Anionic/cationic masonry sealing systems

1. A composition comprising an aqueous first mixture, having a maximum molar ratio of acid to base of 0.6 and providing water repellency having a rating of a maximum of 4 when applied to a substrate surface without etching of said surface, of

A. an anionic aqueous fluoroalkyl phosphate solution which provides at least about 75% of the total fluorine content of said first mixture comprising

1) a second mixture of mono(perfluoroalkyl) phosphate and bis(perfluoroalkyl)phosphate of Formula IA,

[R f —(O) j ] x —P(O)—(O − X + ) (3-x)   Formula 1A

 wherein:

R f is selected from the group consisting of

F(CF 2 CF 2 ) d (CH 2 ) a —,

F(CF 2 CF 2 ) d CH 2 CH 2 (OCH 2 CH 2 ) b —,

F(CF 2 CF 2 ) d —,

F(CF 2 CF 2 ) d CH═CH(CH 2 ) c —, and

C 8 F 17 SO 2 N(R 5 )CH 2 CH 2 —;

a is from about 2 to about 10,

b is from about 3 to about 20,

c is from about 2 to about 20,

d is 1 to about 8, or a mixture thereof,

R 5 is H or an aliphatic group containing 1 to about 4 carbon atoms,

x is from about 1 to about 2,

j is 1 or 0, or a mixture thereof, and

X is hydrogen or M,

M is an ammonium ion, an alkali metal ion, or an alkanolammonium ion, or

2) a phosphate of the structure of Formula IB

wherein

R f ′ is a fluoroaliphatic group having a linear or branched perfluorocarbon chain having from about 2 to about 20 carbon atoms,

R 6 is an alkylene group having from 1 to about 8 carbon atoms,

Z is —O—, —S—, or —NH—, and

M is as defined above in Formula IA, and

B. a cationic fluoroalkyl(meth)acrylate or perfluoroalkylether(meth)acrylate copolymer present at a minimum of 0.3 g per 100 g of said first mixture, and comprising monomers copolymerized in the following percentages by weight:

(a) from about 40% to about 92% of at least one monomer of formula 2A

R f ′-Q-A-C(O)—C(R 7 )═CH 2   2A

wherein:

R f ′ is a fluoroaliphatic group having a linear or branched perfluorocarbon chain having from about 2 to about 20 carbon atoms,

R 7 is H or an aliphatic group containing 1 to about 4 carbon atoms,

A is O, S or NR 1 wherein R 1 is H or an alkyl of 1 to about 4 carbon atoms, and

Q is 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 —, —SO 2 —NR 1 (C n H 2n )—, or —CONR 1 (C n H 2n )—, wherein R 1 is H or alkyl of 1 to about 4 carbon atoms, n is 1 to about 15, q is 2 to about 4, and m is 1 to about 15; and

R is hydrogen or a C1 about C2 alkyl group,

(b) from about 1% to about 50% of a monomer of formula 2B

(CH 2 ═C(R 7 )COW(CH 2 ) r + NR 2 R 3 R 4 )Y −   2B

wherein

R 7 is H or an aliphatic group containing 1 to about 4 carbon atoms,

R 2 and R 3 are each independently alkyl of 1 to about 4 carbon atoms, hydroxyethyl, or benzyl or R 2 and R 3 together with the nitrogen atom form a morpholine, pyrrolidine, or piperidine ring,

R 4 is alkyl of 1 to about 4 carbon atoms or R 2 , R 3 , and R 4 together with the nitrogen form a piperidine ring,

W is —O— or —NR 4 —,

r is 2 to 4, and

Y − is an anion, provided that the nitrogen is from about 40% to 100% quaternized using an acid having a dissociation constant greater than 10 −5 ; and

(c) from 0% to about 20% of an anionic monomer or a monomer which is potentially anionic by varying the pH;

(d) from about 0% to about 10% of a vinyl derivative of formula 2C

R 8 —CH═CH 2   2C

wherein

R 8 is an alkyl carboxylate or alkyl ether group containing from 1 to about 18 carbon atoms; and

(e) from 0 to about 25% of at least one monomer of formula 2D

CH 2 ═C(R 9 )—C(O)—O—V—OH   2D

wherein

R 9 is H or an alkyl of 1 to about 4 carbon atoms, and

V is an alkylene of from about 2 to about 4 carbon atoms; and

(f) from 0 to about 30% of any monomer other than the monomers of components (a) to (e) described above;

provided that the weight percents for components (a) to (f) described above total 100%.

2. The composition of claim 1 wherein the fluoroalkyl phosphate solution of component A is a mixture of mono(perfluoroalkyl)phosphate and bis(perfluoroalkyl)phosphate of Formula IA.

3. The composition of claim 2 wherein the fluoroalkyl phosphate solution of component A is a mixture of perfluoroalkylethyl phosphate diethanolamine salts.

4. The composition of claim 2 wherein the copolymer of component B is a copolymer prepared by copolymerization of formula 2A and formula 2B.

5. The composition of claim 4 wherein component B is a copolymer of perfluoroalkylethyl(meth)acrylate, and dimethylaminoethyl(meth)acrylate.

6. The composition of claim 1 which provides stain resistance when applied to a substrate surface.

7. The composition of claim 1 further comprising a microbicide.

8. The composition of claim 1 wherein the fluoroalkyl phosphate solution provides about 80% of the total fluorine content.

9. The composition of claim 1 wherein the total fluorine content is from about 0.25 to about 7.5 percent by weight.