MXPA01002254A - Aqueous fluorinated polymer dispersions capable to protect asphaltic materials - Google Patents

Abstract

Asphaltic materials are provided with increased resistance to damage from water, oil 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, optionally (B) an effective amount of a penetration assistant, and (C) water to make up 100%.

Description

AQUEOUS DISPERSIONS OF FLUORITE POLYMERS CAPABLE OF PROTECTING ASPHALTIC MATERIALS FIELD OF THE INVENTION The present invention relates to methods and compositions for protecting asphalt materials from water, oil and weather damage. More particularly, it relates to methods and compositions, which comprise applying certain cationic fluorochemical copolymer compositions to asphalt material such as an asphalt surface bearing traffic or coating material to protect the asphalt material against such damage.

Background of the Invention 15 The terms asphalt and bitumen are often used as synonyms in the United States to refer to a generic class of amorphous dark colored thermoplastic materials, composed primarily of high molecular weight hydrocarbons. The main source of Asphalt is petroleum, where it is obtained as the heavy residue that remains after the volatile components of petroleum gasoline have been removed by distillation. The asphalt serves mainly as a binder in mixtures of asphalt and mineral aggregates, which are 1 'v- xZfir. employees in the construction of roads and surfaces that support similar traffic such as access roads, parking areas, and airport runways. As such, it generally comprises from 4 to 10% by weight of the mixture, which is sufficient to coat the mineral aggregate. Asphalt materials for paving roads are also sometimes referred to as asphalt "or bituminous surface". According to the revised article "Asphalt and Bitumin" by Corbett and Urban in Ullmann's Encyclopedia of Industrial Chemistry, Fifth Edition (1985), Vol. A3, pages 169-188, more than 90% of all areas that support traffic are built with asphalt mixtures. Although asphalt areas that support traffic are compacted by hot rolling, they are even more porous than concrete surfaces. There is also a top layer of aggregate coated are asphalt that is exposed directly to sunlight, air, extreme temperatures, rain, snow, ice, vehicle exhaust emissions and fluid leaks (mainly motor oil but also gasoline, diesel fuel and antifreeze solutions), and the salts used to dissolve snow and / or ice. Additionally, surfaces that support air traffic are exposed to aviation fuel spills, hot jet engine exhaust, and, in cold environments, to de-icing aircraft fluids. A main problem 2 > ^ "MVb * im *. in cold climates it is the freeze-thaw damage of the ice, but all the previous exposures lead to the degradation of the asphalt materials that support traffic. As a result, a huge amount of money is spent each year on repairing or coating such materials. Thus, there is a clear need for an effective way to extend the useful life of the asphalt areas that support traffic. Asphalt is also used in coating materials. The asphalt and gravel compositions, which are used as coating materials in more than 95% of private homes in the United States according to the Ullman article mentioned above, consist of a fiberglass or cellulosic support coated on both sides with an asphalt filling and coated on the surface by mineral granules. The filled asphalt serves as a binder for both the support material and the mineral granules. Asphalt is also used as the binder on the upper surface of single or multi-layer coating systems. These asphalt matereological surfaces are subjected to many of the same exposures as a road, that is, sunlight, air, extreme temperatures, rain, snow and freeze-thaw damage, and eventually require 3 ^^^ and j ^ fc? ^ i ^ ig ^ - replacement. An effective way to extend the life time of asphalt composition gravels and other asphalt coating surfaces would therefore also be highly desirable. It is known that flurochemical compounds, particularly certain fluorochemical copolymers, can be used to impart water, oil or grease repellency to 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 certain building materials to water and oil damage. For example JP 9286676 A teaches the use of an aqueous emulsion of a fluororesin which is a copolymer of a fluoro-olefin, a vinyl ester of carboxylic acid and unsaturated monomers having hydrophilic functional groups with a water emulsion of a silane compound which has hydrolysable functional groups to form a water-repellent and weather-resistant coating on the cured concrete surface. EP-A 0 714 921 teaches two component resin compositions for water repellent coatings for textiles and building materials comprising a fluorinated acrylic copolymer component, which also contains cationic amino groups, either in the form of a salt or quaternized, and other functional groups, and a polyisocyanate component. After mixing the two water-based components and applying the mixture to construction materials, they quickly harden to a coating that imparts anti-graffiti and water-repellent properties, stable to the treated substances. U.S. Patent 5,753,569 teaches a two-component coating treatment for rendering substrates selected from the group consisting of natural and synthetic textiles and their blends, leather, mineral substances, thermoplastic and thermosetting polymers and plastic, water and dirt repellents by applying to these compositions which contain components A and B, where component B is a fluorine-free poly (meth) acrylate ester and component A is fluorine-containing and contains repeating units of a) 40 to 85% of (meth) acrylates which contain 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 esters of (meth) acrylate of polyether polyols and d) 1 to 15% by weight of ionic or ionizable monomers containing an amino acid or a carboxyl function.

