MXPA01000470A - Compositions and methods to protect calcitic and/or siliceous surfaces - Google Patents

Abstract

Calcitic and/or siliceous architectural and construction materials are provided with increased resistance to damage from water, oil, grease and weather by a process which comprises treating said materials with an aqueous composition containing:(A) from about 0.1 to 4%by weight on a 100%solids basis of an aqueous solution or self-dispersed emulsion or dispersion of a copolymer which is a reaction product of monomers containing fluorinated groups, cationic groups and nonionic groups, (B) an effective amount of a penetration assistant, and (C) water to make up 100%.

Description

COMPOSITIONS AND METHODS TO PROTECT SKIN AND / OR SILICONE SURFACES The present invention relates to compositions and methods for protecting calcific and / or siliceous architectural and construction materials from water, oil, grease and environmental damage. More particularly, it relates to compositions and methods employing copolymeric and fluoromeric compositions to protect materials such as bricks, tiles, plaster, stone, cement, concrete and masonry against such damage.

BACKGROUND OF THE INVENTION It is known that fluorochemical components, particularly certain fluorochemical copolymers, can be used to impart water, oil or grease repellency or paper and paper products, and to textile fibers such as nylon used in carpets and upholstered furniture.

It is also known that certain fluorochemical copolymers can be used in combination with other substances to improve the resistance of construction materials to damage by water or oil. For example JP 9286676 A teaches the use of an aqueous emulsion of a fluororesin which is a copolymer of a fluoroolefin, a vinyl ester of carboxylic acid and unsaturated monomers having hydrophilic functional groups with an aqueous emulsion of a silane compound having functional groups hydrolysable to form a water-repellent coating, resistant to water on the cured concrete surface. EP-A 0 714 921 teaches two component resin compositions for water repellent coatings for textiles and building materials which comprise a fluorinated acrylic copolymer component which also contains cationic amino groups, either in salt form or quaternized and other functional groups, and a polyisocyanate component. By mixing the two water-based components and applying the mixture to building materials, they quickly harden to a coating which imparts water and oil repellent properties, stable anti-graffiti to the treated substrates. U.S. Patent 5,753,569 teaches a treatment with a two-component coating to move substrates selected from a group consisting of natural and synthetic textiles and their blends, leather, mineral substances, thermoplastic and thermosetting polymers and paper, oil repellents, water and dirt applying to these compositions containing the components A and B, where the component B is a fluorine-free poly (meth) acrylate ester and the component A is fluorine-containing and comprises repeating units of a) 40 to 85% in weight of (meth) acrylates containing perfluoroalkyl groups, b) 1 to 45% by weight of one or more monomers from the group consisting of styrene, acrylonitrile, vinyl acetate, vinyl propionate and (meth) acrylate esters, c) 4 to 30% by weight of polyether poly (meth) acrylate esters and d) 1 to 15% by weight of ionic or ionizable monomers containing an amine or a carboxyl function. EP-A 0 714 870 teaches an oleophobic and hydrophobic treatment for building materials, which comprises applying to the surface of the materials to be treated a mixture of fluorinated acrylic copolymer, cationic, water soluble, of the type described in U.S. Patent 5,493,998 and a polymer film former, polyvinyl alcohol. The copolymers are reaction products of a perfluoroalkylethyl acrylate, a dialkylalkylaminoethyl methacrylate, vinyl acetate and optionally a fourth monomer such as butyl methacrylate. Although some protection can be provided by saturating a surface with an aqueous solution of the copolymer only, the required high concentration of the fluorinated, cationic, water-soluble alkyl copolymer, 20-25%, makes this method unattractive and impractical. A disadvantage of all previous surface treatments for a number of applications, whether they are reticulated resins or physical mixtures with a polymeric film former, they form coatings which seal the surface of the construction material. This often results in an aesthetically undesirable shine and an unnatural appearance. Additionally, a coating will normally make a more slippery surface and will prevent drainage of water. Both of these properties would be highly undesirable in a surface treatment for horizontal surfaces such as concrete floors, sidewalks, roads, parking lots, roads and airport runways for example. It is therefore an object of this invention to find a surface treatment of a component for architectural and calcitic and / or siliceous building materials that is free of crosslinking agents and fluorine-free film-fog polymers that would not impart a bright appearance and would not natural to surfaces, and not impart traction on rough horizontal surfaces. It has now been found that calcitic and / or siliceous architectural and construction materials, such as bricks, tiles, marble, stone, plaster, concrete, cement and mortar, can be provided with greater resistance to damage of water, oil, grease and weathering, remaining still porous and retaining a natural appearance, treating them with a composition comprising a dilute aqueous solution or self dispersing emulsion or dispersion of certain cationic, fluorinated copolymers, optionally in the presence of an effective amount of a penetration aid.

