 1, wherein in formula (1), n is 2 or 3.

6. The coating composition of claim 1, wherein in formula (1), n is 3.

7. The coating composition of claim 1, wherein in formula (1), Y is a divalent group having an formula (4):
—R.sup.3—Z—(R.sup.3).sub.a—  (4) wherein R.sup.3 is independently a C.sub.1-C.sub.30 alkylene group, or a C.sub.7-C.sub.30 alkylene-arylene group containing a C.sub.6-C.sub.20 arylene group, Z is a single bond, or a divalent group selected from the groups consisting of —O—, —S—, —NR—, —C(═O)—, —C(═O)O—, —C(═O)NR—, —OC(═O)NR—, silalkylene group, silarylene group, and straight, branched or cyclic divalent organopolysiloxane residues of 2 to 10 silicon atoms, wherein R is independently a C.sub.1-C.sub.4 alkyl group or phenyl group, and “a” is 0 or 1.

8. The coating composition of claim 1, wherein in formula (1), Y is any one of the following groups: ##STR00068## ##STR00069##

9. The coating composition of claim 1, wherein in formulae (1) and (2), Y is a C.sub.2-C.sub.20 alkylene group.

10. A surface treating agent comprising the coating composition of claim 1.

11. The surface treating agent of claim 10, further comprising a solvent.

12. The surface treating agent of claim 10, further comprising a hydrolytic condensation catalyst.

13. The surface treating agent of claim 10, which cures into a film having a contact angle with oleic acid of up to 30° at 25° C. at relative humidity 40%.

14. The surface treating agent of claim 10, which cures into a film having a haze of up to 10 when sebum is deposited to the cured film under a load of 1 kg.

15. An article having on its surface a cured film of the surface treating agent of claim 10.

16. A coating composition comprising (A) one or more compounds selected from among compounds having a general formula (1) and partial condensates or partial hydrolytic condensates thereof and (B) one or more compounds selected from among compounds having a general formula (2) and partial condensates or partial hydrolytic condensates thereof in a weight ratio of from 50:50 to 90:10, a total of components (A) and (B) being 100, ##STR00070## wherein A is —C(═O)OR.sup.1, —C(═O)NR.sup.1.sub.2, —C(═O)SR.sup.1 or —P(═O)(OR.sup.1).sub.2, R.sup.1 is hydrogen, a C.sub.1-C.sub.30 alkyl group, C.sub.6-C.sub.30 aryl group or C.sub.7-C.sub.30 aralkyl group, Y is independently a divalent organic group which may contain an organopolysiloxane residue, R is independently a C.sub.1-C.sub.4 alkyl group or phenyl group, X is independently a hydroxyl group or hydrolyzable group, and n is 2 or 3, ##STR00071## wherein Rf is a perfluoroalkylene group or divalent perfluoropolyether group, Y is independently a divalent organic group which may contain an organopolysiloxane residue, R is independently a C.sub.1-C.sub.4 alkyl group or phenyl group, X is independently a hydroxyl group or hydrolyzable group, and n is an integer of 1 to 3.

17. The coating composition of claim 16 wherein in formulae (1) and (2), the divalent organic group of Y is independently a C.sub.2-C.sub.30 alkylene group optionally comprising a divalent group selected from among —O—, —S—, —NR—, —C(═O)—, —C(═O)O—, —C(═O)NR—, —OC(═O)NR—, a C.sub.6-C.sub.20 arylene group, silalkylene group, silarylene group, and straight, branched or cyclic divalent organopolysiloxane residues of 2 to 10 silicon atoms, wherein R is C.sub.1-C.sub.4 alkyl or phenyl.

18. The coating composition of claim 16 wherein in formulae (1) and (2), the hydroxyl group or hydrolyzable group of X is independently selected from the group consisting of hydroxyl, C.sub.1-C.sub.10 alkoxy, C.sub.2-C.sub.10 alkoxy-substituted alkoxy, C.sub.1-C.sub.10 acyloxy, C.sub.2-C.sub.10 alkenyloxy, halogen, oxime, isocyanate, and cyanate.

19. The coating composition of claim 16 wherein in formula (2), Rf is a C.sub.3-C.sub.12 perfluoroalkylene group or a divalent perfluoropolyether group having a formula (3): ##STR00072## wherein J is at least one group selected from perfluoroalkylene groups having a structural formulae (a) to (e): ##STR00073## and all J groups may have the same structure or plural structures that may be arrayed randomly or blockwise, and b indicative of a number of repeating units is from 3 to 6.