EP-A-0 714 870 teaches an oleophobic and hydrophobic treatment for certain building materials which comprises applying to the surface of the materials to be treated a water-soluble cationic fluorinated acrylic copolymer mixture of the type described in US Patent 5,493,998 and US Pat. 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 may be provided by saturating a surface with an aqueous solution of the copolymer only, the high concentration of fluorinated acrylic-soluble acrylic copolymer required, 20-25%, makes this method unattractive and impractical. None of the references mentioned above teaches how to protect an asphalt surface. Additionally, all previous surface treatments, whether using crosslinked resins or physical mixtures with a polymer film former, form coatings, which seal the surface of the substrate. In addition to aesthetically undesirable unnatural brightness and appearance, a coating will usually make a slippery surface and prevent drainage of water. Those properties would be highly undesirable in a ^^^^^^^^^^^^^^^^^^^^^^^^ t surface treatment for asphalt areas that support traffic such as access, parking areas, roads and airport runways, for example, and one skilled in the art will avoid such coatings. They would also be excluded from the use on gravel of asphalt composition on aesthetic soils. Therefore, an object of this invention was to find a surface treatment of a component for asphalt materials that were free of crosslinking agents and fluorine-free film forming polymers, which does not impart a shiny and unnatural appearance to the treated surfaces, which does not provide traction on the treated areas that support traffic and that will prolong the useful life of the asphalt materials, providing protection to the asphalt materials against water, oil and weather damage. Surprisingly, it has now been found that asphalt materials, such as traffic-bearing areas and coating materials, can be provided with greater resistance to damage by air, oil and weathering, while retaining porosity and retaining the natural appearance , treating them with a composition comprising a dilute aqueous solution or self dispersing emulsion or dispersion of certain cationic, fluorinated copolymers, 7 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 asphaltic materials with greater resistance to water, oil and weathering damage, which composition comprises: (A) from about 0.1 to 4% by weight, based on 100% solids, of an aqueous emulsion solution or self-dispersing dispersion of a copolymer, which is a reaction product of monomers containing fluorinated groups, cationic groups and non-ionic groups, optionally (B) an effective amount of an aid of penetration, and (C) water to make 100% with the proviso that if copolymer is a reaction product of monomers including 1% or more of vinyl acetate, the composition also contains from about 0.01 to 1% by weight of a penetration aid. Preferably, the treatment compositions comprise from about 0.2 to 2% by weight of the aqueous solution or dispersed emulsion or dispersion of the • --------. . ^ J ^^ ArA? - copolymer on a 100% solids basis, more preferably 0.4-1% of the copolymer, and from about 0.01% to 1% by weight, most preferably 0.05% to 0.04% by weight. Weight of the penetration aid. The treatment compositions may also contain from about 2% by weight of a water miscible organic solvent such as acetone, dioxane, tetrahydrofuran, dimethyl formamide, N-methylpyrrolidone, dimethyl sulfoxide, ethanol, isopropanol, methyl isobutyl ketone, ethylene glycol or propylene glycol, being such solvents commonly used during the synthesis of copolymers. Additionally, the penetration aid can be added as a solution in an organic solvent. Preferably, however, the treatment compositions do not contain or contain only low amounts of organic solvents for health, safety and ecological reasons. The composition of the treatment can also advantageously contain 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 an effective amount of a condom such as an antimicrobial, a bactericide, a fungicide or an algicide. Many such materials and commercial sources are listed in McCutcheon's 1994 Volume 2: Functional Material, 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 nonionic groups. In order 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 polyfluorinated alkyl groups, from about 10 to about about 30% by weight of one or more monomers of meth (acrylate) containing cationic groups which are partially or completely