DETAILED DESCRIPTION OF THE INVENTION The present invention comprises a composition which provides architectural and calcitic materials and / or siliceous materials with greater resistance to water, oil, grease and weathering damage, which composition comprises: (A) of about 0.1 to 4% by weight, on a 100% solids basis, of an aqueous solution or self dispersing emulsion or dispersion of a copolymer which is a reaction product of monomers containing fluorinated groups, cationic groups and non-ionic groups, (B) an effective amount of a penetration aid; and (C) water for 100%. Preferably, the treatment compositions comprise from about 0.2 to 2% by weight of the aqueous solution or self dispersing emulsion or dispersion of the copolymer on a 100% solids basis, more preferably from 0.4 to 1% of the copolymer and from about 0.01 to 1% by weight, more preferably 0.05 to 0.4% by weight of the penetration aid. The treatment composition may also contain up to about 2% by weight of a water-miscible organic solvent such as acetone, dioxane, tetrahydrofuran, dimethyl formamide, N-methylpyrrolidone, di-ethyl sulfoxide, ethanol, isopropanol, methyl isobutyl ketone, ethylene glycol or propylene glycol, such solvents being commonly used during the synthesis of the copolymers. Additionally the penetration aid can be added as a solution in an organic solvent. Preferably, however, the treatment compositions do not contain or only contain low amounts of organic solvents for health, safety and ecological reasons. The treatment composition can advantageously obtain conventional additives which are compatible with the mixture of the aqueous solution or self-dispersing emulsion or dispersion of the copolymer and the penetration aid. In particular, the treatment composition may contain a microbicide. Microbicidal niches and commercial sources thereof are listed in McCutcheon's 1994 Volume 2: Functional Materials, North American Edition, McCutcheon's Division, MC Publishing Co., Glen Rock, NJ. Component (A) suitably contains a copolymer which is a reaction product of one or more met (acrylate) monomers containing polyfluorinated alkyl groups, cationic nitrogen groups which are partially or completely quaternized or in the form of a salt, and non-ionic groups. To obtain a satisfactory balance of hydrophobic and oleophobic properties it is preferred that the copolymer be a reaction product of about 60-90% by weight of one or more met (acrylate) monomers containing fluorinated alkyl groups, from about 10 to about 30. Weight% of one or more monomers of meth (acrylates) containing cationic groups that are partially or fully quaternized or in the form of a salt and from about 1 to about 10% by weight of one or more monomers containing nonionic groups. Suitable monomers containing nonionic groups including ethylene, propylene, isobutene, chloro-3-isobuten-1, butadiene, isoprene, chloro- and dichloro-butadienes, fluoro- and difluorobutadienes, vinylidene chloride, vinyl fluoride or vinylidene, allyl bromide, metalloyl chloride, vinyl toluene, alpha-methylstyrene, alpha-cyanomethylstyrene, divinylbenzene, N-vinylcarbazole, methyl vinyl ketone, allyl acetate, allyl propionate, allyl isobutyrate, allyl eptanoate, cetyl vinyl ether, dodecyl vinyl ether, allyl-, methyl-, ethyl-, propyl-, isopropyl-, butyl-, isobutyl-, hexyl-, heptyl-, ethyl-2-hexyl-, cyclohexyl, lauryl, stearyl or ethoxyethyl esters of acrylic acid, methacrylic, alpha-chloroacrylic, crotonic, maleic, fumaric, itaconic, citraconic and senecioic, diacrylates and. glycol or polyalkylene glycol dimethacrylates, acrylonitrile, methacrylonitrile, chloro-2-acrylonitrile, cyano-2-ethyl acrylate, methylene glutaronitrile, vinylidene cyanate, isopropyl cyanoacrylate, trisacryloyl-hexahydro-s-triazine, allyl alcohol, allyl glycolate, isobutenediol, allyloxy-ethanol, o-allylphenol, divinylcarbinol, glycerol-allyl ether, acrylamide, methacrylamide, maleamide and maleimide, N- (cyanoethyl) acrylamide, N-isopropyl-acrylamide, diacetone-acrylamide, N- (hydroxymethyl) -acrylamide, and methacrylamide, N- (alkoxymethyl) -acrylamides and methacrylamides, glyoxal-bis-acrylamide, amino-3- tolonitrile, monoalylamine, vinylpyridines, acrylate or glycidyl methacrylate and its chlorohydrins, allyl glycidyl ether and acrolein. Nonionic groups containing epoxy or chlorohydrin are preferred with glycidyl methacrylate being especially preferred. The copolymers are known per se can be prepared by the conventional free radical polymerization methods described in the references discussed above, which are incorporated herein by reference. Additionally, some of the copolymers of the references are commercially available.