20. The coating composition of claim 16, wherein in formula (1), Y is a divalent group having an formula (4):
—R.sup.3—Z—(R.sup.3).sub.a—  (4) wherein R.sup.3 is independently a C.sub.1-C.sub.30 alkylene group, or a C.sub.7-C.sub.30 alkylene-arylene group containing a C.sub.6-C.sub.20 arylene group, Z is a single bond, or a divalent group selected from the groups consisting of —O—, —S—, —NR—, —C(═O)—, —C(═O)O—, —C(═O)NR—, —OC(═O)NR—, silalkylene group, silarylene group, and straight, branched or cyclic divalent organopolysiloxane residues of 2 to 10 silicon atoms, wherein R is independently a C.sub.1-C.sub.4 alkyl group or phenyl group, and “a” is 0 or 1.

21. The coating composition of claim 16, wherein in formula (1), Y is any one of the following groups: ##STR00074## ##STR00075##

22. The coating composition of claim 16, wherein in formulae (1) and (2), Y is a C.sub.2-C.sub.20 alkylene group.

23. A surface treating agent comprising the coating composition of claim 16.

24. The surface treating agent of claim 23, further comprising a solvent.

25. The surface treating agent of claim 23, further comprising a hydrolytic condensation catalyst.

26. The surface treating agent of claim 23, which cures into a film having a contact angle with oleic acid of up to 30° at 25° C. at relative humidity 40%.

27. The surface treating agent of claim 23, which cures into a film having a haze of up to 10 when sebum is deposited to the cured film under a load of 1 kg.

28. An article having on its surface a cured film of the surface treating agent of claim claim 23.

Description

EXAMPLES

(1) Synthesis Examples, Examples and Comparative Examples are given below for illustrating the invention, but the invention is not limited by Examples.

(2) [Preparation of Component (A) or Lipophilic Group-Containing Silane]

Synthesis Example 1

(3) A reactor was charged with 45.7 g (2.35×10.sup.−1 mol) of 1,4-bis(dimethylsilyl)benzene, which was heated at 80° C. Then 1.0×10.sup.−2 g of a toluene solution of chloroplatinic acid/vinylsiloxane complex (containing 0.3×10.sup.−6 mol of Pt) was added, after which 10.0 g (4.71×10.sup.−2 mol) of ethyl undecenoate was added dropwise over 3 hours. This was followed by heating and stirring for 1 hour. The solvent and unreacted reactants were distilled off under reduced pressure, obtaining 18.0 g of a compound having the formula (A).

(4) ##STR00037##

(5) .sup.1H-NMR

(6) δ 0.2-0.4 (—Si—CH.sub.3) 12H

(7) δ 0.7 (—(CH.sub.2).sub.7CH.sub.2—Si—) 2H

(8) δ 1.2-1.5 (—(CH.sub.2).sub.7—, —OCH.sub.2CH.sub.3) 17H

(9) δ 1.6 (—OOC—CH.sub.2CH.sub.2(CH.sub.2).sub.7CH.sub.2—Si—) 2H

(10) δ 2.3 (—OOC—CH.sub.2—) 2H

(11) δ 4.1 (—OCH.sub.2CH.sub.3) 2H

(12) δ 4.4 (—Si—H) 1H

(13) δ 7.5 (—Si—C.sub.6H.sub.4—Si—) 4H

(14) A reactor was charged with 10.0 g (2.46×10.sup.−2 mol) of the compound having formula (A).

(15) ##STR00038##

(16) It was heated at 80° C. Then 1.0×10.sup.−2 g of toluene solution of chloroplatinic acid/vinylsiloxane complex (containing 0.3×10.sup.−6 mol of Pt) was added, after which 8.00 g (4.92×10.sup.−2 mol) of allyltrimethoxysilane was added dropwise. This was followed by heating and stirring for 3 hours. The solvent and unreacted reactants were distilled off under reduced pressure, obtaining 13.1 g of compound 1 having the formula (B).

(17) ##STR00039##

(18) .sup.1H-NMR

(19) δ 0.2-0.3 (—Si—CH.sub.3) 12H

(20) δ 0.7 (—(CH.sub.2).sub.7CH.sub.2—Si—, —SiCH.sub.2CH.sub.2CH.sub.2—Si(OCH.sub.3).sub.3) 4H