quaternized or in the form of a salt and from about 1 to about 10% by weight of one or more monomers containing groups non-ionic Suitable monomers containing nonionic groups include ethylene, propylene, isobutene, chloro-3-isobuten-1, butadiene, isoprene, chloro- and dichloro-butadienes, fluoro- and difluorobutadienes, vinylidene chloride, vinyl fluoride or vinylidene, allyl bromide, methallyl chloride, vinyl toluene, alpha-methylstyrene, alpha-cyanomethylstyrene, divinylbenzene, N-vinylcarbazole, methyl vinyl ketone, allyl ketone, 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 acid esters acrylic, methacrylic, alpha-chloroacrylic, crotonic, maleic, fumaric, itaconic, citraconic and senecioic, diacrylates and dimethacrylates of glycol or polyalkylene glycol, acrylonitrile, methacrylonitrile, chloro-2-acrylonitrile, cyano-2-ethyl acrylate, methylene glutaronitrile, vinylidene cyanate, cyanoacrylate of isopropyl, trisacryloyl-hexahydro-s-triazine, allyl alcohol, allyl glycolate, isobutenediol, allyloxy-ethanol, o-allylphenol, divinylcarbinol, glycerol-allyl ether, acrylamine, methacrylamide, maleamide and maleimide, N- (cyanoethyl) acrylamide, N-isopropyl-acrylamide, diacetone-acrylamide, N- (hydroxymethyl) -acrylamide and metacplamide, N- (alkoxymethyl) -acrylamides and methacrylamides, glyoxal-bis-acrylamide, amino-3-crotononitrile, monoallylamine, vinylpyridines, acrylate or methacrylate glycidyl and its chlorohydrins, allyl glycidyl ether and acrolein. Nonionic groups containing epoxy or chlorohydrin are preferred, with glycidyl methacrylate being especially preferred. eleven % 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. Typically, the copolymers are prepared as aqueous solutions or self dispersing dispersions or emulsions containing 20 to 35% of the copolymer. Preferably, the component (A) contains a copolymer which contains copolymerized monomers in the following percentages by weight, based on 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) in which 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 about 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 from 1 to 15, q is from 2 to 4, and m is from 1 to 15; (b) from about 10 to about 40% of at least one monomer of formula II: (R?) 2N-CH2CH2-0-C (0) -C (R2) = CH2 (II) in which Ri is a group alkyl 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 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 C? H2-CH-CH2-O-C (O) -C (R3) = CH2 (III) Cl-CH2-CH (OH) CH2-0-C (0) - C (R4) = CH2 (IV), in which R3 and R4 are each independently H or the same an alkyl radical different from 1 to about 4 carbon atoms. In the compositions above, preferably formula I, Rf is a straight chain perfluoroalkyl group of up 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 perfluoroalkyl ethyl acrylate having the formula CF3CF2 (CF2)? C2H4OC (0) -C (H) = CH2 in which x is an integer from 4 to 18, or a mixture thereof. More preferably, it is a mixture having a carbon chain length distribution of perfluoroalkyl (x) by weight of about 50% chain lengths of 8 carbons, about 29% of 10 carbons, about 11% of 12 carbons and with percentages less than 6 carbons, 14 carbons and longer. Preferably, the monomer of formula II is diethylaminoethyl methacrylate which has undergone total and partial salting 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% by weight, the proportion of the monomer of formula II in the copolymer (in its salt form) is about 13% up to about 19% by 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, when taught that they are useful in the treatment of certain hard surfaces, including building materials such as bricks, stone, wood, concrete, ceramics, tiles, glass, stucco, drywall, boards made of wood or cardboard particles. An especially preferred copolymer of the type described above 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 surface active organic substance that increases the capacity of an aqueous solution or self dispersing emulsion or dispersion of the copolymer to penetrate and wet an asphalt substrate. Suitable penetration aids include ionic and non-ionic surfactants. Preferably, the penetration aid is, or contains a nonionic, cationic or amphoteric surfactant. The penetration aid can be monomeric, oligomeric or polymeric. A large number of commercially available surfactants are described in McCutcheon's 1994 Volume 1: Emulsifiers and Detergents, North American Edition, McCutcheon's Division, MC Publishing Co., Glen Rock, NJ. fifteen - & i i ,.