Preferably the component (A) contains a copolymer which comprises copolymerized monomers in the following percentages by weight, relative to the total weight of the copolymers: (a) from about 60% to about 90% of at least one monomer of formula I: Rf-QAC (0) -C (R) = CH2 (I) Where Rf is a straight or branched chain perfluoroalkyl group of 2 to about 20 carbon atoms, R is H or CH3, A is O, S, or N (R '), where R' is H or an alkyl of 1 to 4 carbon atoms, Q is alkylene of 1 to about 15 carbon atoms, hydroxyalkylene of 3 to 15 atoms carbon - (CnH2n) (OCqH2q) m-, -S02-NR '(CnH2n) -, or -CONR' (CnH2n) -, where R 'is H or an alkyl of 1 to 4 carbon atoms, n is 1 to 15 , q is from 2 to 4, and m is from 1 to 15; (b) from about 10 to about 40% of a monomer of formula II: (Ri) 2N-CH2CH2-0-C (0) -C (R2) = CH2 (II) wherein Ri is an alkyl group of 1 to 3 carbon atoms, R2 is H or an alkyl radical of 1 to 4 carbon atoms, and where the nitrogen is from 40 to 100% quaternized or in the form of a salt; and (c) from about 1 to about 7% of at least one monomer of formula III or IV or a mixture thereof: CH2-CH-CH2-0-C (0) -C (R3) = CH2 (III) 0 Cl-CH 2 -CH (OH) CH 2 -C-C (0) -C (R 4) = CH 2 (IV), wherein R 3 and R 4 are each independently H or the same or different alkyl radical of from 1 to 4 carbon atoms carbon. In the above compositions, preferably in formula I, Rf is a straight chain perfluoroalkyl group of 2 to about 20 carbon atoms or a mixture thereof, A is O and Q is an alkylene of 1 to about 15. carbon atoms. More preferably, the monomer of formula I is a perfluoroalkylethyl acrylate having the formula CF3CF2 (CF2) xC2H4OC (0) -C (H) = CH2 in which x is an even integer from 4 to 18, or a mixture of the same. More preferably, it is a mixture having a carbon chain length distribution of perfluoroalkyl (x) by weight of about 50% of 8 carbons, about 29% of 10 carbons, about 11% of 12 carbons, and with percentages less than 6 carbons, 14 carbons and longer chain lengths. Preferably the monomer of formula I is diethylaminoethyl methacrylate which has undergone partial or total salinization or quaternization and the monomer of formula III is glycidyl methacrylate. Preferably the proportion of the monomer of formula I in the copolymer is from about 79% to about 85%, the proportion of the monomer of formula II in the copolymer (in its salt form) is from about 13% to about 19% in Weight and the proportion of the monomer of formula III or IV or a mixture thereof, in the copolymer is from about 1% to about 5% by weight. The above copolymers are known per se from U.S. Patent 5,674,961, the disclosure of which is incorporated herein by reference, where they are taught to be useful in the treatment of paper and paper products. They are also known per se from WO 97/39072, the disclosure of which is incorporated herein by reference, where they are taught to be useful in the treatment of hard surfaces, including building materials such as bricks, stone, wood, concrete , ceramics, tiles, glass, stucco, dry walls of plaster, boards made of wood particles or sawdust. A composition comprises an especially preferred copolymer of the type described above, but which does not contain component (B) is commercially available from the Consumer Care Division of Ciba Specialty Chemicals Corporation, High Point, NC, as a 30% aqueous composition designated as LODYNE. P-514. Component (B) is a penetration aid. A penetration aid is any tensoactive organic substance that has a tensioactive organic substance that enhances the ability of an aqueous solution or self dispersing emulsion or dispersion of the copolymer to penetrate and wet a calcific and / or silicon substrate. Suitable penetration aids include anionic and non-anionic surfactants. Preferably the penetration aid is, or contains a nonionic, cationic surfactant. "Penetration aid can be monomeric, oligomeric or polymeric A large number of commercially available surfactants are described in McCutchenon's 1994 Volume 1; Emulsifiers and