(21) δ 0.8 (—SiCH.sub.2CH.sub.2CH.sub.2—Si(OCH.sub.3).sub.3) 2H

(22) δ 1.2-1.4 (—(CH.sub.2).sub.7—, —OCH.sub.2CH.sub.3) 17H

(23) δ 1.5 (—SiCH.sub.2CH.sub.2CH.sub.2—Si(OCH.sub.3).sub.3) 2H

(24) δ 1.6 (—OOC—CH.sub.2CH.sub.2(CH.sub.2).sub.7CH.sub.2—Si—) 2H

(25) δ 2.3 (—OOC—CH.sub.2—) 2H

(26) δ 3.5 (—SiCH.sub.2CH.sub.2CH.sub.2—Si(OCH.sub.3).sub.3) 9H

(27) δ 4.1 (—OCH.sub.2CH.sub.3) 2H

(28) δ 7.5 (—Si—C.sub.6H.sub.4—Si—) 4H

Synthesis Example 2

(29) A reactor was charged with 35.4 g (1.82×10.sup.−1 mol) of 1,4-bis(dimethylsilyl)benzene, which was heated at 80° C. Then 1.0×10.sup.−2 g of toluene solution of chloroplatinic acid/vinylsiloxane complex (containing 0.3×10.sup.−6 mol of Pt) was added, after which 10.0 g (3.64×10.sup.−2 mol) of benzyl undecenoate was added dropwise over 3 hours. This was followed by heating and stirring for 1 hour. The solvent and unreacted reactants were distilled off under reduced pressure, obtaining 14.4 g of a compound having the formula (C).

(30) ##STR00040##

(31) .sup.1H-NMR

(32) δ 0.2-0.4 (—Si—CH.sub.3) 12H

(33) δ 0.7 (—(CH.sub.2).sub.7CH.sub.2—Si—) 2H

(34) δ 1.2-1.5 (—(CH.sub.2).sub.7—) 14H

(35) δ 1.6 (—OOC—CH.sub.2CH.sub.2(CH.sub.2).sub.7CH.sub.2—Si—) 2H

(36) δ 2.3 (—OOC—CH.sub.2—) 2H

(37) δ 4.4 (—Si—H) 1H

(38) δ 5.1 (—OCH.sub.2—C.sub.6H.sub.5) 2H

(39) δ 7.3 (—OCH.sub.2—C.sub.6H.sub.5) 5H

(40) δ 7.5 (—Si—C.sub.6H.sub.4—Si—) 4H

(41) A reactor was charged with 10.0 g (2.13×10.sup.−2 mol) of the compound having formula (C).

(42) ##STR00041##
It was heated at 80° C. Then 1.0×10.sup.−2 g of toluene solution of chloroplatinic acid/vinylsiloxane complex (containing 0.3×10.sup.−6 mol of Pt) was added, after which 4.9 g (2.99×10.sup.−2 mol) of allyltrimethoxysilane was added dropwise. This was followed by heating and stirring for 3 hours. The solvent and unreacted reactants were distilled off under reduced pressure, obtaining 9.9 g of compound 2 having the formula (D).

(43) ##STR00042##

(44) .sup.1H-NMR

(45) δ 0.2-0.3 (—Si—CH.sub.3) 12H

(46) δ 0.7 (—(CH.sub.2).sub.7CH.sub.2—Si—, —SiCH.sub.2CH.sub.2CH.sub.2—Si(OCH.sub.3).sub.3) 4H

(47) δ 0.8 (—SiCH.sub.2CH.sub.2CH.sub.2—Si(OCH.sub.3).sub.3) 2H

(48) δ 1.2-1.4 (—(CH.sub.2).sub.7—) 14H

(49) δ 1.5 (—SiCH.sub.2CH.sub.2CH.sub.2—Si(OCH.sub.3).sub.3) 2H

(50) δ 1.6 (OOC—CH.sub.2CH.sub.2(CH.sub.2).sub.7CH.sub.2—Si—) 2H

(51) δ 2.3 (—OOC—CH.sub.2—) 2H

(52) δ 3.5 (—SiCH.sub.2CH.sub.2CH.sub.2—Si(OCH.sub.3).sub.3) 9H

(53) δ 5.1 (—OCH.sub.2—C.sub.6H.sub.5) 2H

(54) δ 7.3 (—OCH.sub.2—C.sub.6H.sub.5) 5H

(55) δ 7.5 (—Si—C.sub.6H.sub.4—Si—) 4H

Synthesis Example 3

(56) A reactor was charged with 34.7 g (1.78×10.sup.−1 mol) of 1,4-bis(dimethylsilyl)benzene, which was heated at 80° C. Then 1.0×10.sup.−2 g of toluene solution of chloroplatinic acid/vinylsiloxane complex (containing 0.3×10.sup.−6 mol of Pt) was added, after which 10.0 g (3.57×10.sup.−2 mol) of cyclohexylmethyl undecenoate was added dropwise over 3 hours. This was followed by heating and stirring for 1 hour. The solvent and unreacted reactants were distilled off under reduced pressure, obtaining 13.1 g of a compound having the formula (E).

(57) ##STR00043##

(58) .sup.1H-NMR

(59) δ 0.2-0.4 (—Si—CH.sub.3) 12H

(60) δ 0.7 (—(CH.sub.2).sub.7CH.sub.2—Si—) 2H

(61) δ 1.2-1.5 (—(CH.sub.2).sub.7—, —OCH.sub.2—C.sub.6H.sub.11) 25H

(62) δ 1.6 (—OOC—CH.sub.2CH.sub.2(CH.sub.2).sub.7CH.sub.2—Si—) 2H

(63) δ 2.3 (—OOC—CH.sub.2—) 2H

(64) δ 3.9 (—OCH.sub.2—C.sub.6H.sub.11) 2H

(65) δ 4.4 (—Si—H) 1H

(66) δ 7.5 (—Si—C.sub.6H.sub.4—Si—) 4H

(67) A reactor was charged with 8.0 g (1.68×10.sup.−2 mol) of the compound having formula (E).