Advantageously, the penetration aid is used in liquid form, either as a pure liquid or as an aqueous or non-aqueous solution of the active substance. A particularly preferred penetration aid is a patented liquid mixture known as Solvent-D, which is available from Polypore, Inc., Tucson, AZ. Solvent-D contains propylene carbonate as a solvent. The amount of penetration aid to be used can vary widely. Generally, an effective amount of the penetration aid will reduce the surface tension of the water by at least 15%, preferably by 20 to 60 percent. Advantageously, the 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% 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 material is ignored. Since the dilute aqueous solution or the self-dispersing emulsion or dispersion of the fluorochemical copolymer already has a surface tension substantially less than that of water, the effect of lowering the surface tension of the penetration aid will normally be less than with pure water.

The present invention also comprises a process which provides asphaltic materials with greater resistance to water, oil and weathering damage, which process comprises treating the materials with an aqueous composition containing: (A) from about 0.1 to 4% by weight, on a 100% solids basis, an aqueous solution or self dispersing emulsion or dispersion of a copolymer, which is a reaction product of monomers comprising fluorinated groups, cationic groups and optionally nonionic groups, optionally (B) an amount effective penetration aid; and (C) water to do 100%. Preferably, the process comprises treating the above substrates with an aqueous composition comprising 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 from about 0.01% by weight. 1% by weight of the penetration aid. In a preferred process, the copolymer in (A) is a reaction product of about 60-90% by weight of one or more meta (acrylate) monomers containing polyfluorinated alkyl groups, from about 10 to about 40% by weight of one or more met (acrylate) monomers that 17 • * «& they contain cationic groups and from about 1 to about 10% by weight of one or more monomers containing nonionic groups. Preferably, the nonionic group is selected from the group consisting of ethylene, propylene, utene, chloro-3-uten-1-butadiene, rene, 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 utyrate, heptanoate of allyl, cetyl vinyl ether, dodecyl vinyl ether, allyl-, methyl-, ethyl-, propyl-, ropyl-, butyl-, utyl-, hexyl-, heptyl-, ethyl-2-hexyl-, cyclohexyl-, lauryl- , stearyl- or ethoxyethyl esters 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, cyanoacrylate -2-ethyl, methyleneglutaronitrile, vinyl cyanate ene, ropyl cyanoacrylate, trisacryloyl-hexahydro-s-triazine, allylic alcohol, allyl glycolate, utenediol, allyloxy-ethanol, o-allylphenol, divinylcarbinol, glycerol-allyl ether, acrylamide, metacphamide, 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-crotononitrile , monoalylamine, vinylpyridines, acrylate or glycidyl methacrylate and its 5-chlorohydrins, allyl glycidyl ether and acrolein. It is especially preferred that the nonionic monomer comprises at least one monomer selected from the group consisting of glycidyl acrylate and its chlorohydrins. A particularly preferred process comprises Treat the above substrates with an aqueous composition wherein the copolymer (A) is a reaction product of the copolymerized monomer 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-Q-A-C (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 from 1 to 4 carbon atoms, 19 ailÉÍÍMMU ----------------------- ^ ------ M - ^ -------------- ?? ----- a - te ---? Y* * -****** *.