Détergents, North American Edition, McCutcheon's Division, MC Publishing Co., Glen Rock, NJ. Advantageously, the penetration aid is used in liquid form, either as a pure liquid or with an aqueous or non-aqueous solution of the active substance. A particularly preferred penetration aid is a known patented liquid mixture known as Solvent-D, which contains polyethylene carbonate and is commercially available from Polypore, Inc., Tucson, AZ. The amount of the penetration aid to be used may vary. In general, an effective amount of the penetration aid will reduce the surface tension of water by at least 15 percent, preferably from 20 to 60 percent. Advantageously, a composition contains from about 0.01 to 1% by weight of a penetration aid, preferably from 0.05 to 0.4% and more preferably from 0.08 to 0.15% by weight of the penetration aid. Those percentages by weight are on an "as is" basis which means that the presence or absence of a solvent or diluent in the commercially available surface active material is ignored. The present invention also comprises a process which provides calcitic and / or silicon architectural and construction materials with greater resistance to water, oil, grease and weather damage, which process comprises treating the materials with an aqueous composition containing: (A ) of about 0.2 to 4% by weight of an aqueous solution or self dispersing emulsion or dispersion of a copolymer which is a reaction product of monomers containing fluorinated groups, cationic groups and optionally nonionic groups, (B) an effective amount of a penetration aid, and (C) water for 100%. Preferably the process comprises treating the above substrates with an aqueous composition which comprises from about 0.2 to 2% by weight of the aqueous solution or self dispersing emulsion or dispersion of the copolymer on a 100% solids basis, and at about 0.01% by weight. 1% by weight of the penetration aid. In one process the copolymer (A) is a reaction product of about 60-90% by weight of one or more monomers of meth (acrylate) containing polyfluorinated alkyl groups, from about 10 to about 40% by weight of one or more monomers of met (acrylate) containing cationic groups in about 1 to about 10% by weight of one or more monomers comprising nonionic groups. More preferably, the nonionic group is selected from the group consisting of ethylene, propylene, isobutene, chloro-3-isobuten-1, butadiene, isoprene, chloro- and dichloro-butadienes, fluoro- and difluoro-butadienes, vinylidene, vinyl fluoride or vinylidene, allyl bromide, methallyl chloride, vinyl toluene, alpha-methylstyrene, alpha-cyanomethylstyrene, divinylbenzene, N-vinylcarbazole, methyl vinyl ketone, allyl acetate, allyl propionate, allyl isobutyrate, allyl heptanoate, cetyl vinyl ether, dodecyl vinyl ether, allyl, methyl-ethyl-, propyl, isopropyl-, butyl-, isobutyl, hexyl-, heptyl-, ethyl-2-hexyl-, cyclohexyl-, lauryl-, stearyl -, or ethoxyethyl ethers of acrylic, methacrylic, alpha-chloroacrylic, crotonic, maleic, fumaric, itaconic, citraconic and senecioic acid, diacrylates and dimethacrylates of glycol or polyalkylene glycol, acrylonitrile, methacrylonitrile, chloro-2-acrylonitrile, cyano-2 acrylate -ethyl, methylene glutaronitrile, cyanate vinylidene, isopropyl cyanoacrylate, trisacryloyl-hexahydro-s-triazine, allyl alcohol, allyl glycolate, isobutenediol, allyloxy-ethanol, o-allylph, divinylcarbinol, glycerol-allyl ether, acrylamide, methacrylamide, maleamide and maleimide, N- (cinnaethyl) ) acrylamide, N-isopropyl-acrylamide, diacetone-acrylamide, N- (hydroxymethyl) -acrylamide and methacrylamide, N- (alkoxymethyl) -acrylamides and ethacrylamides, glyoxal-bis-acrylamide, amino-3-crotononitrile, monoalylamine, vinylpyridines, acrylate or glycidyl methacrylate and its chlorohydrins, allyl glycidyl ether and acrolein. It is especially preferred that the non-anionic monomer comprises at least one monomer selected from the group consisting of acrylate or glycidyl methacrylate and its chlorohydrins.