(68) ##STR00044##

(69) It was heated at 80° C. Then 1.0×10.sup.−2 g of toluene solution of chloroplatinic acid/vinylsiloxane complex (containing 0.3×10.sup.−6 mol of Pt) was added, after which 3.8 g (2.36×10.sup.−2 mol) of allyltrimethoxysilane was added dropwise. This was followed by heating and stirring for 3 hours. The solvent and unreacted reactants were distilled off under reduced pressure, obtaining 6.9 g of compound 3 having the formula (F).

(70) ##STR00045##

(71) .sup.1H-NMR

(72) δ 0.2-0.3 (—Si—CH.sub.3) 12H

(73) δ 0.7 (—(CH.sub.2).sub.7CH.sub.2—Si—, —SiCH.sub.2CH.sub.2CH.sub.2—Si(OCH.sub.3).sub.3) 4H

(74) δ 0.8 (—SiCH.sub.2CH.sub.2CH.sub.2—Si(OCH.sub.3).sub.3) 2H

(75) δ 1.2-1.5 (—(CH.sub.2).sub.7—, —OCH.sub.2—C.sub.6H.sub.11) 25H

(76) δ 1.5 (—SiCH.sub.2CH.sub.2CH.sub.2—Si(OCH.sub.3).sub.3) 2H

(77) δ 1.6 (—OOC—CH.sub.2CH.sub.2(CH.sub.2).sub.7CH.sub.2—Si—) 2H

(78) δ 2.3 (—OOC—CH.sub.2—) 2H

(79) δ 3.5 (—SiCH.sub.2CH.sub.2CH.sub.2—Si(OCH.sub.3)3) 9H

(80) δ 3.9 (—OCH.sub.2—C.sub.6H.sub.11) 2H

(81) δ 7.5 (—Si—C.sub.6H.sub.4—Si—) 4H

Synthesis Example 4

(82) A reactor was charged with 10.0 g (2.46×10.sup.−2 mol) of the compound having formula (A) in Synthesis Example 1.

(83) ##STR00046##
It was heated at 80° C. Then 1.0×10.sup.−2 g of toluene solution of chloroplatinic acid/vinylsiloxane complex (containing 0.3×10.sup.−6 mol of Pt) was added, after which 8.0 g (3.44×10.sup.−2 mol) of 7-octenyltrimethoxysilane was added dropwise. This was followed by heating and stirring for 3 hours. The solvent and unreacted reactants were distilled off under reduced pressure, obtaining 13.4 g of compound 4 having the formula (G).

(84) ##STR00047##

(85) .sup.1H-NMR

(86) δ 0.2-0.3 (—Si—CH.sub.3) 12H

(87) δ 0.7 (—(CH.sub.2).sub.7CH.sub.2—Si—, —SiCH.sub.2(CH.sub.2).sub.6CH.sub.2—Si(OCH.sub.3).sub.3) 4H

(88) δ 0.8 (—SiCH.sub.2(CH.sub.2).sub.6CH.sub.2—Si(OCH.sub.3).sub.3) 2H

(89) δ 1.2-1.4 (—(CH.sub.2).sub.7—, —OCH.sub.2CH.sub.3) 17H

(90) δ 1.5 (—SiCH.sub.2(CH.sub.2).sub.6CH.sub.2—Si(OCH.sub.3).sub.3) 12H

(91) δ 1.6 (—OOC—CH.sub.2CH.sub.2(CH.sub.2).sub.7CH.sub.2—Si—) 2H

(92) δ 2.3 (—OOC—CH.sub.2—) 2H

(93) δ 3.5 (—SiCH.sub.2(CH.sub.2).sub.6CH.sub.2—Si(OCH.sub.3).sub.3) 9H

(94) δ 4.1 (—OCH.sub.2CH.sub.3) 2H

(95) δ 7.5 (—Si—C.sub.6H.sub.4—Si—) 4H

(96) [Preparation of Component (B) or Fluorocarbon Group-Containing Silane or Siloxane]

Synthesis Example 5

(97) A reactor was charged with 18.6 g (9.58×10.sup.−2 mol) of 1,4-bis(dimethylsilyl)benzene, which was heated at 80° C. Then 1.0×10.sup.−2 g of toluene solution of chloroplatinic acid/vinylsiloxane complex (containing 0.3×10.sup.−6 mol of Pt) was added, after which 10.0 g (1.92×10.sup.−2 mol) of CF.sub.3CF.sub.2CF.sub.2—O—CF(CF.sub.3)CF.sub.2—O—CF(CF.sub.3)—CH.sub.2—O—CH.sub.2CH═CH.sub.2 was added dropwise over 3 hours. This was followed by heating and stirring for 1 hour. The solvent and unreacted reactants were distilled off under reduced pressure, obtaining 8.0 g of a compound having the formula (H).

