MXPA06007616A - Latex paint compositions and coatings - Google Patents

Abstract

A latex paint composition comprises (a) a polymer having interpolymerized units that comprise units derived from styrene, methyl styrene, vinyl, or combinations thereof and units derived from one or more acrylates, methacrylates, acrylonitrile, or combinations thereof, (b) hiding pigment, (c) non-cellulosic thickener, and (d) at least about 0.01 weight per volume percent fluorochemical acrylic polymer additive comprising:(1) at least one perfluoroalkyl moiety selected from the group consisting of heptafluoropropanesulfonamido, nonafluorobutanesulfonamido, undecafluoropentanesulfonamido, and tridecafluorohexanesulfonamido moieties, (2) at least one polyoxyalkylene block comprising at least one (a) alkyleneoxy moiety or (b) alkylene group interrupted by a carboxyester moiety, e.g., a caprolactone acrylate, and (3) at least one water-solubilizing group. Also, methods for providing paint coatings with such compositions.

Description

COMPOSITIONS AND LATEX PAINT COATINGS FIELD OF THE INVENTION The present invention relates to latex paint compositions and coatings comprising short chain fluoroglycos and to methods for imparting improved stain and dirt resistance to latex paints.

BACKGROUND OF THE INVENTION Latex paints are often preferred over solvent based paints, due to their improved safety, lower toxicity, and lower volatile organic contents. Generally, however, latex paints, particularly smooth latex paints, have poor resistance to stains and dirt. Due to its highly porous nature and rough surface texture, smooth latex paints tend to absorb stains. Penetrating stains, such as inks, light beverages, wines and other colored liguids, have easy access to the interior of a smooth paint film through numerous pores and microchannels, and surface dirt, such as handprints, smudges , dust and other particulate matter, can get caught in the rough, uneven texture of the paint surface. REF .: 174234 In recent years, smooth latex paints have been formulated which have improved resistance to staining and soiling with resultant improved cleaning performance (see for example, EP 0 614 955). In addition, various additives, including acrylic hydrocarbon polymers and fluorine containing compounds, have been used to impart improved-resistance to staining and fouling to latex paints. Consumers, however, want smooth latex paints, which can provide even better stain and fouling resistance, with resultant improved cleaning ability. PCT Patent Application No. US03 / 14831, discloses the use of minor amounts of short chain fluoroguimics, to impart improved stain and fouling resistance in latex paints comprising a pigment volume concentration of at least 20% and less of its critical concentration of pigment volume.

SUMMARY OF THE INVENTION In view of the foregoing, it is recognized that there is a need to improve the resistance to staining and soiling of latex paints, particularly smooth latex paints, without departing from the other desirable properties of the paint, such as, for example, improved security and minimized environmental impact.