A particularly preferred process comprises treating the above substrates with an aqueous composition, wherein the copolymer in (A) is a reaction product of copolymerized monomers in the following percentages by weight, total weight ratio of the copolymers: (a) of about 60 % up to about 90% of at least one monomer of formula I: Rf-QAC (0) -C (R) = CH2 (I) in which Rf is a straight or branched chain perfluoroalkyl group of 2 to about 20 carbon atoms carbon, R is H or CH3, A is O, S, or N (R '), where R' is H or an alkyl of 1 to 4 carbon atoms, Q is alkylene of 1 to about 15 carbon atoms, hydroxyalkylene from 3 to 15 carbon atoms, - (CnH2n) (OCqH2q) m-, -S02-NR '(CnH2r-, or -CONR' (CnH2n) -, where R 'is H or an alkyl of 1 to 4 carbon atoms carbon, n is 1 to 15, q is 2 to 4, and m is 1 to 15, (b) from about 10 to about 40% of a monomer of formula II: (RI) 2N-CH2CH2-0-C ( O) -C (R2) = CH2 (II) in which Ri is an alkyl group of 3 carbon atoms, R2 is H or an alkyl radical of 1 to 4 carbon atoms and where the nitrogen is from 40 to 100 Quaternized% or in the form of a salt; and (c) from about 1 to about 7% of at least one monomer of formula III or IV, a mixture thereof: CH2-CH-CH2-0-C (0) -C (R3) = CH2 (III) or Cl-CH2-CH (OH) CH2-0-C (0) -C (R4) = CH2 (IV), where R3 and R are each independently H or the same or different alkyl radical from 1 to 4 carbon atoms. carbon. In the above process, preferably, Rf is a straight chain perfluoroalkyl group of 2 to about 20 carbon atoms, or a mixture thereof, A is O and Q is an alkylene of 1 to about 15 carbon atoms, the monomer of formula II is diethylaminoethyl methacrylate which has undergone partial or total saltinization or quaternization and a monomer of formula III is glycidyl methacrylate. The present invention also relates to an architectural or calcific construction material and / or silicon that has greater resistance to water damage, grease oil and weathering, material which has been treated with a composition comprising: (A) of about 0.1 at 4% by weight, on a 100% solids basis, of an aqueous solution or self dispersing emulsion or dispersion of a copolymer is a reaction product of monomers containing fluorinated groups, cationic groups and non-ionic groups, (B) an effective amount of a penetration aid; and (C) water for 100%. The compositions of the present invention are prepared simply by combining the fluorochemical copolymer and the penetration aid and, if desired, any conventional additives, in particular a microbicide, with water of approximately neutral pH with gentle agitation. Preferably, the compositions are prepared by adding the fluorochemical copolymer and the penetration aid and, if desired, any conventional water additives. Advantageously, deionized or distilled water of approximately neutral pH is used. If desired, a concentrate of the composition of the invention can be prepared by combining the fluorochemical copolymer, the penetration aid and any conventional additives and, optionally, nothing or preferably only part of the water. The composition The concentrate is then diluted with the appropriate amount of water to obtain an adequate concentration of the fluorochemical copolymer before it is used in the treatment process of the invention. The compositions of the present invention can be applied to the surface of an architectural or calcific building material and / or silicon by any known method, for example by soaking, impregnation, dipping, brushing, roller or spray application. Advantageously, the treatment compositions of the present invention are applied to the surface to be protected by spraying, and in particular by spraying with a compressed air sprayer. The proper spray equipment is commercially available. The amount of compositions of the present invention to be applied to the surface of an architectural or calcific building material and / or silicon is not critical. The amount should be enough to perfectly wet the surface, but excessive shifting should be avoided for ecological reasons. Naturally some very porous substrates, such as Saltillo tile from Mexico, will absorb substantial amounts of the treatment composition while others, such as stone, will absorb very little. After application of the composition of the invention to a substrate, the treated surface should be allowed to dry perfectly before being exposed to water, oil or grease. Interestingly, a porous substrate largely retains its porosity after the treatment of the invention, and thus air and humeral vapor can still pass through it. This shows that the surface is sealed as it would be with any conventional coating. Even liquid water, oil or fat are strongly repelled as a result of the treatment of the invention. The treated substrate also retains its natural appearance. The surface of a large variety of calcitic and / or silicon architectural or construction materials can be successfully treated with the compositions of the invention. These include concrete, paving stones, granite blocks, marble, natural stone, calcite, slate including slate slate, brick, porcelain, glazed and unglazed ceramic tile, Saltillo tile, terracotta tiles, terrazzo and roofing. The surfaces to be treated can be vertical or essentially vertical, such as the exteriors of buildings, including historic buildings that need protection against soot, acid rain and erosion, as well as statues and monuments, diagonal surfaces such as slate or tile roofs, or they can be horizontal surfaces such as concrete floors, sidewalks and streets, and brick or tile sidewalks. Of special interest are concrete floors, automotive service stations and aircraft hangar bays which are routinely exposed to new and residual water, oil and grease as well as other fluids such as antifreeze solutions and brake and transmission fluids, and roads. of concrete, especially those that are exposed to freeze-thaw cycles and treated with salts to melt snow and ice. The treatment of a concrete road with the composition of the present invention can greatly mitigate the freeze-thaw damage and thus make the minimum maintenance and extend the life of the road in a very cheap way. The effectiveness of the surface treatment by the compositions of the invention is evaluated principally visually by applying drops of water or motor oil OX) (pennzoil of weight 30) to a horizontal surface treated and dried. While the water normally wets an architectural material of calcific construction and / or silicon and forms a continuous sheet or film, or is absorbed by it, depending on its porosity, the water is strongly repelled as a result of the treatment of the invention which, from In general, it simply forms small, almost hemispherical beads on the surface of the treated material. Normally somewhat wider beads are obtained which exhibit a lower contact angle after treatment in the absence of the wetting agent. The water can be left on the surface. treated for an indefinite period of time. Eventually it simply evaporates without leaving any indication of damage to the surface. In motor oil it also normally wets and disperses through an architectural or calcific building material and / or silicon and, if the surface is porous, slowly absorbs this. However, if the surface of an architectural or calcific construction material and / or silicon is treated according to the process of the invention there is substantially less dispersion and no absorption. Consequently even after a prolonged period the oil can be easily removed by absorbing it with an absorbent material or by rinsing it with a hose. The surface of an architectural material or calcitic and / or silicon construction treated according to the process of the invention shows improved properties in relation to the same surface treated only with the copolymer. Some of the materials treated according to the process of the invention still exhibit excellent water and oil repellency after more than one year of storage. The following non-limiting examples illustrate the preparation and use of the compositions of the invention. However, the invention is not limited to these. All parts are in weight.