(98) ##STR00048##

(99) .sup.1H-NMR

(100) δ 0.2-0.4 (—Si—CH.sub.3) 12H

(101) δ 0.7 (—(CH.sub.2).sub.2CH.sub.2—Si—) 2H

(102) δ 1.6 (—O—CH.sub.2CH.sub.2CH.sub.2—Si—) 2H

(103) δ 3.5 (O—OCH.sub.2—) 2H

(104) δ 3.9 (—OCH.sub.2CF.sub.2) 2H

(105) δ 4.4 (—Si—H) 1H

(106) δ 7.5 (—Si—C.sub.6H.sub.4—Si—) 4H

(107) A reactor was charged with 7.0 g (9.77×10.sup.−3 mol) of the compound having formula (H).

(108) ##STR00049##
It was heated at 80° C. Then 1.0×10.sup.−2 g of toluene solution of chloroplatinic acid/vinylsiloxane complex (containing 0.3×10.sup.−6 mol of Pt) was added, after which 2.2 g (1.37×10.sup.−2 mol) of allyltrimethoxysilane was added dropwise. This was followed by heating and stirring for 3 hours. The solvent and unreacted reactants were distilled off under reduced pressure, obtaining 7.7 g of compound 6 having the formula (I).

(109) ##STR00050##

(110) .sup.1H-NMR

(111) δ 0.1 (—Si—CH.sub.3) 12H

(112) δ 0.7 (—(CH.sub.2).sub.2CH.sub.2—Si—) 2H

(113) δ 0.8 (—Si—CH.sub.2(CH.sub.2).sub.2—Si(OCH.sub.3).sub.3, —Si—(CH.sub.2).sub.2CH.sub.2—Si(OCH.sub.3).sub.3) 4H

(114) δ 1.6 (—O—CH.sub.2CH.sub.2CH.sub.2—Si—, —Si—CH.sub.2CH.sub.2CH.sub.2—Si(OCH.sub.3).sub.3) 4H

(115) δ 3.5 (—Si(CH.sub.2).sub.3—Si(OCH.sub.3).sub.3, —O—CH.sub.2—) 11H

(116) δ 3.9 (—OCH.sub.2CF.sub.2) 2H

(117) δ 7.5 (—Si—C.sub.6H.sub.4—Si—) 4H

Synthesis Example 6

(118) A reactor was charged with 77.5 g (5.77×10.sup.−1 mol) of bis(dimethylsilyl) ether, which was heated at 80° C. Then 3.0×10.sup.−2 g of toluene solution of chloroplatinic acid/vinylsiloxane complex (containing 0.9×10.sup.−6 mol of Pt) was added, after which 30.0 g (1.15×10.sup.−1 mol) of CF.sub.3(CF.sub.2).sub.3CH.sub.2CH═CH.sub.2 was added dropwise over 3 hours. This was followed by heating and stirring for 1 hour. The solvent and unreacted reactants were distilled off under reduced pressure, obtaining 40.1 g of a compound having the formula (J).

(119) ##STR00051##

(120) .sup.1H-NMR

(121) δ 0.1-0.2 (—Si—CH.sub.3) 12H

(122) δ 0.7 (—(CH.sub.2)2CH.sub.2—Si—) 2H

(123) δ 1.6 (CF.sub.2—CH.sub.2CH.sub.2CH.sub.2—Si—) 2H

(124) δ 2.1 (CF.sub.2—CH.sub.2(CH.sub.2).sub.2—Si—) 2H

(125) δ 4.7 (—Si—H) 1H

(126) A reactor was charged with 30.0 g (7.61×10.sup.−2 mol) of the compound having formula (J).

(127) ##STR00052##
It was heated at 80° C. Then 3.0×10.sup.−2 g of toluene solution of chloroplatinic acid/vinylsiloxane complex (containing 0.9×10.sup.−6 mol of Pt) was added, after which 15.8 g (1.06×10.sup.−1 mol) of vinyltrimethoxysilane was added dropwise. This was followed by heating and stirring for 3 hours. The solvent and unreacted reactants were distilled off under reduced pressure, obtaining 35.5 g of compound 7 having the formula (K).