Briefly, in one aspect, the present invention provides compositions and coatings of latex paints (as used herein, the term "coating" refers to the latex paint composition that has been applied to a substrate and has been applied to a substrate. dried), which have improved resistance to staining - and fouling with resultant improved cleaning capacity. The compositions comprise a latex paint comprising: (a) a polymer having interpolymerized units comprising units derived from styrene, methylstyrene, vinyl or combinations thereof and one or more units derived from acrylates, methacrylates, acrylonitrile or combinations of the same, (b) opaque pigment, (c) non-cellulosic thickener, and (d) at least 0.05 weight percent by volume of fluoroguimic acrylic polymer additive which comprises: (1) at least one portion of perfluoroalguyl selected from the group consists of portions of heptafluoropropansulfonamido, nonafluorobutanesulfonamido, undecafluoropentanesulfonamido and tridecafluorohexansulfonamido, (2) at least one polyoxyalogylene blogue comprising at least a portion (a) alkyloxy or (b) an aliphenylene group interrupted by a carboxy ester moiety, for example, an acrylate of caprolactone, and (3) at least one polar stabilizing group in water; wherein said fluoroguimic acrylic polymer comprises about 5 to about 30 weight percent of fluorine attached to carbon (i.e., covalently attached), based on the total weight of said fluoroguimic acrylic polymer, and said latex paint composition, which has a pigment volume concentration of at least 20% and equal to or greater than its critical concentration of pigment volume. In other aspects, this invention also provides articles with at least one surface of the article coated with the paint compositions of the invention, and methods for imparting resistance to staining and soiling to a latex paint. The methods comprise: (a) providing a latex paint composition comprising: (1) a polymer having interpolymerized units comprising units derived from styrene, methylstyrene, vinyl or combinations thereof, and units derived from one or more acrylates , methacrylates, acrylonitrile or combinations thereof, (2) opaque pigment, and (3) non-cellulosic thickener; wherein said latex paint has a pigment volume concentration of at least 20% and equal to or greater than its critical concentration of pigment volume; (b) adding at least about 0.05 volume percent by weight of a fluoroguimic acrylic polymer additive comprising: (1) at least one portion of perfluoroalguyl selected from the group consisting of portions of heptafluoropropanesulfonamido, nonafluorobutanesulfonamido, undecafluoropentanesulfonamido and tridecafluorohexansulfonamido, ( 2) at least one polyoxyalogylene blogue comprising at least (a) a portion of the alkyloxy or (b) an aliphenylene group interrupted by a carboxy ester portion, eg, a caprolactone acrylate, and (3) at least one polar group solubilizer in water; wherein said fluoroguimic acrylic polymer has from about 5 to about 30 weight percent of fluorine bonded to carbon, based on the total weight of said fluoroguimic acrylic polymer in said latex paint composition; (c) apply the resulting composition of (b) to a substrate surface; and (d) allowing said resultant composition to dry in such a way that a coating with a fluorinated surface is formed on said surface of the substrate. As used herein, a "fluorinated surface" refers to a coating that contains more fluoride on the surface than in the volume.

DETAILED DESCRIPTION OF THE INVENTION It has been found that the fluoroguimic acrylic polymer additives described herein, particularly those derived from perfluorobutanesulphonyl fluoride (PBSF), impart improved stain and dirt resistance and repellency in the latex paint composition of the invention. . Surprisingly, these fluoroguimic acrylic polymers impart comparable resistance and repellency to stains and dirt, and in some cases better than fluoroguimic acrylic polymers with longer perfluoroalguyl segments such as perfluoroactansulfonyl fluoride (POSF). In view of the prior art, it could be expected that coatings derived from shorter fluoroguimic chains could not be as effective in imparting resistance and repellency to stains and dirt, as those derived from longer fluoroguimic chains. For example, in the surfactant technique, particularly surfactants with fluoroguimic chains, there is a preference for those with longer fluorochemical chains (eg, C6-C? Or in U.S. Patent No. 2,803,615 (Ahlbrecht et al.) And C6- C? 2 in U.S. Patent No. 3,787,351 (Olson)): It has been observed in hydrocarbon surfactants and in surfactants derived from perfluorocarboxylic acids and sulfonic acids, that increasing the chain length of the hydrocarbon chains decreases the critical concentration of micelles (that is, less surfactant is needed to obtain the desired surface modification) (see, for example, AMPHOTERIC SURFACTANTS AND THEIR INDUSTRIAL APPLICATIONS, edited by RE Banks, Ellis Horwood Ltd.-, p.56 (1979); JO Hendricks, Ind. Eng. Chern., 45, 103 (1953), MK Bernett and WA Zisman, J. Phys. Chem. 63_, 1912 (1959)). The repellency results, in part, from the low surface energies. The prior art suggests that only after the seven outer carbon atoms of a perfluorinated carboxylic acid are completely fluorinated do the energy of the surface of several liguides on the surface near the glue of a monolayer of perfluoroalguyl acid, which has an energy of surface area among the lowest still recorded (see for example, NO Brace, J. Org. Chem. 27, 4491 (1962) and WA Zisman, Advan. Chem., 22 (1964)). One might therefore expect that the same is true for fluoroguimic acrylic polymers derived from PBSF. That is, one would expect that the surface energy of the polymer could be tightly bound to the chain length of the fluorinated monomer. Still, the fluoroguimic acrylic polymers of the invention impart comparable resistance and stain and soil repellency, and in some cases better, than fluoroguimic acrylic polymers with longer perfluoroalguyl segments. It is particularly advantageous to use short chain perfluoroalkanesulfonyl fluorides, such as PBSF, to make the starting intermediates for the paint additives preferably using POSF, because they can be produced at a lower cost by weight due to their higher yields (e.g. , by electrofluorination, the yield of PBSF is approximately 58% and the yield of POSF is approximately 31% (PREPARATION, PROPERTIES, AND INDUSTRIAL APPLICATIONS OF ORGANOFLUORINE COMPOUNDS, edited by R. E. Banks, Ellis Horwood Ltd., P. 23 (1982)) and still maintain their potency as repellents at the same weight percentage. In addition, it has been reported that certain compounds containing perfluorooctyl can bioaccumulate in living organisms (see for example, U.S. Patent No. 5,688,884 (Baker et al.)). The short chain sulfonic acids, however, are less toxic and less bioaccumulative than the longer chain homologs. For example, PBSF, tested in the form of its potassium salt, are removed from the body much more efficiently than POSF and perfluorohexansulfonate (see, for example, WO 01/30873). Thus, the compositions of the invention meet the need in the art for latex paints which have improved stain and dirt resistance while maintaining the other desirable properties of the paint. It has now been discovered that a polar water-solubilizing group is incorporated into the fluoroguimic acrylic polymer additive so that the resulting additive will surprisingly impart improved staining and fouling resistance to paints, in particular to paints having a high volume concentration. pigment which is equal to or greater than the volume of critical pigment in the paint. As a result, the present invention provides improved resistance to staining and soiling which have historically been considered poor quality paints.