Preparation of a composition of the invention A vessel containing 100 parts of deionized water was gradually added with moderate stirring 2.0 parts of LODYNE P-514, an aqueous composition comprising about 30% by weight of a cationic fluorochemical copolymer which is commercially available available from Consumer Care Division of Ciba Specialty Chemicals Corporation, High Point, NC, followed by 0.1 parts of Solvent-D, a patented liquid which is available from Polypore, Inc., Tucson, AZ. If desired, a microbicide is then added and the mixture is stirred until it is visually homogeneous. This is stable during storage.

Application of the composition of the invention to a surface A solution having the above composition is placed in a compressed air spray apparatus. Samples of various architectural materials and calcitic and / or silicon construction including concrete, paving stone, granite blocks, marble, natural stone, calcite, slate, including slate slate, brick, porcelain, glazed and unglazed ceramic tiles, Saltillo tile, terracotta tiles, terrazzo and roofing, are placed flat on a protected surface and then sprayed with the composition of the invention until the surfaces are completely wet. The treated materials are then allowed to dry perfectly before being evaluated as described above. Additionally, concrete surfaces and cement surfaces treated according to the process of the invention were evaluated and found to be slip resistant as measured by the UL 410 Laboratory's method.

Claims (18)

1. A composition which provides calcitic and / or silicon architectural and construction materials with greater resistance to water, oil, grease and weathering damage, which composition is characterized in that it comprises: (A) from about 0.1 to 4% by weight, about a base of 100% solids, an aqueous self-dispersing emulsion solution or dispersion of a copolymer which is a reaction product of monomers containing fluorinated groups, cationic groups and non-ionic groups, (B) an effective amount of an penetration, and (C) water for 100%.

2. The composition according to claim 1, characterized in that it comprises from about 0.2 to 2% by weight of the aqueous solution or self dispersing emulsion or dispersion of the copolymer on a base of 100% solids, and from about 0.01 to 1% by weight. Weight of the penetration aid.

3. The composition according to claim 1, characterized in that the copolymer (A) is a reaction product of about 60-90% by weight of one or more monomers of meth (acrylate) containing polyfluorinated alkyl groups, of about 10. up to about 40% by weight of one or more monomers of meth (acrylate) containing cationic groups and from about 1 to about 10% by weight of one or more monomers containing nonionic groups.

The composition according to claim 1, characterized in that the copolymer (A) is a reaction product of one or more monomers containing nonionic groups selected from the group consisting of ethylene, propylene, isobutene, chloro-3-isobuten -l, butadiene, isoprene, chloro- and dichloro-butadienes, fluoro- and difluoro-butadienes, vinylidene chloride, vinyl fluoride or vinylidene, allyl bromide, methallyl chloride, vinyl toluene, alpha-methylstyrene, alpha-cyanomethylstyrene , divinylbenzene, N-vinylcarbazole, methyl vinyl ketone, ethyl acetate, allyl propionate, allyl isobutyrate, allyl heptanoate, cetyl vinyl ether, dodecyl vinyl ether, allyl, methyl-, ethyl-, propyl, isopropyl-, butyl -, isobutyl, hexyl-, heptyl-, ethyl-2-hexyl-, cyclohexyl-, lauryl-, stearyl-, or ethoxyethyl ethers of acrylic, methacrylic, alpha-chloroacrylic, crotonic, maleic, fumaric, itaconic, citraconic and senecioic acid , glycol diacrylates and dimethacrylates or polyalkylene glycol, acrylonitrile, methacrylonitrile, chloro-2-acrylonitrile, cyano-2-ethyl acrylate, methylene glutaronitrile, vinylidene cyanate, isopropyl cyanoacrylate, trisacryloyl-hexahydro-s-triazine, allyl alcohol, allyl glycolate, isobutenediol, allyloxy- ethanol, o-allylphenol, divinylcarbinol, glycerol-allyl ether, acrylamide, methacrylamide, maleamide and maleimide, N- (cyanoethyl) acrylamilide, N-isopropyl-acrylamide, diacetone-acrylamide, N- (hydroxymethyl) -acrylamide and methacrylamide, N- (alkoxy ethyl) -acrylamides and methacrylamides, glyoxal-bis-acrylamide, amino-3-crotononitrile, onoalylamine, vinylpyridines, acrylate or glycidyl methacrylate and its chlorohydrins, allyl glycidyl ether and acrolein.