(128) ##STR00053##

(129) .sup.1H-NMR

(130) δ 0-0.1 (—Si—CH.sub.3) 12H

(131) δ 0.7 (—(CH.sub.2).sub.2CH.sub.2—Si—, —Si—CH.sub.2—CH.sub.2—Si(OCH.sub.3).sub.3, —Si—CH.sub.2—CH.sub.2—Si(OCH.sub.3).sub.3) 6H

(132) δ 1.6 (CF.sub.2—CH.sub.2CH.sub.2CH.sub.2—Si—) 2H

(133) δ 2.1 (CF.sub.2—CH.sub.2(CH.sub.2).sub.2—Si—) 2H

(134) δ 3.5 (—Si(CH.sub.2)2—Si(OCH.sub.3).sub.3) 9H

Synthesis Example 7

(135) A reactor was charged with 186.9 g (9.61×10.sup.−1 mol) of 1,4-bis(dimethylsilyl)benzene, which was heated at 70° C. Then 5.0×10.sup.−2 g of toluene solution of chloroplatinic acid/vinylsiloxane complex (containing 1.5×10.sup.−6 mol of Pt) was added, after which 50.0 g (1.92×10.sup.−1 mol) of CF.sub.3(CF.sub.2).sub.3CH.sub.2CH═CH.sub.2 was added dropwise over 3 hours. This was followed by heating and stirring for 1 hour. The solvent and unreacted reactants were distilled off under reduced pressure, obtaining 76.1 g of a compound having the formula (L).

(136) ##STR00054##

(137) .sup.1H-NMR

(138) δ 0.2-0.4 (—Si—CH.sub.3) 12H

(139) δ 0.7 (—(CH.sub.2).sub.2CH.sub.2—Si—) 2H

(140) δ 1.6 (CF.sub.2—CH.sub.2CH.sub.2CH.sub.2—Si—) 2H

(141) δ 2.1 (CF.sub.2—CH.sub.2(CH.sub.2).sub.2—Si—) 2H

(142) δ 4.4 (—Si—H) 1H

(143) A reactor was charged with 10.0 g (2.20×10.sup.−2 mol) of the compound having formula (L).

(144) ##STR00055##
It was heated at 80° C. Then 1.0×10.sup.−2 g of toluene solution of chloroplatinic acid/vinylsiloxane complex (containing 0.3×10.sup.−6 mol of Pt) was added, after which 5.0 g (3.09×10.sup.−2 mol) of allyltrimethoxysilane was added dropwise. This was followed by heating and stirring for 3 hours. The solvent and unreacted reactants were distilled off under reduced pressure, obtaining 11.8 g of compound 8 having the formula (M).

(145) ##STR00056##

(146) .sup.1H-NMR

(147) δ 0.2-0.3 (—Si—CH.sub.3) 12H

(148) δ 0.7 (—(CH.sub.2).sub.2CH.sub.2—Si—) 2H

(149) δ 0.8 (—Si—CH.sub.2(CH.sub.2).sub.2—Si(OCH.sub.3).sub.3, —Si—(CH.sub.2).sub.2CH.sub.2—Si(OCH.sub.3).sub.3) 4H

(150) δ 1.4 (CF.sub.2—CH.sub.2CH.sub.2CH.sub.2—Si—) 2H

(151) δ 1.6 (—Si—CH.sub.2CH.sub.2CH.sub.2—Si(OCH.sub.3).sub.3) 2H

(152) δ 2.1 (CF.sub.2—CH.sub.2(CH.sub.2).sub.2—Si—) 2H

(153) δ 3.5 (—Si(CH.sub.2).sub.3—Si(OCH.sub.3).sub.3) 9H

(154) δ 7.5 (—Si—C.sub.6H.sub.4—Si—) 4H

Synthesis Example 8

(155) A reactor was charged with 56.0 g (4.17×10.sup.−1 mol) of bis(dimethylsilyl) ether, which was heated at 60° C. Then 3.0×10.sup.−2 g of toluene solution of chloroplatinic acid/vinylsiloxane complex (containing 0.9×10.sup.−6 mol of Pt) was added, after which 30.0 g (8.33×10.sup.−2 mol) of CF.sub.3(CF.sub.2).sub.5CH.sub.2CH═CH.sub.2 was added dropwise over 3 hours. This was followed by heating and stirring for 1 hour. The solvent and unreacted reactants were distilled off under reduced pressure, obtaining 38.3 g of a compound having the formula (N).

(156) ##STR00057##

(157) .sup.1H-NMR

(158) δ 0.1-0.2 (—Si—CH.sub.3) 12H

(159) δ 0.7 (—(CH.sub.2).sub.2CH.sub.2—Si—) 2H

(160) δ 1.6 (CF.sub.2—CH.sub.2CH.sub.2CH.sub.2—Si—) 2H

(161) δ 2.1 (CF.sub.2—CH.sub.2(CH.sub.2).sub.2—Si—) 2H

(162) δ 4.7 (—Si—H) 1H

(163) A reactor was charged with 30.0 g (6.07×10.sup.−2 mol) of the compound having formula (N).