Q is alkylene of 1 to about 15 carbon atoms, hydroxyalkylene of 3 to about 15 carbon atoms, - (Cn H2n) (0Cq H2q) m-, -S02-NR (Cn H2n) -, or - CONR '(Cn) H2n) -, where R 'is H or an alkyl of 1 to 4 carbon atoms, n is from 1 to 15, q is from 2 to 4 and m is from 1 to 15; (b) from about 10 to about 40% of at least one monomer of formula II: (Ri) 2-CH2CH2-0-C (O) -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 wherein 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: or CI-CH2-CH (OH) CH2-O-C (0) - C (R4) = CH2 (IV) -vA .. ^ fc "** at, - ^. wherein R3 and R4 are each independently H or the same or different alkyl radical of 1 to about 4 carbon atoms. 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 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% by weight, the proportion of the monomer of formula II in the copolymer (in its salt form) is from about 13% to about 19% by 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 present invention also relates to an asphaltic material, which has greater resistance to water, oil and weathering damage, material which has been treated with a composition, which comprises: (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 comprising fluorinated groups, cationic groups and nonionic groups, optionally (B) an effective amount of a penetration aid, and (C) water to do 100%. The compositions of the present invention are prepared simply by combining an aqueous dispersion or self dispersing dispersion solution which typically contains from 20 to 35% by weight of fluorochemical copolymer and, if desired, the penetration aid and any conventional additives, for example a condom. such as an antimicrobial, a bactericide, a fungicide or an algaecide, with water of approximately neutral pH with gentle agitation. Preferably, the compositions are prepared by adding the fluorochemical copolymer and, if desired, the penetration aid and any conventional additives to the water. Advantageously, deionized water or distilled water of approximately neutral pH is used. If desired, a concentrate of the composition of the invention can be prepared by combining an aqueous solution of a more concentrated self dispersing emulsion or dispersion typically containing between 20 to 35% by weight of the fluorochemical copolymer., the penetration aid and any conventional additives and, optionally, all or preferably only a part of the water. The concentrated composition is then diluted with the appropriate amount of water to obtain a suitable concentration of the fluorochemical copolymer before being used in the treatment process of the invention. The compositions of the present invention can be applied to the surface of an asphaltic material by any known method, for example by washing, impregnation, dipping, brushing, rolling or spraying. Advantageously, the treatment compositions of the present invention are applied to the surface to be protected by sprinkling, and in particular by spraying with a compressed air sprinkler. The proper spray equipment is commercially available. The amount of compositions of the present invention to be applied to the surface of an asphaltic material is not critical. The quantity should be sufficient to perfectly wet the surface, but excessive spillage should be avoided for ecological reasons. Naturally, a relatively porous substrate, such as a road prepared from a mixture of asphalt and relatively large mineral aggregates, will absorb substantially greater amounts of the treatment composition due to subsurface penetration while other similar asphalt covering surfaces will require very little. After the application of a composition of the invention to a substrate, the treated surface should be allowed to dry perfectly before being exposed to water or oil. Interestingly, a porous substrate retains its porosity to a large extent after the treatment of the invention, so that air and wet steam can still pass through it. This shows that the surface is not sealed as it would be by a conventional coating. Although the liquid water and the oil are strongly repelled as a result of the treatment of the invention. The treated substrate also retains its natural appearance. The surface of a wide variety of asphalt materials can be treated advantageously with the compositions of the invention. These include roads and asphalt surfaces that support similar traffic, such as accesses, parking areas and runways for airport takeoffs, as well as gravel systems of asphalt composition and coating covered with asphalt. Of special interest are roads and asphalt surfaces that support similar traffic, especially those that are exposed to freeze-thaw cycles and treated with salts for 24 * ^ - melt snow and ice. The treatment of such surfaces with the compositions of the present invention can greatly mitigate the damage by freezing-thawing and thereby decrease maintenance and prolong the life time of the road in a very cheap way. The effectiveness of the surface treatment by the compositions of the invention was evaluated mainly visually by applying drops of water or motor oil (Pennzoil "of weight 30) to a horizontal surface treated and dry. While water normally wets asphaltic material and forms a continuous sheet or film, or is slowly absorbed by it, depending on its porosity, water is strongly repelled as a result of the treatment of the invention which, in general, simply forms small pearls, almost hemispherical on the surface of the treated material. Normally somewhat wider pearls are obtained which exhibit a lower contact angle with the treatment in the absence of the wetting agent. The water can be left on the treated surface during a indefinite period of time. Eventually, it simply evaporates without leaving any signs of surface damage. Even after an extensive freeze-thaw cycle, since the water does not penetrate the treated surface and the adhesion of the ice is damaged in a substantial, there is no evidence of surface damage.

Motor oil also normally wets and diffuses through an asphaltic material and is slowly absorbed by it. However, if the surface of an asphalt material is treated according to the process of the invention, there is a substantially smaller dispersion and absorption. Consequently, even after contact for a prolonged period, the oil can be easily removed by cleaning it with an absorbent material or rinsing it with a stream of water. The surface of an asphalt material treated according to the process of the invention shows improved properties in relation to the same surface only treated with the copolymer. 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 To a vessel containing 100 parts of deionized water was added gradually, with moderate agitation, 2.0 parts of LODYNE P-514, an aqueous composition comprising about 30% by weight of a cationic fluorochemical copolymer, which is commercially available from Ciba Specialty Chemical Corporation, High Point, NC, followed by 0.1 parts of Solvent-D, a liquid 26 patented which is available from Polypore, Inc., Tucson, AZ. If desired, a condom or other compatible additive can then be added and agitation is continued until the mixture is visually homogeneous. This is stable to storage.

