Durable architectural coatings containing crosslinkable polymeric additives

1. A composition comprising

a. a coating base selected from a water-dispersed coating, an epoxy polymer coating, an alkyd coating, a Type I urethane coating, or an unsaturated polyester coating; and

b. a crosslinkable polymer made by reacting:

i. a fluoropolymer comprising the repeat Unit A, at least one of repeat Units B or C, and optionally one or more of repeat Units D or E, in any order; with

ii. a hydroxy-reactive compound or carboxylic acid-reactive compound selected from the group consisting of a polyamine compound having at least 2 amine groups, an isocyanate-terminated silane, an isocyanate-terminated vinylic or (meth)acrylic compound, a glycidyl group-containing vinylic or (meth)acrylic compound, a carbodiimide compound, a blend of polyisocyanate with a hydroxyl-terminated vinylic or (meth)acrylic compound, and mixtures thereof;

wherein

the composition comprises (a) the coating base in an amount of from about 95 to 99.98% and (b) the crosslinkable polymer in an amount of from about 0.02 to 5% by weight, based on the total weight of (a) and (b);

R f is a straight or branched-chain perfluoroalkyl group of 2 to 20 carbon atoms, optionally interrupted by one or more ether oxygens —O—, —CH 2 —, —CFH—, or combinations thereof;

A is O, S, or N(R 2 );

Q is a straight chain, branched chain or cyclic structure of alkylene, alkoxy, arylene, aralkylene, sulfonyl, sulfoxy, sulfonamido, carbonamido, carbonyloxy, urethanylene, ureylene, or combinations thereof;

v is 0 or 1;

R 1 is H or CH 3 ;

R 2 is independently selected from H or a linear or branched alkyl of 1 to about 4 carbon atoms;

Z is a hydrophilic group selected from a hydroxy-terminated straight or branched alkyl of 1 to 10 carbons; hydroxy-terminated straight or branched alkoxylate having 2 to 20 alkoxylate repeat units; or hydroxyalkyl-terminated straight or branched alkoxylate having 2 to 20 alkoxylate repeat units;

R 3 is a straight or branched alkyl chain of 2 to 30 carbons having 1 to 15 olefinic units, or mixtures thereof;

Y is selected from CH 2 O—, —C(O)O—, —OC(O)—, —R 5 OC(O)—, —C(O)O(CH 2 CH 2 O) m (CH 2 CH(CH 3 )O) n —, or —C(O)OR 5 O—;

R 5 is a straight or branched alkylene of 1 to 10 carbons;

m and n are independently integers of 0 to 20, provided that m+n>0;

R 4 is a straight chain, branched chain, or cyclic structure alkyl group of 1 to 30 carbons;

R 6 is H, Na, Li, Cs, K, HN(R 2 ) 3 , or mixtures thereof;

Unit A is present in an amount of about 10 to 60 mol %;

Unit B is present in an amount of about 0 to 40 mol %;

Unit C is present in an amount of about 0 to 40 mol %;

Unit D is present in an amount of about 0 to 50 mol %; and

Unit E is present in an amount of about 0 to 50 mol %;

wherein the sum of Units B and C amounts is a positive mol %, and

wherein the sum of monomer repeat units is equal to 100%.

2. The composition of claim 1 , where the crosslinkable polymer has a number average molecular weight Mn of about 1500 to about 50,000 Daltons.

3. The composition of claim 1 , where the amount of Unit C is a positive mol %.

4. The composition of claim 3 , where the crosslinkable polymer is made by reacting Unit C with a carboxylic acid-reactive compound selected from a polyamine compound having at least 2 amine groups, a glycidyl group-containing vinylic or (meth)acrylic compound, or a carbodiimide compound.

5. The composition of claim 1 , where the amount of Unit B is a positive mol %.

6. The composition of claim 5 , where the crosslinkable polymer is made by reacting Unit B with a hydroxyl-reactive compound selected from an isocyanate-terminated vinylic or (meth)acrylic compound, an isocyanate-terminated silane, or a blend of polyisocyanate with a hydroxyl-terminated vinylic or (meth)acrylic compound.

7. The composition of claim 1 , where the fluoropolymer further comprises a residue from a hydrophilic chain transfer agent of formula (I)

(V—X—S) g H 2-g   (I),

wherein

g is 1 or 2

X is a linear or branched alkylene of 1 to about 4 carbon atoms, optionally substituted with one or more hydrophilic functional groups selected from hydroxyl, carboxyl, or amine; and

V is a hydrophilic functional group selected from hydroxyl, carboxyl, thiol, or amine.

8. The composition of claim 1 , where the coating base is a water-dispersed coating selected from an aqueous acrylic latex paint.

9. The composition of claim 1 , where the coating base comprises an additive selected from TiO 2 , clays, asbestos, calcium carbonate, zinc oxide, chromium oxide, barium sulfate, iron oxide, tin oxide, calcium sulfate, talc, mica, silicas, dolomite, zinc sulfide, antimony oxide, zirconium dioxide, silicon dioxide, cadmium sulfide, cadmium selenide, lead chromate, zinc chromate, nickel titanate, diatomaceous earth, glass fibers, glass powders, glass spheres, blue pigments, red pigments, yellow pigments, orange pigments, process aggregated crystals, brown pigments, or green pigments.