(164) ##STR00058##
It was heated at 80° C. Then 3.0×10.sup.−2 g of toluene solution of chloroplatinic acid/vinylsiloxane complex (containing 0.9×10.sup.−6 mol of Pt) was added, after which 12.6 g (8.49×10.sup.−2 mol) of vinyltrimethoxysilane was added dropwise. This was followed by heating and stirring for 3 hours. The solvent and unreacted reactants were distilled off under reduced pressure, obtaining 32.7 g of compound 9 having the formula (O).

(165) ##STR00059##

(166) .sup.1H-NMR

(167) δ 0-0.1 (—Si—CH.sub.3) 12H

(168) δ 0.7 (—(CH.sub.2).sub.2CH.sub.2—Si—, —Si—CH.sub.2—CH.sub.2—Si(OCH.sub.3).sub.3, —Si—CH.sub.2—CH.sub.2—Si(OCH.sub.3).sub.3) 6H

(169) δ 1.6 (CF.sub.2—CH.sub.2CH.sub.2CH.sub.2—Si—) 2H

(170) δ 2.1 (CF.sub.2—CH.sub.2(CH.sub.2).sub.2—Si—) 2H

(171) δ 3.5 (—Si(CH.sub.2).sub.2—Si(OCH.sub.3).sub.3) 9H

Synthesis Example 9

(172) A reactor was charged with 81.0 g (4.17×10.sup.−1 mol) of 1,4-bis(dimethylsilyl)benzene, which was heated at 80° C. Then 3.0×10.sup.−2 g of toluene solution of chloroplatinic acid/vinylsiloxane complex (containing 0.9×10.sup.−6 mol of Pt) was added, after which 30.0 g (8.33×10.sup.−2 mol) of CF.sub.3(CF.sub.2).sub.5CH.sub.2CH═CH.sub.2 was added dropwise over 3 hours. This was followed by heating and stirring for 1 hour. The solvent and unreacted reactants were distilled off under reduced pressure, obtaining 36.1 g of a compound having the formula (P).

(173) ##STR00060##

(174) .sup.1H-NMR

(175) δ 0.2-0.4 (—Si—CH.sub.3) 12H

(176) δ 0.7 (—(CH.sub.2).sub.2CH.sub.2—Si—) 2H

(177) δ 1.6 (CF.sub.2—CH.sub.2CH.sub.2CH.sub.2—Si—) 2H

(178) δ 2.1 (CF.sub.2—CH.sub.2(CH.sub.2).sub.2—Si—) 2H

(179) δ 4.4 (—Si—H) 1H

(180) A reactor was charged with 30.0 g (5.42×10.sup.−2 mol) of the compound having formula (P).

(181) ##STR00061##
It was heated at 80° C. Then 3.0×10.sup.−2 g of toluene solution of chloroplatinic acid/vinylsiloxane complex (containing 0.9×10.sup.−6 mol of Pt) was added, after which 12.0 g (7.41×10.sup.−2 mol) of allyltrimethoxysilane was added dropwise. This was followed by heating and stirring for 3 hours. The solvent and unreacted reactants were distilled off under reduced pressure, obtaining 33.7 g of compound 10 having the formula (Q).

(182) ##STR00062##

(183) .sup.1H-NMR

(184) δ 0.2-0.3 (—Si—CH.sub.3) 12H

(185) δ 0.7 (—(CH.sub.2).sub.2CH.sub.2—Si—) 2H

(186) δ 0.8 (—Si—CH.sub.2(CH.sub.2).sub.2—Si(OCH.sub.3).sub.3, —Si—(CH.sub.2).sub.2CH.sub.2—Si(OCH.sub.3).sub.3) 4H

(187) δ 1.4 (CF.sub.2—CH.sub.2CH.sub.2CH.sub.2—Si—) 2H

(188) δ 1.6 (—Si—CH.sub.2CH.sub.2CH.sub.2—Si(OCH.sub.3).sub.3) 2H

(189) δ 2.1 (CF.sub.2—CH.sub.2(CH.sub.2).sub.2—Si—) 2H

(190) δ 3.5 (—Si(CH.sub.2).sub.3—Si(OCH.sub.3).sub.3) 9H

(191) δ 7.5 (—Si—C.sub.6H.sub.4—Si—) 4H

Examples 1 to 11

(192) A surface treating agent was prepared by mixing compound 1 as the lipophilic group-containing silane or component (A), KBM-7603 (CF.sub.3—(CF.sub.2).sub.5—C.sub.2H.sub.4—Si(OCH.sub.3).sub.3, Shin-Etsu Chemical Co., Ltd.) as the fluorocarbon group-containing silane or siloxane or component (B), and compound 5 having the formula (R):

(193) ##STR00063##
or compounds 6 to 10 in Synthesis Examples, in the ratio shown in Tables 1 and 2, dissolving them in propylene glycol monomethyl ether (PGME) to form a 0.1 wt % solution, and adding acetic acid in a concentration of 0.1 wt %. The surface treating agent was spray coated onto Gorilla glass (Corning Inc.) and cured at 80° C. for 12 hours to form a cured film of ˜2 nm thick.

