Fluorinated ether composition, method for its production, coating liquid, substrate having surface-treated layer and method for its production
To provide a fluorinated ether composition useful for surface treatment to impart water/oil repellency to the surface of a substrate, a method for producing the fluorinated ether composition, and a coating liquid containing the fluorinated ether composition, as well as a substrate having a surface-treated layer, and a method for producing the same. Said composition comprises at least two fluorinated ether compounds which are represented by A-O-Q-(C b F 2b O) d —X—O—B 10 and which are different in B 10 . X is a divalent organic group having no CF 2 O. B 10 is —CH 2 CH 2 CH 2 SiL m R n , —CH 2 CH(SiL m R n )CH 3 , —CH 2 CH═CH 2 or —CH═CHCH 3 . A is a perfluoroalkyl group or group B 10 . Of the total of group B 10 in said composition, the proportion of —CH 2 CH 2 CH 2 SiL m R n is from 90 to 99 mol %, and the proportion of —CH═CHCH 3 is from 1 to 10 mol %. L is a hydrolyzable group, and R is a monovalent hydrocarbon group. b is an integer of from 1 to 10, and d is an integer of from 1 to 200.
1. A fluorinated ether composition, comprising:
at least three fluorinated ether compounds of the formula (1) having different group B 10 ,
wherein, of the total of group B 10 present in the composition, a proportion of a group of the formula (2-1) is from 90 to 99 mol %, a proportion of a group of the formula (2-2) is from 0 to 9 mol %, a proportion of a group of the formula (2-3) is from 0 to 9 mol %, and a proportion of a group of the formula (2-4) is from 1 to 10 mol %:
A-O-Q-(C b F 2b O) d —X—O—B 10 (1)
wherein in the formula (1),
A: a C 1-20 perfluoroalkyl group or B 10 ,
Q: a single bond, —CH 2 —, —CHF—, -Q 1 -CH 2 —, -Q 1 -CHF—, -Q 1 -O—CH 2 —, -Q 1 -O—CHF—, -Q 1 -CH 2 —O— or -Q 1 -CHF—O—,
Q 1 : a C 1-10 fluoroalkylene group, a C 2-10 fluoroalkylene group having an etheric oxygen atom between carbon-carbon atoms, a C 10 alkylene group, or a C 2-10 alkylene group having an etheric oxygen atom between carbon-carbon atoms,
b, d: b is an integer of from 1 to 10, and d is an integer of from 1 to 200, provided that when d is at least 2, (C b F 2b O) d is optionally composed of at least two types of C b F 2b O different in b,
X: a divalent organic group having no CF 2 O,
B 10 : a group of the formula (2-1), formula (2-2), formula (2-3) or formula (2-4):
—CH 2 CH 2 CH 2 SiL m R n (2-1),
—CH 2 CH(SiL m R n )CH 3 (2-2),
—CH 2 CH═CH 2 (2-3),
—CH═CHCH 3 (2-4),
wherein in the formulae (2-1) to (2-4),
L: a hydrolysable group,
R: a monovalent hydrocarbon group,
m and n: m is an integer of from 1 to 3, n is an integer of from 0 to 2, and m+n=3.
2. The fluorinated ether composition according to claim 1 , wherein of the total of group B 10 present in the composition, the total proportion of the group of the formula (2-1) and the group of the formula (2-4) is from 95 to less than 100 mol %.
3. The fluorinated ether composition according to claim 2 , wherein of the total of group B 10 present in the composition, the proportion of the group of the formula (2-1) is from 92 to less than 99 mol %, the proportion of the group of the formula (2-2) is from 0 to 5 mol %, the proportion of the group of the formula (2-3) is from 0 to 5 mol %, and the proportion of the group of the formula (2-4) is from 1 to less than 8 mol %.
4. The fluorinated ether composition according to claim 1 , wherein A is a C 1-20 perfluoroalkyl group.
5. A method for producing the fluorinated ether composition of claim 1 , comprising:
reacting a compound of the formula (3) and the compound of the formula (4) in the presence of a transition metal catalyst (C) and at least one compound (D) selected from the group consisting of nitrogen-containing compounds and sulfur-containing compounds:
A 1 -O-Q-(C b F 2b O) d —X—O—B 20 (3)
HSiL 1 m R n (4)
wherein in the formulae (3) and (4),
A 1 : the same C 1-20 perfluoroalkyl group as A in the formula (1) or B 20 ,
Q: the same group as Q in the formula (1),
b, d: the same numerical values as b and d in the formula (1), respectively,
X: the same group as X in the formula (1),
B 20 : a group represented by the formula (2-3),
L 1 : a hydrolyzable group,
R: the same group as R in the formula (1),
m and n: the same numerical values as m and n in the formula (1).
6. The method according to claim 5 , wherein the compound (D) is an aromatic amine compound or a sulfoxide compound.
7. The method according to claim 6 , wherein the compound (D) is dimethyl sulfoxide or tetramethylene sulfoxide.
8. The method according to claim 5 , wherein the transition metal catalyst (C) is a platinum catalyst.
9. The method according to claim 8 , wherein the transition metal catalyst (C) is a Pt/divinyltetramethyldisiloxane complex or a Pt/tetramethyltetravinylcyclotetrasiloxane complex.