The composition according to claim 4, characterized in that the nonionic monomer comprises at least one monomer selected from the group consisting of acrylate or glycidyl methacrylate and its chlorohydrins.

The composition according to claim 1, characterized in that the copolymer in (A) is a reaction product of copolymerized monomers in the following percentages by weight, based on the total weight of the copolymers: (a) of about 60 % up to about 90% of at least one monomer of formula I: Rf-QAC (0) -C (R) = CH2 (I) wherein Rf is a straight or branched chain perfluoroalkyl group of 2 to about 20 carbon atoms, R is H or CH3, A is O, S or N (R '), where R' is H or an alkyl of 1 to 4 carbon atoms, Q is alkylene of 1 to about 15 carbon atoms, hydroxyalkylene of 3 to 15 carbon atoms, - (CnH2n) (OCqH2q) m-, -S02-NR '(CnH2n) -, or -CONR' (CnH2n) -, where R 'is H or an alkyl of 1 to 4 carbon atoms, n is 1 to 15 , q is from 2 to 4, and m is from 1 to 15; (b) from about 10 to about 40% of a monomer of formula II: (RI) 2N-CH2CH2-0-C (O) 7C (R2) = CH2 (II) where Ri is an alkyl group of the 3-carbon atoms carbon, R2 is H or an alkyl radical of 1 to 4 carbon atoms, and where the nitrogen is from 40 to 100% quaternized or in the form of a salt; and (c) from about 1 to about 7% of at least one monomer of formula III or IV, a mixture thereof:, or CH2-CH-CH2-0-C (0) -C (R3) = CH2 (III) C1-CH2-CH (OH) CH2-0-C (O) - C (R4) = CH2 (IV) where R3 and R4 are each independently H or the same or radical _alkyl different from 1 to 4 carbon atoms .

The composition according to claim 6, characterized in that Rf is a straight chain perfluoroalkyl group of 2 to about 20 carbon atoms, or a mixture thereof, A is O and Q is an alkylene of 1 to about 15. carbon atoms, the monomer of formula II is diethylaminoethyl methacrylate which has undergone partial or total saltinization or quaternization and the monomer of formula III is glycidyl methacrylate.

8. A process which provides calcitic and / or silicon materials and construction with greater resistance to water, oil, grease and weather damage, which process is characterized in that it comprises treating the materials with an aqueous composition comprising: (A) from about 0.1 to 4% by weight, on a 100% solids basis, of an aqueous solution or self dispersing emulsion or dispersion of a copolymer which is a reaction product of monomers containing fluorinated groups, cationic groups and nonionic groups , (B) an effective amount of a penetration aid, and (C) water for 100%.

9. The process according to claim 8, characterized in that the aqueous composition comprises from about 0.2 to 2% by weight of the aqueous solution or self dispersing emulsion or dispersion of the copolymer on a base of 100% solids, and from about 0.01 to 1% in weight of the penetration aid.

The process according to claim 8, characterized in that the copolymer in (A) is a reaction product of about 60-90% by weight of one or more metha (acrylate) monomers containing perfluorinated alkyl groups, of about 10 to about 40% by weight of one or more monomers of meth (acrylate) containing cationic groups and from about 1 to about 10% by weight of one or more monomers containing nonionic groups.

