Fluorinated ether compound, fluorinated ether composition, coating liquid, article and its production method

Patent metadata

Field	Value
Publication number	US-11634374-B2
Application number	US-202117469008-A
Country	US
Kind code	B2
Filing date	Sep 8, 2021
Priority date	May 26, 2017
Publication date	Apr 25, 2023
Grant date	Apr 25, 2023

Abstract

To provide a fluorinated ether compound capable of forming a surface layer excellent in initial water/oil repellency, fingerprint stain removability, abrasion resistance and light resistance; a fluorinated ether composition and a coating liquid containing the fluorinated ether compound; an article having a surface layer excellent in initial water/oil repellency, fingerprint stain removability, abrasion resistance and light resistance and a method for producing it. A fluorinated ether compound having a poly(oxyperfluoroalkylene) chain having a unit (α) which is an oxyperfluoroalkylene unit having 5 or 6 carbon atoms, and a unit (β) which is an oxyperfluoroalkylene unit having at most 4 carbon atoms, and having at least one of a hydrolysable silyl group and a silanol group on at least one terminal of the poly(oxyperfluoroalkylene) chain via a linking group.

First claim

The invention claimed is:

1. A fluorinated ether compound having a poly(oxyperfluoroalkylene) chain having a unit (α) which is an oxyperfluoroalkylene unit having 5 or 6 carbon atoms, and a unit (β) which is an oxyperfluoroalkylene unit having at most 4 carbon atoms, and having at least one of a hydrolysable silyl group and a silanol group on both terminals of the poly(oxyperfluoroalkylene) chain via a linking group,
wherein in the poly(oxyperfluoroalkylene) chain, a proportion of a number of the unit (α) to a total number of the unit (α) and the unit (β) is from 0.02 to 0.2.

2. The fluorinated ether compound according to claim 1 , wherein in the poly(oxyperfluoroalkylene) chain, the proportion of the number of the unit (α) to the total number of the unit (α) and the unit (β) is from 0.02 to 0.16.

3. The fluorinated ether compound according to claim 1 , wherein the poly(oxyperfluoroalkylene) chain contains a structure having the unit (α) and the unit (β) alternately arranged.

4. The fluorinated ether compound according to claim 1 , wherein the unit (α) is (CF 2 CF 2 CF 2 CF 2 CF 2 O) or (CF 2 CF 2 CF 2 CF 2 CF 2 CF 2 O).

5. The fluorinated ether compound according to claim 1 , wherein the unit (β) is (CF 2 O) or (CF 2 CF 2 O).

6. The fluorinated ether compound according to claim 1 , which is a compound represented by the following formula (11):
B 1 —O—[(R f1 O) m1 (R f2 O) m2 (R f3 O) m3 (R f4 O) m4 (R f5 O) m5 (R f6 O) m6 ]—B 1   (11)

wherein
R f1 is a C 1 perfluoroalkylene group,
R f2 is a C 2 perfluoroalkylene group,
R f3 is a C 3 perfluoroalkylene group,
R f4 is a C 4 perfluoroalkylene group,
R f5 is a C 5 perfluoroalkylene group,
R f6 is a C 6 perfluoroalkylene group,
m1, m2, m3, m4, m5 and m6 are each 0 or an integer of at least 1, m1+m2+m3+m4 is an integer of at least 1, m5+m6 is an integer of at least 1, and m1+m2+m3+m4+m5+m6 is an integer of from 2 to 200,
B 1 is -Q[-SiR n L 3-n ] k ,
Q is a (k+1) valent linking group,
R is a hydrogen atom or a monovalent hydrocarbon group,
L is a hydrolysable group or a hydroxy group,
n is an integer of from 0 to 2, and
k is an integer of from 1 to 10.

7. The fluorinated ether compound according to claim 6 , wherein B 1 is a group represented by any one of the following formulae (g1) to (g7):
—R f7 —(X 1 ) p -Q 1 -SiR n L 3-n   (g1)

—R f7 —(X 2 ) r -Q 2 -N[-Q 22 -SiR n L 3-n ] 2   (g2)

-R f7 -[C(O)N(R 31 )] s -Q 31 -(O) t —C[—(O) u -Q 32 -SiR n L 3-n ] 3   (g3)

—R f7 -Q 41 -Si[-Q 42 -SiR n L 3-n ] 3   (g4)

—R f7 —[C(O)N(R 5 )] v -Q 51 -Z[-Q 52 -SiR n L 3-n ] w   (g5)

—R f7 -Q 61 -G(R 6 )[-Q 62 -SiR n L 3-n ] 2   (g6)

