Protecting agent for concrete, masonry surface, bricks, clay roofing, tiles, marble, granite, concrete slate, stucco, paving stones, unglazed ceramic, sandstone, limestone, wood and other objects against stains, dirt, water and oil penetration

Abstract

An aqueous composition of a non-siliceous fluorocarbon polymer forms a dry deposit derived from the non-siliceous fluorocarbon polymer on the surface of construction material; the non-siliceous fluorocarbon polymer being characterized by the presence of fluorocarbon units of up to 6 carbon atoms; this non-siliceous fluorocarbon polymer is a protecting agent imparting an excellent water and oil repellency and also protection against stains and dirt, to bricks, clay roofing, different kinds of tiles, marble, granite, slate, stucco, paving stones, unglazed ceramic, sandstones, limestone, wood and other objects; it is durable and can be processed at low temperature; the composition may also include silicone based agents and acrylics and can provide a natural, satin or wet look to the construction material surface.

1 . A method of imparting water and oil repellency and resistance to staining to a surface of a construction material, which comprises applying to the surface an aqueous composition of a non-siliceous fluorocarbon polymer to form a dry deposit derived from the non-siliceous fluorocarbon polymer on the surface; the non-siliceous fluorocarbon polymer being characterized by the presence of fluorocarbon units of up to 6 carbon atoms. 
     
     
         2 . The method of  claim 1 , wherein said non-siliceous fluorocarbon polymer is a fluoroalkyl acrylate copolymer derived from a first monomer having a polyfluoroalkyl group, wherein the melting point of fine crystals derived from the polyfluoroalkyl groups in a homopolymer of the monomer, does not exist or is at most 50° C.; and a second monomer having an organic group other than a polyfluoroalkyl group and wherein the melting point of fine crystal derived from the organic groups in a homopolymer of the second monomer, is at least 30° C. 
     
     
         3 . The method of  claim 2 , wherein polyfluoroalkyl group has up to 6 carbon atoms. 
     
     
         4 . The method of  claim 3 , wherein the construction material is selected from concrete, masonry surfaces, bricks, clay roofing, tiles, marble, granite, concrete slate, stucco, paving stones, unglazed ceramic, sandstone, limestone or wood. 
     
     
         5 . The method of  claim 1 , wherein said aqueous composition further comprises one or more of: micro silicone emulsion, macro silicone emulsion, silane, siloxane, siliconates, and acrylic polymer. 
     
     
         6 . The method of  claim 1 , wherein said aqueous composition is an aqueous solution having a pH less than 10. 
     
     
         7 . The method of  claim 1 , wherein said non-siliceous fluorocarbon polymer is present in said aqueous composition in an amount of 0.1% to 10%, by weight, based on the weight of the aqueous composition. 
     
     
         8 . The method of  claim 1 , wherein said aqueous composition is applied to said surface by a method selected from wiping, brushing, immersing, rolling or spraying. 
     
     
         9 . The method of  claim 1 , wherein said aqueous composition is applied to said surface at room temperature and is fixed and cured at the same temperature without additional heat. 
     
     
         10 . The method of  claim 9 , wherein said non-siliceous fluorocarbon polymer is present in said aqueous composition in an amount of 2 to 5%, by weight, based on the weight of the aqueous composition. 
     
     
         11 . The method of  claim 1 , wherein said non-siliceous fluorocarbon polymer is anionic-cationic or non-ionic and cures, dries or fixes on said surface at ambient temperature, without need for addition of heat. 
     
     
         12 . An aqueous composition for imparting water and oil repellency and resistance to staining to a surface of a construction material, which comprises a non-siliceous fluorocarbon polymer characterized by the presence of fluorocarbon units of up to 6 carbon atoms; in an aqueous vehicle. 
     
     
         13 . The aqueous composition of  claim 12 , wherein said non-siliceous fluorocarbon polymer is a fluoroalkyl acrylate copolymer derived from a first monomer having a polyfluoroalkyl group, wherein the melting point of fine crystals derived from the polyfluoroalkyl groups in a homopolymer of the monomer, does not exist or is at most 50° C.; and a second monomer having an organic group other than a polyfluoroalkyl group and wherein the melting point of fine crystal derived from the organic groups in a homopolymer of the second monomer, is at least 30° C. 
     
