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

Patent metadata

Field	Value
Publication number	US-11155508-B2
Application number	US-201916679454-A
Country	US
Kind code	B2
Filing date	Nov 11, 2019
Priority date	May 26, 2017
Publication date	Oct 26, 2021
Grant date	Oct 26, 2021

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 represented by the following formula (11):
A 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 A 1 is a C 1-20 perfluoroalkyl group,
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 hydrolyzable group or a hydroxy group,
n is an integer of from 0 to 2,
k is an integer of from 1 to 10, and
all the (R f5 O) and (R f6 O) are located on the A 1 -O— side from the [0.5×(m1+m2+m3+m4+m5+m6)]th unit as counted from the A 1 -O— side.

2. The fluorinated ether compound according to claim 1 , 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 21 -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 hydrolyzable 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 1 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.

3. A fluorinated ether composition, comprising at least one type of the fluorinated ether compound as defined in claim 1 , and other fluorinated ether compound.

4. A coating liquid comprising the fluorinated ether compound as defined in claim 1 , and a liquid medium.

5. A method for producing an article, which comprises applying the coating liquid as defined in claim 4 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.

6. An article having a surface layer formed of the fluorinated ether compound as defined in claim 1 , on a surface of a substrate.

7. A method for producing an article, which comprises treating a surface of a substrate by dry coating method using the fluorinated ether compound as defined in claim 1 to form a surface layer on the surface of the substrate.

8. A fluorinated ether compound, which is a compound represented by the following formula (10):
[A 10 -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 }] j —B 10   (10)

wherein A 10 is a C 1-20 perfluoroalkyl group or B 10 ,
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,
j is an integer of from 2 to 10,
B 10 is Q 10 [—SiR n L 3-n ] k ,
Q 10 is a (k+j) valent linking group,
R is a hydrogen atom or a monovalent hydrocarbon group,
L is a hydrolyzable group or a hydroxy group,
n is an integer of from 0 to 2, and
k is an integer of from 1 to 10.

9. The fluorinated ether compound according to claim 8 , wherein in the formula (10), A 1

Assignees

• Agc Inc

Inventors

• Hoshino Taiki
• Uno Makoto
• Ito Masahiro

Classifications

• C07C43/126 Primary

  having more than one ether bond · CPC title

• C09D7/63

  organic · CPC title

• C08G65/336 Primary

  containing silicon · 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

• B05D7/24

  for applying particular liquids or other fluent materials · CPC title