—R f7 -Q 71 -[CH 2 C(R 71 )(-Q 72 -SiR n L 3-n )] y —R 72   (g7)

wherein
R f7 is a C 1-6 perfluoroalkylene group,
R is a hydrogen atom or a monovalent hydrocarbon group,
L is a hydrolysable group or a hydroxy group,
n is an integer of from 0 to 2,
in the formula (g1),
X 1 is an etheric oxygen atom or —C(O)N(R 1 )— provided that N is bonded to Q 1 ,
R is a hydrogen atom or an alkyl group,
p is 0 or 1, and
Q 1 is an alkylene group, a group having an etheric oxygen atom or a silphenylene skeleton between carbon atoms of an alkylene group having at least 2 carbon atoms, or a group having a bivalent organopolysiloxane residue or a dialkylsilylene group between carbon atoms or at a terminal on the side bonded to (X 1 ) p of an alkylene group having at least 2 carbon atoms,
in the formula (g2),
X 2 is an etheric oxygen atom, —NH— or —C(O)N(R 2 )— provided that N is bonded to Q 21 ,
R 2 is a hydrogen atom or an alkyl group,
r is 0 or 1 provided that it is 0 when Q 21 is a single bond,
Q 21 is a single bond, an alkylene group, or a group having an etheric oxygen atom, —NH—, —C(O)—, —C(O)O— or —OC(O)— between carbon atoms of an alkylene group having at least 2 carbon atoms,
Q 22 is an alkylene group, or a group having an etheric oxygen atom, —NH— or a bivalent organopolysiloxane residue between carbon atoms of an alkylene group having at least 2 carbon atoms, and
two [-Q 22 -SiR n L 3-n ] may be the same or different,
in the formula (g3),
R 31 is a hydrogen atom or an alkyl group,
s is 0 or 1,
Q 31 is a single bond, an alkylene group, or a group having an etheric oxygen atom between carbon atoms of an alkylene group having at least 2 carbon atoms,
t is 0 or 1 provided that it is 0 when Q 31 is a single bond,
u is 0 or 1,
Q 32 is an alkylene group, a group having an etheric oxygen atom or a silphenylene skeleton between carbon atoms of an alkylene group having at least 2 carbon atoms, or a group having —C(O)N(R 32 )—, a bivalent organopolysiloxane residue or a dialkylsilylene group between carbon atoms or at a terminal on the side bonded to (O) u of an alkylene group having at least 2 carbon atoms,
R 32 is a hydrogen atom or an alkyl group, and
three [—(O) u -Q 32 -SiR n L 3-n ] may be the same or different,
in the formula (g4),
Q 41 is an alkylene group, or a group having an etheric oxygen atom between carbon atoms of an alkylene group having at least 2 carbon atoms,
Q 42 is an alkylene group, or a group having an etheric oxygen atom or a bivalent organopolysiloxane residue between carbon atoms of an alkylene group having at least 2 carbon atoms, and
three [-Q 42 -SiR n L 3-n ] may be the same or different,
in the formula (g5),
R 5 is a hydrogen atom or an alkyl group,
v is 0 or 1,
Q 51 is an alkylene group, or a group having an etheric oxygen atom between carbon atoms of an alkylene group having at least 2 carbon atoms,
Z is a (w+1) valent organopolysiloxane residue,
Q 52 is an alkylene group, or a group having an etheric oxygen atom or a bivalent organopolysiloxane residue between carbon atoms of an alkylene group having at least 2 carbon atoms,
w is an integer of from 2 to 7, and
w [-Q 52 -SiR n L 3-n ] may be the same or different,
in the formula (g6),
Q 61 is a single bond, an alkylene group, or a group having an etheric oxygen atom between carbon atoms of an alkylene group having at least 2 carbon atoms,
G is a carbon atom or a silicon atom,
R 6 is a hydroxy group or an alkyl group,
Q 62 is an alkylene group, or a group having an etheric oxygen atom or a bivalent organopolysiloxane residue between carbon atoms of an alkylene group having at least 2 carbon atoms, and
two [-Q 62 -SiR n L 3-n ] may be the same or different, and
in the formula (g7),
Q 71 is a single bond, an alkylene group, or a group having an etheric oxygen atom between carbon atoms of an alkylene group having at least 2 carbon atoms,
R 71 is a hydrogen atom or an alkyl group,
Q 72 is a single bond or an alkylene group,
R 72 is a hydrogen atom or a halogen atom,
y is an integer of from 1 to 10, and
two to ten [-Q 72 -SiR n L 3-n ] may be the same or different.

8. A fluorinated ether composition, comprising at least one of the fluorinated ether compound according to claim 1 , and at least one other fluorinated ether compound.

9. A coating liquid comprising the fluorinated ether composition according to claim 8 , and a liquid medium.

10. A method for producing an article, which comprises applying the coating liquid according to claim 9 by wet coating method to a surface of a substrate, and removing the liquid medium, to form a surface layer on the surface of the substrate.

11. An article having a surface layer formed of the fluorinated ether composition according to claim 8 , on a surface of a substrate.

12. A method for producing an article, which comprises treating a surface of a substrate by dry coating method using the fluorinated ether composition according to claim 8 to fo

Assignees

• Agc Inc

Inventors

• Hoshino Taiki
• Uno Makoto
• Ito Masahiro

Classifications

• C09K3/18

  for application to surfaces to minimize adherence of ice, mist or water thereto (rendering particulate materials free flowing, in general, e.g. making them hydrophobic B01J2/30); Thawing or antifreeze materials for application to surfaces (used in liquids for heat-transfer, heat-exchange or heat-storage or for the production of heat or cold other than by combustion, e.g. radiator liquids, C09K5/00) · CPC title

• C07F7/18 Primary

  Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages · CPC title

• C09D5/00

  Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced {(electrically insulating plastics, resins or waxes H01B3/30)}; Filling pastes · CPC title

• C09D171/02

  Polyalkylene oxides · CPC title

• C08G65/336 Primary

  containing silicon · CPC title