# US 7,745,653 B2 · Fluorochemical compounds having pendent silyl groups

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- Number: US 7,745,653 B2
- Document ID: US7745653B2
- Status: Granted
- Kind: B2
- Application number: 11/683,823
- Filed: 2007-03-08
- Published: 2008-09-11
- Granted: 2010-06-29
- Earliest claimed: 2007-03-08
- Assignees: 3M Innovative Properties Company
- Inventors: Suresh Iyer; Thomas P. Klun; Oscar S. Benz; Wayne W. Fan
- Web page: https://patentgrep.com/patent/US7745653B2

## CPC

- C09D 4/00: Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond {; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16}
- C07F 7/1804: {Compounds having Si-O-C linkages (Si-O-acyl linkages C07F7/1896)}
- Y10T 428/31663: As siloxane, silicone or silane
- C09D: COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR (cosmetics A61K; processes for applying liquids or other fluent materials to surfaces, in general, B05D; staining wood B27K5/02; glazes or vitreous enamels C03C; natural resins, French polish, drying-oils, driers, turpentine, per se, C09F; polishing compositions other than French polish, ski waxes C09G; adhesives or use of materials as adhesives C09J; materials for sealing or packing joints or covers C09K3/10; materials for stopping leaks C09K3/12; processes for the electrolytic or electrophoretic production of coatings C25D)
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)
- Y10T: TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION

## Abstract

Fluorochemical silane compounds and coating compositions derived therefrom are described. The compounds and compositions may be used in treating substrates, in particular substrates having a hard surface such as ceramics or glass, to render them water, oil, stain, and soil repellent.

## Claims

### Claim 1

A compound of the formula
wherein
Rf is a fluorine-containing group of the formula:
wherein
Rf 1 is a monovalent perfluorooxyalkyl group, or a divalent a perfluorooxyalkylene group comprising one or more perfluorinated repeating units selected from the group consisting of —(CnF2nO)—, —(CF(Z)O)—, —(CF(Z)CnF2nO)—, —(CnF2nCF(Z)O)—, —(CF2CF(Z)O)—, and combinations thereof, wherein n is 1 to 4 and Z is a perfluoroalkyl group, a perfluoroalkoxy group, or perfluorooxyalkyl group,
Q is a covalent bond, or a divalent alkylene or arylene group, said alkylene optionally containing one or more catenary heteroatoms,
X2 is —O—, —NR4— or —S—, where R4 is H or C1-C4 alkyl,
z is 1 or 2, and
v is 0 or 1;
Rl is a covalent bond, a polyvalent alkylene or arylene group, or combinations thereof, said alkylene groups optionally containing one or more catenary oxygen or nitrogen atoms:
R2 is of the formula:
wherein
X2 is —O, —S—or —NR4—, where R4 is H or C1-C4 alkyl,
R5 is C1-C4 alkyl, or —R6—Si(Yp)(R7)3-p or (Rf)x—R1—X2—C(O)—CH2CH2—;
R6 is a divalent alkylene group, said alkylene groups optionally containing one or more catenary oxygen atoms;
Y is a hydrolysable group,
R7 is a monovalent alkyl or aryl group,
p is 1, 2 or 3, and
x and y are each independently at least 1, and z is 1 or 2.

### Claim 2 (depends on 1)

The compound of claim 1 wherein R2 is a silane-containing moiety derived from a Michael reaction between a fluorine-containing acryloyl compound and an aminosilane.

### Claim 3 (depends on 1)

The compound of claim 1 wherein Rf1 comprises a group of the formula
W—Rf3—O—Rf4—(Rf5)q—
wherein
W is F for monovalent perfluorooxyalkyl, and an open valence (“—”) for divalent perfluorooxyalkylene;
Rf3 represents a perfluoroalkylene group,
Rf4 represents a perfluoroalkyleneoxy group consisting of perfluorooxyalkylene groups having 1, 2, 3 or 4 carbon atoms or a mixture of such perfluorooxyalkylene groups,
Rf5 represents a perfluoroalkylene group, and
q is 0 or 1.