     
         14 . The aqueous composition of  claim 13 , wherein said polyfluoroalkyl group has up to 6 carbon atoms. 
     
     
         15 . The aqueous composition of  claim 12 , further comprising one or more of:
 micro silicone emulsion, macro silicone emulsion, silane, siloxane, siliconates, acrylic polymer and urea.   
     
     
         16 . The aqueous composition of  claim 12 , wherein said non-siliceous fluorocarbon polymer is present in said aqueous composition in an amount of at least 0.01%, by weight based on the weight of the aqueous composition. 
     
     
         17 . A protected construction material having a surface which is water and oil repellent and resistant to staining, said surface having a dry deposit derived from a non-siliceous fluorocarbon polymer characterized by the presence of fluorocarbon units of up to 6 carbon atoms, wherein said construction material is selected from concrete, masonry surfaces, bricks, clay roofing, tiles, marble, granite, concrete slate, stucco, paving stones, unglazed ceramic, sandstone, limestone or wood. 
     
     
         18 . The protected construction material of  claim 17 , wherein said non-siliceous fluorocarbon polymer is a fluoroalkyl acrylate copolymer derived from a first monomer having a polyfluoroalkyl group which has up to 6 carbon atoms, wherein the melting point of fine crystals derived from the polyfluoroalkyl groups in a homopolymer of the monomer, does not exist or is at most 50° C.; and a second monomer having an organic group other than a polyfluoroalkyl group and wherein the melting point of fine crystal derived from the organic groups in a homopolymer of the second monomer, is at least 30° C. 
     
     
         19 . (canceled) 
     
     
         20 . The protected construction material of  claim 17 , wherein said dry deposit further comprises one or more of: silicone from a micro silicone emulsion, silicone from a macro silicone emulsion, silane, siloxane, siliconates, acrylic polymer and urea. 
     
     
         21 . The protected construction material of  claim 20 , wherein said acrylic polymer comprises at least one or more of the following monomers, ethyl acrylate, methyl methacrylate, ethyl hexylacrylate, ethyl hexyl methacrylate, butyl acrylate, methacrylic acid, and ethyl methacrylate. 
     
     
         22 . The method of  claim 1 , wherein said non-siliceous fluorocarbon polymer is a fluorine-containing polymer having an aliphatic monocyclic structure in the polymer trunk chain, which has a number average molecular weight of from 500 to 1,000,000 and is represented by the formula:
   (M a ): -(M1)-(M2 a )-(N)—  (Ma)
   
       in which the structural unit M1 is a structural unit derived from an ethylenic monomer having 2 or 3 carbon atoms and at least one fluorine atom, the structural unit M2a is at least one structural unit which introduces an aliphatic monocyclic structure in the polymer trunk chain and is represented by the formula: 
       
         
           
           
               
               
           
         
       
       wherein R 1  is at least one hydrocarbon group selected from the group consisting of a divalent hydrocarbon group which has 1 to 8 carbon atoms and constitutes a ring (which may be further substituted with a hydrocarbon group or a fluorine-containing alkyl group) and a divalent hydrocarbon group having ether bond which has the sum of carbon atoms and oxygen atoms of 2 to 8 and constitutes a ring (which may be further substituted with a hydrocarbon group or a fluorine-containing alkyl group); R 2  is an alkylene group which has 1 to 3 carbon atoms and constitutes a ring; R 3  and R 4  are the same or different and each is a divalent alkylene group having 1 or 2 carbon atoms; n1, n2 and n3 are the same or different and each is 0 or 1, the structural unit N is a structural unit derived from a monomer copolymerizable with the monomers to introduce the structural units M1 and M2a; (Z)n4 is H or each Z is the same or different and each is:
   —(R 5 ) n5 Z 1  
 
 
       wherein Z 1  is at least one functional group selected from the group consisting of OH group, COOH group, a derivative of carboxylic acid group and a functional group protected by a protective group which can convert the functional group to OH group by reaction with an acid; R 5  is a divalent organic group; n5 is 0 or 1; n4 is an integer of from 1 to 3, and wherein the structural units M1, M2a and N are contained in amounts of from 1 to 99% by mole, from 1 to 99% by mole and from 0 to 98% by mole, respectively.