Application of the composition of the invention to a surface In a compressed air spray apparatus a solution having the above composition is placed. Samples of asphalt pavement obtained from the demolition of a road are placed flat on a protected surface and then sprayed with the composition of the invention until their surfaces are perfectly wet. Then, the treated materials are allowed to dry perfectly before being evaluated as described above. The treated materials still exhibit excellent water and oil repellency after approximately one year of storage. Several small sections of an asphalt road in Tucson, Arizona were sprayed with the composition of the invention as described above. The water still forms pearls on the treated surfaces after almost a year of exposure. The asphalt composition gravels are placed flat on a protected surface and then sprayed with the composition of the invention as described above until their surfaces were perfectly wetted. Then, the treated materials were allowed to dry perfectly before being evaluated. After prolonged storage and a periodic freeze-thaw cycle there was no evidence of surface damage.

Claims (19)

1. A composition that provides asphaltic materials with greater resistance to water, oil and weathering damage, composition which is characterized in that it comprises: (A) from about 0.1 to 4% by weight, on a 100% solids basis, of a solution aqueous emulsion or self-dispersing dispersion of a copolymer, which is a reaction product of monomers containing fluorinated groups, cationic groups and non-ionic groups, optionally (B) an effective amount of a penetration aid, and (C) water for do 100% with the proviso that if copolymer is a reaction product of monomers including 1% or more of vinyl acetate, the composition also contains from about 0.01 to 1% by weight of a penetration aid.

2. The composition according to claim 1, characterized in that it comprises from about 0.2 to about 2% of the aqueous solution or self-dispersed emulsion or dispersion of the polymer on a 100% solids basis, and 29 about 0.01 to 1 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 plus meth (acrylate) monomers containing cationic groups and about 1 to about 10% by weight of 1 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 difluor-butadienes, vinylidene chloride, vinyl fluoride or vinylidene, allyl bromide, methallyl chloride, vinyl toluene, alpha-methylstyrene, alpha-cyanomethylstyrene , divinylbenzene, N-vinylcarbazole, methyl vinyl ketone, allyl ketone, allyl propionate, allyl isobutyrate and allyl heptanoate, cetyl vinyl ether, dodecyl vinyl ether, allyl-, methyl-, ethyl-, propyl-, isopropyl-, butyl -, isobutyl-hexyl-, heptyl-ethyl-2-hexyl-, cyclohexyl-, lauryl-, 30 ^^^^^ s ^^^^^ & ^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^ ^^ x stearyl- or ethoxyethyl esters 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, acrylate of cyano-2- ethyl, methylene glutaronitrile, vinylidene cyanate, isopropyl cyanoacrylate, trisacryloyl-hexahydro-s-triacma, 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-crotononitrile, monoalylamine, vinylpipdines, 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 the monomer selected from the group consisting of glycidyl acrylate or methacrylate and its chlorohydrins.

6. The composition according to claim 1, characterized in that the copolymer (A) is a reaction product of copolymerized monomers in the 31 following percentages by weight, based on 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 ) in which Rf 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 about 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 1 to 15; (b) from about 10 to about 40% of at least one monomer of formula II: (Ri) 2N-CH2CH2-0-C (O) -C (R2) = CH2 (II) in which Ri is an alkyl group from 1 to 3 carbon atoms, R 2 is H or an alkyl radical of 1 to 4 carbon atoms, and where the nitrogen is 40 to 100% quaternized or in the form of a salt; Y 32 (c) from about 1 to about 7% of at least one monomer of formula III or IV, or a mixture thereof C? H2-CH-CH2-O-C (O) -C (R3) = CH2 (III) Cl-CH2-CH (OH) CH2-0-C (0) - C (R4) = CH2 (IV), in which R3 and R4 are each independently H or the same an alkyl radical different from 1 to about 4 carbon atoms.