10. A process for forming a coating with improved dirt pickup resistance comprising

a. contacting a coating base selected from a water-dispersed coating, an epoxy polymer coating, an alkyd coating, a Type I urethane coating, or an unsaturated polyester coating; with a crosslinkable polymer to form a coating composition;

b. applying the coating composition to a substrate to form a coating;

c. allowing the crosslinkable polymer to migrate to the coating surface to form a crosslinkable surface coating, and

d. subsequently reacting the crosslinkable surface coating; wherein

the coating comprises the coating base in an amount of from about 95 to 99.98% and the crosslinkable polymer in an amount of from about 0.02 to 5% by weight, based on the total weight of the coating base and the crosslinkable polymer;

the crosslinkable polymer is the reaction product of

i. a fluoropolymer comprising the repeat Unit A, at least one of repeat Units B or C, and optionally one or more of repeat Units D or E, in any order; with

ii. a hydroxyl-reactive compound or carboxylic acid-reactive compound selected from the group consisting of a polyamine compound having at least 2 amine groups, an isocyanate-terminated silane, an isocyanate-terminated vinylic or (meth)acrylic compound, a glycidyl group-containing vinylic or (meth)acrylic compound, a carbodiimide compound, a blend of polyisocyanate with a hydroxyl-terminated vinylic or (meth)acrylic compound, and mixtures thereof;

wherein

R f is a straight or branched-chain perfluoroalkyl group of 2 to 20 carbon atoms, optionally interrupted by one or more ether oxygens —O—, —CH 2 —, —CFH—, or combinations thereof;

A is O, S, or N(R 2 );

Q is a straight chain, branched chain or cyclic structure of alkylene, alkoxy, arylene, aralkylene, sulfonyl, sulfoxy, sulfonamido, carbonamido, carbonyloxy, urethanylene, ureylene, or combinations thereof;

v is 0 or 1;

R 1 is H or CH 3 ;

R 2 is independently selected from H or a linear or branched alkyl of 1 to about 4 carbon atoms;

Z is a hydrophilic group selected from a hydroxy-terminated straight or branched alkyl of 1 to 10 carbons; hydroxy-terminated straight or branched alkoxylate having 2 to 20 alkoxylate repeat units; or hydroxyalkyl-terminated straight or branched alkoxylate having 2 to 20 alkoxylate repeat units;

R 3 is a straight or branched alkyl chain of 2 to 30 carbons having 1 to 15 olefinic units, or mixtures thereof;

Y is selected from —CH 2 O—, —C(O)O—, —OC(O)—, —R 5 OC(O)—, —C(O)O(CH 2 CH 2 O) m (CH 2 CH(CH 3 )O) n —, or —C(O)OR 5 O—;

R 5 is a straight or branched alkylene of 1 to 10 carbons;

m and n are independently integers of 0 to 20, provided that m+n>0;

R 4 is a straight chain, branched chain, or cyclic structure alkyl group of 1 to 30 carbons;

R 6 is H, Na, Li, Cs, K, HN(R 2 ) 3 , or mixtures thereof;

Unit A is present in an amount of about 10 to 60 mol %;

Unit B is present in an amount of about 0 to 40 mol %;

Unit C is present in an amount of about 0 to 40 mol %;

Unit D is present in an amount of about 0 to 50 mol %; and

Unit E is present in an amount of about 0 to 50 mol %;

wherein the sum of Units B and C amounts is a positive mol %, and

wherein the sum of monomer repeat units is equal to 100%.

11. The process of claim 10 , where the crosslinkable polymer has a number average molecular weight Mn of about 1500 to about 50,000 Daltons.

12. The composition of claim 1 , where the amount of Unit C is a positive mol %, and the crosslinkable polymer is made by reacting Unit C with a carboxylic acid-reactive compound selected from a polyamine compound having at least 2 amine groups, a glycidyl group-containing vinylic or (meth)acrylic compound, or a carbodiimide compound.

13. The composition of claim 1 , where the amount of Unit B is a positive mol %, and the crosslinkable polymer is made by reacting Unit B with a hydroxyl-reactive compound selected from an isocyanate-terminated vinylic or (meth)acrylic compound, an isocyanate-terminated silane, or a blend of polyisocyanate with a hydroxyl-terminated vinylic or (meth)acrylic compound.

14. The process of claim 10 , where the hydroxyl-reactive compound or carboxylic acid-reactive compound is selected from the group consisting of an isocyanate-terminated vinylic or (meth)acrylic compound, a glycidyl group-containing vinylic or (meth)acrylic compound, a blend of polyisocyanate with a hydroxyl-terminated vinylic or (meth)acrylic compound, and mixtures thereof, and the curing step occurs by radiation-initiated polymerization.

15. A coated substrate made by the process of claim 10 .

16. The coated substrate of claim 15 , where the substrate is selected from the group consisting of wood, metal, wallboard, masonry, concrete, fiberboard, and paper.