10. A coating liquid, comprising:
the fluorinated ether composition of claim 1 ; and
at least one fluorinated organic solvent (E) selected from the group consisting of a fluorinated alkane, a fluorinated aromatic compound and a fluoroalkyl ether.
11. A method for producing a substrate having a surface-treated layer, comprising:
applying the coating liquid of claim 10 to a surface of a substrate, followed by drying.
12. A method for producing a substrate having a surface-treated layer, comprising:
vacuum vapor depositing the fluorinated ether composition of claim 1 on a surface of a substrate.
13. The method according to claim 12 , wherein a material of the surface of the substrate is metal, plastic, glass, ceramic or a composite material thereof.
14. A substrate having a surface-treated layer, treated with the fluorinated ether composition of claim 1 .
15. A touch panel having, at its input side, a substrate having a surface-treated layer, treated with the fluorinated ether composition of claim 1 .
16. The fluorinated ether composition according to claim 1 , wherein in the formula (1), Q is —CH 2 —, —CHF—, -Q 1 -CH 2 —, -Q 1 -CHF—, -Q 1 -O—CH 2 —, -Q 1 -O—CHF—, -Q 1 -CH 2 —O— or -Q 1 -CHF—O—.
17. The fluorinated ether composition according to claim 1 , wherein of the total of group B 10 present in the composition, the proportion of the group of the formula (2-1) is from 92 to less than 99 mol %, the proportion of the group of the formula (2-2) is 0 mol %, the proportion of the group of the formula (2-3) is 5 mol % or less, and the proportion of the group of the formula (2-4) is from 1 to less than 8 mol %.
18. A fluorinated ether composition comprising:
at least two fluorinated ether compounds of the formula (1) having different group B 10 ,
wherein, of the total of group B 10 present in the composition, a proportion of a group of the formula (2-1) is from 90 to 99 mol %, a proportion of a group of the formula (2-2) is from 0 to 9 mol %, a proportion of a group of the formula (2-3) is from 0 to 9 mol %, and a proportion of a group of the formula (2-4) is from 1 to 10 mol %:
A-O-Q-(C b F 2b O) d —X—O—B 10 (1)
wherein in the formula (1),
A: a C 1-20 perfluoroalkyl group or B 10 ,
Q is —CH 2 —, —CH—CH 2 —CHF—, -Q 1 -CH 2 —, -Q 1 -CHF—, -Q 1 -O—CH 2 —, -Q 1 -O—CHF—, -Q 1 -CH 2 —O— or -Q 1 -CHF—O—,
Q 1 : a C 1-10 fluoroalkylene group, a C 2-10 fluoroalkylene group having an etheric oxygen atom between carbon-carbon atoms, a C 1-10 alkylene group, or a C 2-10 alkylene group having an etheric oxygen atom between carbon-carbon atoms,
b, d: b is an integer of from 1 to 10, and d is an integer of from 1 to 200, provided that when d is at least 2, (C b F 2b O) d is optionally composed of at least two types of C b F 2b O different in b,
X: a divalent organic group having no CF 2 O,
B 10 : a group of the formula (2-1), formula (2-2), formula (2-3) or formula (2-4):
—CH 2 CH 2 CH 2 SiL m R n (2-1),
—CH 2 CH(SiL m R n )CH 3 (2-2),
—CH 2 CH═CH 2 (2-3),
—CH═CHCH 3 (2-4),
wherein in the formulae (2-1) to (2-4),
L: a hydrolysable group,
R: a monovalent hydrocarbon group,
m and n: m is an integer of from 1 to 3, n is an integer of from 0 to 2, and m+n=3.
19. The fluorinated ether composition according to claim 18 , wherein of the total of group B 10 present in the composition, the total proportion of the group of the formula (2-1) and the group of the formula (2-4) is from 95 to 100 mol %.
20. The fluorinated ether composition according to claim 19 , wherein of the total of group B 10 present in the composition, the proportion of the group of the formula (2-1) is from 92 to 99 mol %, the proportion of the group of the formula (2-2) is from 0 to 5 mol %, the proportion of the group of the formula (2-3) is from 0 to 5 mol %, and the proportion of the group of the formula (2-4) is from 1 to 8 mol %.
21. The fluorinated ether composition according to claim 18 , wherein A is a C 1-20 perfluoroalkyl group.
22. A coating liquid, comprising:
the fluorinated ether composition of claim 18 ; and
at least one fluorinated organic solvent (E) selected from the group consisting of a fluorinated alkane, a fluorinated aromatic compound and a fluoroalkyl ether.
23. A substrate having a surface-treated layer, treated with the fluorinated ether composition of claim 18 .
24. A touch panel having, at its input side, a substrate having a surface-treated layer, treated with the fluorinated ether composition of claim 18 .