US 12,240,993 B2
Article with water and oil repellent layer
Yusuke Tomiyori, Tokyo (JP); Motoshi Aoyama, Tokyo (JP); and Kenji Ishizeki, Tokyo (JP)
Assigned to AGC Inc., Tokyo (JP)
Filed by AGC Inc., Tokyo (JP)
Filed on Mar. 21, 2022, as Appl. No. 17/655,671.
Application 17/655,671 is a continuation of application No. PCT/JP2020/037757, filed on Oct. 5, 2020.
Claims priority of application No. 2019-185182 (JP), filed on Oct. 8, 2019.
Prior Publication US 2022/0220318 A1, Jul. 14, 2022
Int. Cl. C09D 5/00 (2006.01); C03C 17/42 (2006.01); C08G 77/26 (2006.01); C09D 1/02 (2006.01); C09D 183/08 (2006.01); C23C 14/12 (2006.01); C23C 14/24 (2006.01)
CPC C09D 5/002 (2013.01) [C03C 17/42 (2013.01); C08G 77/26 (2013.01); C09D 1/02 (2013.01); C09D 183/08 (2013.01); C23C 14/12 (2013.01); C23C 14/24 (2013.01); C03C 2217/76 (2013.01); C03C 2218/116 (2013.01); C03C 2218/151 (2013.01); C03C 2218/31 (2013.01)] 7 Claims
OG exemplary drawing
 
1. An article comprising:
a substrate;
a water and oil repellent layer consisting of a hydrolyzed condensation product of a fluorinated compound represented by the formula (1-3); and
a silicon oxide layer containing alkali metal atoms, the silicon oxide layer disposed between the substrate and the water and oil repellent layer,
wherein in the silicon oxide layer, the average value of the concentration of the alkali metal atoms in a region with a depth of from 0.1 to 0.3 nm from the surface in contact with the water and oil repellent layer is at least 2.0×1019 atoms/cm3:
[L3-n(R)nSi—]k3Y32—(OX)m—O—Y31[—Si(R)nL3-n]g3  (1-3),
m is an integer of at least 2,
R is a monovalent hydrocarbon group,
n is an integer of from 0 to 2,
L is a hydrolyzable group or a hydroxy group,
X is a fluoroalkylene group having at least one fluorine atom,
k3 is an integer of at least 1,
Y32 is a (k3+1) valent linking group,
Y31 is a (g3+1) valent linking group, and
g3 is an integer of at least 1,
wherein OX includes at least one selected from the group consisting of —OCHF—, —OCF2CHF—, —OCHFCF2—, —OCH2CF2—, —OCF2CF2CHF—, —OCHFCF2CF2—, —OCH2CF2CF2—, —OCH2CF2CF2CF2—, —OCH2CF2CF2CF2CF2—, —OCF2CF2CF2CF2CF2CH2—, —OCH2CF2CF2CF2CF2CF2—, —OCF2CF2CF2CF2CF2—, —OCF2CF2CF2CF2CF2CF2—, —O-cycloC4F6—, —O-cycloC5F8— and —O-cycloC6F10—,
wherein Y31 and Y32 in the formula (1-3) are each independently the group (g2-2) when g3=e2, k3=e2, the group (g2-3) when g3=2, k3=2, the group (g2-4) when g3=h2, k3=h2, the group (g2-5) when g3=i2, k3=i2, the group (g2-7) when g3=i3+1, k3=i3+1, or the group (g2-9) when g3=i5, k3=i5, or the fluorinated compound represented by the formula (1-3) conforms to formula (1-3′),

OG Complex Work Unit Chemistry
(-A1-)e1C(Re2)4-e1-e2(-Q22-)e2  (g2-2)
-A1-N(-Q23-)2  (g2-3)
(-A1-)h1Z1(-Q24-)h2  (g2-4)
(-A1-)i1Si(Re3)4-i1-i2(-Q25-)i2  (g2-5)
-A1-CH(-Q22-)—Si(Re3)3-i3(-Q25-)i3  (g2-7)
-A1-Za(-Q28-)i5  (g2-9)
an A1 side is connected to (OX)m, and a Q22, Q23, Q24, Q25 or Q28 side is connected to [—Si(R)nL3-n],
A1 is a single bond, an alkylene group, or a group having —C(O)—, —C(O)O—, —OC(O)O—, —OC(O)O—, —C(O)NR6—, —NR6C(O)—, —NHC(O)O—, —NHC(O)NR6—, —O— or —SO2NR6-between carbon-carbon atoms of an alkylene group with two or more carbon atoms,
Of is —(OX)m—O—,
Q22 is an alkylene group, a group having —C(O)NR6—, —C(O)—, —NR6— or —O— between carbon-carbon atoms of an alkylene group with two or more carbon atoms, a group having —C(O)NR6—, —C(O)—, —NR6— or —O— at the terminal of an alkylene group not connected to Si, or a group having —C(O)NR6—, —C(O)—, —NR6— or —O— between carbon-carbon atoms of an alkylene group with two or more carbons and having ˜C(O)NR6—, —NR6C(O)—, —C(O)—, —C(O)O—, —OC(O)—, —NR6— or —O— at the terminal not connected to Si,
Q23 is an alkylene group, or a group having —C(O)NR6—, —C(O)—, —NR6— or —O— between carbon-carbon atoms of an alkylene group having two or more carbon atoms, and the two Q23 may be the same or different,
Q24 is Q22 if the atom in Z1 to which Q24 is bonded is a carbon atom, and is Q23 if the atom in Z1 to which Q24 is bonded is a nitrogen atom,
Q25 is an alkylene group, or a group having —C(O)NR6—, —C(O)—, —NR6— or —O— between carbon-carbon atoms of an alkylene group with two or more carbon atoms,
Q28 is an alkylene group, or a group having an etheric oxygen atom or a divalent organopolysiloxane residue between carbon-carbon atoms in an alkylene group with two or more carbon atoms,
R6 is a hydrogen atom, a C1-6 alkyl group, or a phenyl group,
Z1 is a group having a h1+h2 valent ring structure which has a carbon or nitrogen atom to which A1 is directly bonded and has a carbon or nitrogen atom to which Q24 is directly bonded,
Za is a (i5+1) valent organopolysiloxane residue,
Re2 is a hydrogen atom, a hydroxy group, an alkyl group, or an acyloxy group,
Re3 is an alkyl group,
e1 is 1,
e2 is 2 or 3,
h1 is 1,
h2 is an integer of at least 1,
i1 is 1,
i2 is 2 or 3,
i3 is 2 or 3, and
i5 is an integer of from 2 to 7.