Anionic/cationic masonry sealing systems

Abstract

A composition comprising a mixture, having a maximum molar ratio of acid to base of 0.6 and providing water repellency 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 composition, and B) a cationic copolymer of fluoroalkyl(meth)acrylate or perfluoroalkylether(meth)acrylate present at a minimum of 0.3 g per 100 g of said composition.

1 . A composition comprising an aqueous first mixture, having a maximum molar ratio of acid to base of 0.6 and providing water repellency 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 to 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 H or 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; 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 4  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.  
   
   
       10 . A process for the preparation of a composition of  claim 1  comprising 1) addition of water to a dispersion of the cationic copolymer of component B and mixing to yield a diluted copolymer, 2) addition of the anionic fluoroalkyl phosphate solution of component A to the diluted copolymer of component B, and 3) mixing or homogenizing.  
   
   
       11 . The process of  claim 10  wherein the amount of water added to component B per 100 g of composition is equal to 100 minus the total weight of component A and component B.  
   
   
       12 . A method of treating a substrate comprising application to the surface of the substrate of a composition of  claim 1 .  
   
   
       13 . The method of  claim 12  wherein the composition is applied as a first coating followed by at least one additional coating.  
   
   
       14 . The method of  claim 13  wherein the additional coating is applied prior to the first coating becoming dry.  
   
   
       15 . The method of  claim 12  wherein the substrate is a composition containing calcium carbonate.  
   
   
       16 . The method of  claim 12  wherein the substrate is unglazed concrete, brick, tile, stone, granite, limestone, grout, mortar, composite materials such as terrazzo, gypsum board, marble, statuary, monuments, or wood.  
   
   
       17 . A substrate treated with the composition of  claim 1 .  
   
   
       18 . The substrate of  claim 17  which is a composition containing calcium carbonate.  
   
   
       19 . The substrate of  claim 17  which is unglazed concrete, brick, tile, stone, granite, limestone, grout, mortar, composite materials such as terrazzo, gypsum board, marble, statuary, monuments, or wood.  
   
   
       20 . The substrate of  claim 17  which after treatment has water repellency, oil repellency and stain resistance.