The composition according to claim 6, characterized in that Rf is a straight chain perfluoroalkyl group of about 2 to about 20 carbon atoms, or a mixture thereof, A is O and Q is an alkylene of about 15 atoms of carbon, 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 asphalt materials with greater resistance to damage with water, oil, and weathering, which process comprises treating the materials with an aqueous composition, characterized in that it comprises: (A) from about 0.1 to 4% by weight, on a 100% solids basis, an aqueous solution or self dispersing emulsion or dispersion of a copolymer which is a reaction product of monomers comprising fluorinated groups, cationic groups and nonionic groups, optionally (B) an effective amount of a penetration aid, and (C) water to do 100%.

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% by 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 meta (acrylate) monomers containing polyfluorinated alkyl groups, of about 10 to about 40% by weight of one or more met (acrylate) monomers containing cationic groups and from about 1 to about 10% by weight of one or more monomers containing nonionic groups.

11. The process according to claim 8, characterized in that the copolymer (A) is a reaction product of one or more monomers containing -f 'nonionic groups selected from the group consisting of ethylene, propylene, isobutene, chloro- 3-isobuten-1-butadiene, isoprene, chloro- and dichloro-butadienes, fluoro- and difluorobutadienes, 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, 10 allyl-, methyl-, ethyl-, propyl-, isopropyl-, butyl-, isobutyl-, hexyl-, heptyl-, ethyl-2-hexyl-, cydohexyl-, lauryl-, stearyl-p-ethoxyethyl esters of acrylic acid, methacrylic, alpha-chloroacrylic, crotonic, maleic, fumaric, itaconic, citraconic and senecioic, diacrylates and dimethacrylates of 15 glycol or polyalkylene glycol, acrylonitrile, methacrylonitrile, chloro-2-acrylonitrile, cyano-2-ethyl acrylate, methyleneglutaronitrile, vinylidene cyanate, isopropyl cyanoacrylate, crisacryloyl-hexahydro-striazine, allyl alcohol, allyl glycolate , isobutenediol, 20 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-25-acrylamide, amino-3-crotononitrile, monoalylamine, vinylpyridines, acrylate or glycidyl m-phenyl acrylate and its chlorohydrins, allyl glycidyl ether and acrolein.

12. 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.

The process according to claim 8, characterized in that the copolymer (A) is a reaction product of copolymerized monomers in the following percentages by weight, based on the total weight of the copolymers: (a) from about 60% up to about 90% of at least one monomer of formula I: Rf-Q-A-C (O) -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 CH 3, 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 about 15 carbon atoms, - (Cn H2n) (OC H2q) m_, -S02-NR (Cn H2n) - or -CONR '(Cn Ü2) ~ r where R is H or an alkyl of 1 to 4 carbon atoms, n is from 1 to 15, q is from 2 to 4 and m is from 1 to 15; (b) from about 10 to about 40% of at least one monomer of formula II: (R1) 2-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 wherein 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: OR CH-CH-CH-O-C (O) -C (R3) = CH2 (III) or Cl-CH2-CH (OH) CH2-0-C (0) - C (R4) = CH2 (IV) in which 37 : * ^ fa t ^ i ^ B R3 and R4 are each independently H or the same or different alkyl radical of 1 to about 4 carbon atoms.

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 13, characterized in that the proportion of the monomer of formula I in the copolymer is from about 79% to about 85% by weight, the proportion of the monomer of formula II in the copolymer (in its form of salt) is from about 13% to about 19% by 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.

16. The process according to claim 8, characterized in that the aqueous composition is sprayed on the surface of the asphalt material with a compressed air sprinkler. 38

17. The process * f-d according to claim 13, characterized in that the aqueous composition is sprayed on the surface of the asphalt material with a compressed air sprinkler.

18. The process according to claim 8, characterized in that the asphalt material is an asphalt surface bearing traffic, gravel of asphalt composition or a coating system coated with asphalt.

19. An asphalt material which has greater resistance to water, oil and weather damage, material which has been treated with a composition, characterized in that it comprises: (A) from about 0.1 to 4% by weight, on a base of 100 % solids, an aqueous solution or self-dispersing emulsion or dispersion of a copolymer, which is a reaction product of monomers comprising fluorinated groups, cationic groups and non-ionic groups, optionally (B) an effective amount of a penetration aid , and (C) water to do 100%. 39 ^^^ é