Paint Compositions Binding Polymer The polymers useful as component (a), the "binder polymer" of the latex paints of the invention, are copolymerization products of a mixture of co-monomers which comprise monomers selected from styrene, methylstyrene, vinyl , or combinations thereof. Preferably, the co-monomers comprise (more preferably, essentially consist of) at least 40 mole percent of monomers selected from styrene, methylstyrene or combinations thereof and at least 10 mole percent of one or more monomers selected from acrylates. , methacrylates and acrylonitrile. Preferably, the acrylates and methacrylates contain from 4 to 16 carbon atoms, such as, for example, 2-ethylhexylacrylate and methyl methacrylates. It is also preferable that the monomers be used in a proportion such that the final polymer has a glass transition temperature (Tg) greater than 21 ° C and lower than 95 ° C. The polymers preferably have a weight average molecular weight of at least 100,000. Preferably, the binder polymer comprises interpolymerized units derived from 2-ethylhexyl acrylate. More preferably, the binder polymer comprises polymerized units comprising from 50 to 70 percent mole of units derived from styrene, methylstyrene or combinations thereof; from 10 to 30 percent in mole of units derived from 2-ethylhexylacrylate; and from 10 to 30 percent mole of units derived from methylacrylate, acrylonitrile or combinations thereof. Illustrative examples of suitable binder polymers include a copolymer whose interpolymerized units are derived from about 49 percent by mole of styrene, 11 percent by mole of a-methylstyrene, 22 percent by mole of 2-ethylhexyl acrylate and 18 percent by mole of methyl methacrylates with a Tg of about 45 ° C (available as Neocryl ™ XA-6037 polymer emulsion from ICI Americas, Inc., Bridgewater, NJ); a copolymer whose interpolymerized units are derived from about 51 percent by mole of styrene, 12 percent by mole of a-methylstyrene, 17 percent by mole of 2-ethylhexyl acrylate, and 19 percent by mole of methylmethacrylates with a Tg of about 44 ° C (available as Joncryl ™ polymer emulsion from SC Johnson &Sons, Racine, Wl); and a terpolymer whose interpolymerized units are derived from about 54 percent by mole of styrene, 23 percent by mole of 2-ethylhexylacrylate, and 23 percent by mole of acrylonitrile with a Tg of about 44 ° C (available from BF Goodrich Co. as Carboset ™ polymer emulsion XPD-1468). Preferably, the binder polymer is Joncryl ™ 537.