Examples 12 to 14

(194) A surface treating agent was prepared by mixing compounds 2 to 4 as the lipophilic group-containing silane or component (A) and compound 5 as the fluorocarbon group-containing silane or siloxane or component (B) in the ratio shown in Table 2, dissolving them in PGME to form a 0.1 wt % solution, and adding acetic acid in a concentration of 0.1 wt %. The surface treating agent was spray coated onto Gorilla glass (Corning Inc.) and cured at 80° C. for 12 hours to form a cured film of ˜2 nm thick.

Comparative Example 1

(195) A surface treating agent was prepared by dissolving compound 5 in PGME to form a 0.1 wt % solution, and adding acetic acid in a concentration of 0.1 wt %. The surface treating agent was spray coated onto Gorilla glass (Corning Inc.) and cured at 80° C. for 12 hours to form a cured film of ˜2 nm thick.

Comparative Example 2

(196) A surface treating agent was prepared by mixing compound 1 as the lipophilic group-containing silane or component (A), compound 5 as the fluorocarbon group-containing silane or component (B) in the ratio shown in Table 2, dissolving them in PGME to form a 0.1 wt % solution, and adding acetic acid in a concentration of 0.1 wt %. The surface treating agent was spray coated onto Gorilla glass (Corning Inc.) and cured at 80° C. for 12 hours to form a cured film of ˜2 nm thick.

(197) [Evaluation of Fingerprint Visibility]

(198) Sebum was deposited on the glass sample with the cured film, prepared above, under a load of 1 kg. Visibility was evaluated in 4 grades by a sensory test of visual observation. The results are shown in Tables 1 and 2.

(199) 4: fingerprints little visible

(200) 3: fingerprints fairly visible

(201) 2: fingerprints thinly, but definitely visible

(202) 1: fingerprints definitely visible

(203) [Evaluation of Haze]

(204) Sebum was deposited on the glass sample with the cured film, prepared above, under a load of 1 kg. Haze was measured by a haze meter NDH 5000 (Nippon Denshoku Industries Co., Ltd.). The results are shown in Tables 1 and 2.

(205) [Evaluation of Wettability]

(206) The glass sample with the cured film, prepared above, was tested using a contact angle meter Drop Master (Kyowa Interface Science Co., Ltd.). The cured film was measured for a contact angle with water or oleic acid (droplet 2 μL, temperature 25° C., humidity 40% RH, measuring time 40 seconds). The results (contact angle with water or oleic acid) are shown in Tables 1 and 2.

(207) TABLE-US-00001 TABLE 1 Amount Example (wt %) 1 2 3 4 5 6 7 8 Compound 1 90 90 90 90 90 90 90 50 Compound 2 Compound 3 Compound 4 KBM-7603 10 Compound 5 10 50 Compound 6 10 Compound 7 10 Compound 8 10 Compound 9 10 Compound 10 10 Evaluation Fingerprint visibility 4 4 4 4 4 4 4 4 Fingerprint haze (%) 6.9 1.7 5.3 3.4 2.7 3.6 4.6 1.7 Contact angle with water (°) 82 81 81 82 83 82 83 83 Contact angle with oleic acid (°) 8 7 13 7 10 7 12 8

(208) TABLE-US-00002 TABLE 2 Compar- ative Example Example Amount (wt %) 9 10 11 12 13 14 1 2 Compound 1 70 70 70 10 Compound 2 90 Compound 3 90 Compound 4 90 KBM-7603 Compound 5 10 10 10 100 90 Compound 6 Compound 7 30 Compound 8 30 Compound 9 30 Compound 10 Evaluation Fingerprint 4 4 4 4 4 4 1 2 visibility Fingerprint haze 3.1 4.7 4.3 1.9 2.5 3.1 15.3 17.4 (%) Contact angle 82 86 83 78 80 84 92 88 with water (°) Contact angle 7 21 11 7 8 9 48 27 with oleic acid (°)

(209) In the evaluation of fingerprint visibility, it was demonstrated in Examples that fingerprints were not visible. In Comparative Example 1 containing only the fluorocarbon group-containing silane, but free of a lipophilic group, fingerprints were definitely visible. In Comparative Example 2 in which the fluorocarbon group-containing silane is extremely more than the lipophilic group-containing silane, fingerprints were visible.

(210) In the haze measurement by haze meter, all Examples showed low haze values, which are compatible with the results of the sensory test.

(211) In the evaluation of wettability, Examples showed satisfactory lipophilicity.