The process according to claim 8, characterized in that the copolymer in (A) is a reaction product of one or more monomers containing nonionic groups selected from the group consisting of ethylene, propylene, isobutene, chloro-3- isobuten-1, butadiene, isoprene, chloro- and dichloro-butadienes, fluoro- and difluoro-butadienes, vinylidene chloride, vinyl fluoride or vinylidene, allyl bromide, methallyl chloride, vinyl toluene, alpha-methylstyrene, alpha- cyanomethylstyrene, divinylbenzene, N-vinylcarbazole, methyl vinyl ketone, allyl acetate, allyl propionate, allyl isobutyrate, allyl heptanoate, cetyl vinyl ether, dodecyl vinyl ether, allyl, methyl-, ethyl-, propyl, isopropyl-, butyl-, isobutyl, hexyl-, heptyl-, ethyl-2-hexyl-, cyclohexyl-, lauryl-, stearyl- or ethoxyethyl ethers of acrylic, methacrylic, alpha-chloroacrylic, crotonic, maleic, fumaric, itaconic, citraconic and senecic acid , glycol diacrylates and dimethacrylates or polyalkylene glycol, acrylonitrile, methacrylonitrile, chloro-2-acrylonitrile, cyano-2-ethyl acrylate, methylene glutaronitrile, vinylidene cyanate, isopropyl cyanoacrylate, trisacryloyl-hexahydro-s-triazine, allyl alcohol, allyl glycolate, isobutenediol, allyloxy- ethanol, o-allylphenol, divinylcarbinol, glycerol-allyl ether, acrylamide, methacrylamide, maleamide and aleimide, N- (cinnaethyl) acrylamilide, N-isopropyl-acrylamide, diacetone-acrylamide, N- (hydroxymethyl) -acrylamide and methacrylamide, N- (alkoxymethyl) -acrylamides and methacrylamides , glyoxal-bis-acrylamide, amino-3-crotononitrile, monoalylamine, vinylpyridines, acrylate or glycidyl methacrylate and its chlorohydrins, allyl glycidyl ether and acrolein.

The process according to claim 11, characterized in that the nonionic monomer comprises at least one monomer selected from the group consisting of acrylate or glycidyl methacrylate and its chlorohydrins.

13. The process in accordance with the claim 8, characterized in that the copolymer in (A) is a reaction product of copolymerized monomers in the following percentages by weight, in relation to the total weight of the copolymers: (a) from about 60% to about 90% of at least one monomer of formula I: Rf-QAC (O) -C (R) = CH 2 (I) wherein R f is a straight or branched chain perfluoroalkyl group of 2 to about 20 carbon atoms, R is H or CH 3, A is 0 , S or N (R '), where R' is H or an alkyl of 1 to 4 carbon atoms, Q is alkylene of 1 to about 15 carbon atoms, hydroxyalkylene of 3 to 15 carbon atoms, - (CnH2n) (OCqH2q) m-, -S02-NR '(CnH2n) -, or -CONR' (CnH2n) -, where R 'is H or an alkyl of 1 to 4 carbon atoms, n is 1 to 15, q is 2 to 4, and m is from 1 to 15; (b) from about 10 to about 40% of a monomer of formula II: (Ri) 2N-CH2CH2-0-C (O) -C (R2) = CH2 (II) wherein Ri is an alkyl group of 1 to 3 carbon atoms, R 2 is H or an alkyl radical of 1 to 4 carbon atoms, and where the nitrogen is from 40 to 100% quaternized or in the form of a salt; and (c) from about 1 to about 7% of at least one monomer of formula III or IV or a mixture thereof: CH-CH-CH2-0-C (0) -C (R3) = CH2 (III) O Cl-CH2-CH (OH) CH2-0-C (0) - C (R4) = CH2 (IV), where R3 and R are each independently H or the same or different alkyl radical of 1 to 4 atoms of carbon.

The process according to claim 13, characterized in that Rf is a straight chain perfluoroalkyl group of 2 to about 20 carbon atoms, or a mixture thereof, A is O and Q is an alkylene of 1 to about 15. carbon atoms, the monomer of formula II is diethylaminoethyl methacrylate which has undergone partial or total saltinization or quaternization and the monomer of formula III is glycidyl methacrylate.

15. The process according to claim 8, characterized in that the aqueous composition is sprayed onto the surface of the architectural or calcific building material and / or silicon with a compressed air sprinkler.

16. The process according to claim 13, characterized in that the aqueous composition is sprayed on the surface of the architectural or calcific building material and / or silicon with a compressed air sprinkler.

The process according to claim 8, characterized in that the calcific and / or silicon architectural or construction material is selected from the group consisting of concrete, paving stones, granite blocks, marble, natural stone, calcite, slate including slate slate, brick, porcelain, glazed and unglazed ceramic tile, tile from Saltillo, terracotta tiles, terrazzo and roof.

18. An architectural or calcific construction material and / or silicon which has greater resistance to water damage oil, grease, weather, material which has been treated with a composition characterized by comprising: (A) from about 0.1 to 4 % by weight, on a 100% solids basis, of an aqueous solution or self dispersing emulsion or dispersion of a copolymer which is a reaction product of monomers containing fluorinated groups, cationic groups and nonionic groups, (B) a effective amount of a penetration aid; and (C) water for 100%.