# US 2013/0251908 A1 · Acid etch resistance for calcareous substrates

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- Number: US 2013/0251908 A1
- Document ID: US20130251908A1
- Status: Published application
- Kind: A1
- Application number: 13/424,731
- Filed: 2012-03-20
- Published: 2013-09-26
- Earliest claimed: 2012-03-20
- Assignees: E. I. Du Pont de Nemours and Company
- Inventors: Brad M. Rosen; Siddhartha R. Shenoy; Anilkumar Raghavanpillai; Ernest Bryon Wysong; Joel M. Pollino; James J. Hughes; John Russell Crompton, JR.
- Web page: https://patentgrep.com/patent/US20130251908A1

## CPC

- C09D 133/16: Homopolymers or copolymers of esters containing halogen atoms
- C04B 41/009: {characterised by the material treated}
- C04B 41/4842: {Fluorine-containing polymers}
- C04B 2111/203: {Oil-proof or grease-repellant materials}
- C04B 2111/23: Acid resistance, e.g. against acid air or rain
- C04B 2111/27: Water resistance, i.e. waterproof or water-repellent materials
- Y10T 428/3154: Of fluorinated addition polymer from unsaturated monomers
- 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)
- C04B: LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE {(roofing granules E04D7/005)}; CERAMICS (devitrified glass-ceramics C03C10/00); REFRACTORIES; TREATMENT OF NATURAL STONE
- Y10T: TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION

## Abstract

A method to provide acid etch resistance to contacting a calcareous substrate with a copolymer prepared from fluorinated methacrylate, short chain branched (meth)acrylate, and (meth)acrylic acid salt and a treated substrate.

## Claims

### Claim 1

A method of providing acid etch resistance, water repellency, oil repellency and stain resistance to a substrate surface comprising contacting the substrate surface with a copolymer of formula (I)
wherein
Rf is C1 to C10 linear or branched fluoroalkyl, optionally interrupted by one or more —O—, —CH2—, —CFH—, or combinations thereof;
Q is an alkylene of 1 to about 15 carbon atoms, hydroxyalkylene of 3 to about 15 carbon atoms, —(CnH2n)(OCqH2q)m—, —(CnH2n)(NR′)z—SO2—NR′(CnH2n)—, or —CONR′(CnH2n)—, wherein each R′ is independently H or an alkyl of from 1 to about 4 carbon atoms, n is independently 1 to about 15, q is 2 to about 4, m is 1 to about 15, and z is 0 or 1;
Ra is a C3 to C4 branched alkyl;
M is H, NH4, Na, Li, Cs, K, HNR3 or mixtures thereof;
R is C1 to C4 linear or branched alkyl;
a is an integer from about 20 to about 50 mol %;
b is an integer from about 5 to about 35 mol %; and
c is an integer from about 15 to about 60 mol %;
wherein the sum of a+b+c is equal to 100%.

### Claim 2 (depends on 1)

A method of claim 1, wherein the copolymer of Formula I is in the form of a dispersion.

### Claim 3 (depends on 2)

A method of claim 2, wherein the dispersion further comprises at least one surfactant.

### Claim 4 (depends on 2)

A method of claim 2, wherein the dispersion further comprises at least one sealer.

### Claim 5 (depends on 2)

A method of claim 2, wherein the dispersion further comprises at least one surfactant and at least one sealer.

### Claim 6 (depends on 1)

A method of claim 1 further comprising curing the copolymer of Formula I on the substrate.

### Claim 7 (depends on 1)

A method of claim 1, wherein the curing occurs from about 20° C. to from about 150° C. for a time from about 2 minutes to from about 14 days.

### Claim 8 (depends on 7)

A method of claim 7, wherein the curing occurs at about 20° C. for about 14 days.

### Claim 9 (depends on 7)

A method of claim 7, wherein the curing occurs at about 150° C. for about 2 minutes.

### Claim 10 (depends on 1)

A method of claim 1, wherein Rf is C4 to C6 fluoroalkyl and Q is —CH2CH2—.

### Claim 11 (depends on 1)

A method of claim 1, wherein Ra is isopropyl(meth)acrylate.

### Claim 12 (depends on 1)

A method of claim 1, wherein Ra is tert-butyl(meth)acrylate.

### Claim 13 (depends on 1)

A method of claim 1, wherein M is NH4.

### Claim 14 (depends on 1)

A method of claim 1 wherein the contacting is by brushing, spraying, rollering, dipping, padding, doctor blade, wipe, dip techniques, or wet-on-wet procedure.

### Claim 15 (depends on 1)

A method of claim 1 wherein the substrate contains calcium.

### Claim 16 (depends on 15)

A method of claim 15 wherein the substrate is white marble, black marble, limestone, or travertine.

### Claim 17 (depends on 1)

A substrate treated with a method of claim 1, which is white marble, black marble, limestone, or travertine.

### Claim 18 (depends on 2)

A substrate treated with a method of claim 2.

### Claim 19 (depends on 3)

A substrate treated with a method of claim 3.

### Claim 20 (depends on 4)

A substrate treated with a method of claim 4.