### Claim 4 (depends on 1)

The compound of claim 1 wherein said perfluorooxyalkylene group is selected from one or more of —[CF2—CF2—O]r—; —[CF(CF3)—CF2—O]s—; —[CF2CF2—O]r—, [CF2O]t—, —[CF2CF2CF2CF2—O]u and —[CF2—CF2—O]r —[CF(CF3)—CF2—O]s—; wherein each of r, s, t and u each are integers of 1 to 50.

### Claim 5 (depends on 1)

The compound of claim 1 wherein Rf1 is a monovalent perfluorooxyalkyl group and z is 1.

### Claim 6 (depends on 1)

The compound of claim 1 wherein Rf is derived from a fluorinated mono- or polyol.

### Claim 7 (depends on 1)

The compound of claim 1, wherein Y is a halogen, a C1-C4 alkoxy group, or a C1-C4 acyloxy group.

### Claim 8 (depends on 1)

The compound of claim 1 wherein the molar ratio of silane groups to Rf groups is greater than 1:1.

### Claim 9 (depends on 1)

The compound of claim 1 derived from a nucleophilic acryloyl compound of the formula
Rf is a fluorine-containing group;
R1 is a covalent bond, a polyvalent alkylene or arylene group, or combinations thereof, said alkylene groups optionally containing one or more catenary oxygen or nitrogen atoms:
X2 is —O, —S—or —NR4—, where R4 is H or C1-C4 alkyl,
y is at least 1, and z is 1 or 2.

### Claim 10 (depends on 1)

The compound of claim 1, derived from an aminosilane is of the formula:
wherein
R5 is C1-C4 alkyl, or —R6—Si(Yp)(R7)3-p;
R6 is a divalent alkylene group, said alkylene groups optionally containing one or more catenary oxygen atoms;
Y is a hydrolysable group,
R7 is a monovalent alkyl or aryl group,
p is 1, 2 or 3, preferably 3.

### Claim 11 (depends on 1)

A coating composition comprising at least one compound of claim 1 and a solvent.

### Claim 12 (depends on 11)

The coating composition of claim 11 further comprising a silsesquioxane.

### Claim 13 (depends on 11)

A method of coating comprising the step of contacting a substrate with the coating composition of claim 11.

### Claim 14 (depends on 1)

A compound of claim 1 comprising a Michael addition reaction product of an aminosilane with a fluorine-containing compound having pendent acrylate groups; said fluorine-containing compound comprising the reaction product of an electrophilic fluorochemical compound, and a nucleophilic acryloyl compound.

### Claim 15 (depends on 1)

A compound of claim 1 of the formula:
wherein
Rf is a fluorine-containing group;
X2 is —O, —S—or —NR4—, where R4 is H or C1-C4 alkyl,
R5 is C1-C4 alkyl, or —R6—Si(Yp)(R7)3-p or (Rf)x—X2—C(O)—CH2CH2—;
R6 is a divalent alkylene group, said alkylene groups optionally containing one or more catenary oxygen atoms;
Y is a hydrolysable group,
R7 is a monovalent alkyl or aryl group,
p is 1, 2 or 3, and
z is 1 or 2.

### Claim 16 (depends on 1)

A coated article comprising a substrate having a cured coating of the silane compounds of claim 1.

### Claim 17 (depends on 16)

The coated article of claim 16 wherein the substrate is an antireflective substrate comprising an antireflective surface of a metal oxide film having one or more metal oxides.

### Claim 18 (depends on 17)

The article of claim 17 wherein the antireflective surface comprises a vacuum deposited metal oxide film.

### Claim 19 (depends on 16)

The article of claim 16, wherein the silane compounds are coated by vapor deposition.

### Claim 20 (depends on 16)

The article of claim 16 comprising: a transparent substrate having a first surface and a second surface; an antireflective coating on at least a portion of the first surface; and a coating of the silane disposed on the antireflective coating.

### Claim 21 (depends on 20)

The article of claim 20 wherein the transparent substrate comprises a flexible organic polymeric material.