Acid etch resistance for calcareous substrates
View Patent ↗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.
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
R f is C 1 to C 10 linear or branched fluoroalkyl, optionally interrupted by one or more —O—, —CH 2 —, —CFH—, or combinations thereof;
Q is an alkylene of 1 to about 15 carbon atoms, hydroxyalkylene of 3 to about 15 carbon atoms, —(C n H 2n )(OC q H 2q ) m —, —(C n H 2n )(NR′) z —SO 2 —NR′(C n H 2n )—, or —CONR′(C n H 2n )—, 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;
R a is a C 3 to C 4 branched alkyl;
M is H, NH 4 , Na, Li, Cs, K, HNR 3 or mixtures thereof;
R is C 1 to C 4 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%.
2. A method of claim 1 , wherein the copolymer of Formula I is in the form of a dispersion.
3. A method of claim 2 , wherein the dispersion further comprises at least one surfactant.
4. A method of claim 2 , wherein the dispersion further comprises at least one sealer.
5. A method of claim 2 , wherein the dispersion further comprises at least one surfactant and at least one sealer.
6. A method of claim 1 further comprising curing the copolymer of Formula I on the substrate.
7. A method of claim 6 , wherein the curing occurs from about 20° C. to from about 150° C. for a time from about 2 minutes to about 14 days.
8. A method of claim 7 , wherein the curing occurs at about 20° C. for about 14 days.
9. A method of claim 7 , wherein the curing occurs at about 150° C. for about 2 minutes.
10. A method of claim 1 , wherein R f is C 4 to C 6 fluoroalkyl and Q is —CH 2 CH 2 —.
11. A method of claim 1 , wherein R a is isopropyl(meth)acrylate.
12. A method of claim 1 , wherein R a is tert-butyl(meth)acrylate.
13. A method of claim 1 , wherein M is NH 4 .
14. 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.
15. A method of claim 1 wherein the substrate contains calcium.
16. A method of claim 15 wherein the substrate is white marble, black marble, limestone, or travertine.
17. A substrate treated with a method of claim 1 , which is white marble, black marble, limestone, or travertine.
18. A substrate treated with a method of claim 2 .
19. A substrate treated with a method of claim 3 .
20. A substrate treated with a method of claim 4 .