Opaque Pigment The latex paint of the invention comprises an opaque pigment to give the paints better "opaque power" or coverage. Preferably, the opaque pigment has a refractive index above about 1.8. Suitable opaque pigments include opaque opacifying pigments and colored organic and inorganic pigments. Representative examples of suitable white opaque opacifying pigments include, titanium dioxides anatase and rutile, lithopone, zinc sulphide, silver titanate, antimony oxide, zirconium oxide, barium sulphide, white silver, zinc oxide, zinc oxide silver and the like, and mixtures thereof. A white organic opaque pigment is rutile titanium dioxide. More preferred is rutile titanium dioxide having an average particle size between about 0.2 to 0.4 microns. Examples of colored organic pigments are blue phthalo and yellow hansa. Examples of colored inorganic pigments are red iron oxide, brown oxide, ocher and earth.

Thickener Most known latex paints contain thickeners to modify the rheological properties of the paint, to ensure good distribution, handling and application characteristics. The latex paint of the invention comprises a non-cellulose thickener (preferably, an associative thickener); more preferably, an associative urethane thickener). Associative thickeners such as, for example, acrylic copolymers expandable hydrophobically modified alkalis and hydrophobically modified urethane copolymers generally impart more Newtonian rheology to emulsion paints compared to conventional thickeners such as, for example, cellulosic thickeners. Representative examples of suitable associative thickeners include polyacrylic acids (available, for example, from Rohm &Haas Co., Philadelphia, PA, as Rheology Modifiers Acrysol ™ RM-825 and QR-708) and activated attapulgite (available from Engelhard, Iselin, NJ as Attagel ™ 40).

Fluorochemical Admixture The latex paint of the invention comprises at least about 0.01 volume percent by weight of a fluoroguimic acrylic polymer additive ("additive, fluoroguimic"), which imparts improved stain and fouling resistance to paint compositions. The fluoroguimic additive comprises: (1) at least one portion of perfluoroalguyl selected from the group consisting of portions of heptafluoropropanesulfonamido, nonafluorobutanesulfonamido, undecafluoropentanesulfonamido, and tridecafluorohexansulfonamido, (2) at least one polyoxyalogylene blogue comprising at least (a) an alkyloxygen portion or (b) an alkenylene group interrupted by a carboxy ester moiety, for example, a caprolactone acrylate, and (3) at least one polar water solubilizing moiety. The perfluoroalguyl portions used in the invention are generally soluble over a wide polarity range. Preferably, the perfluoroalguyl portion is heptafluoropropansulfonamido or nanfluorobutansulfonamido. More preferably, the perfluoroalguyl portion is nonafluorobutanesulfonamido. Preferably, a plurality of perfluoroalguyl portions are each linked in at least one polyoxyalogylene block by a polymer chain. The polyoxyalogylene blocks comprise at least one portion of allyloxy. The alkyleneoxy portion generally has 2 to 6 carbon atoms (preferably 2 to 4 carbon atoms, more preferably 2 or 3 carbon atoms). Preferred alkyloxyxy moieties include, for example, ethyleneoxy moieties and propyleneoxy moieties. The propyleneoxy moieties may be branched or linear. When the ethyleneoxy moieties and propyleneoxy moieties are linked together, they are formed from polyoxyethylene and polyoxypropylene blogs, respectively. Preferably, at least one polyoxypropylene blog is linked to a polyoxyethylene blog. Additional polioxyethylene or polyoxypropylene blogs may be present in random order as well. Such materials having an average molecular weight of from about 500 to about 1,500 are commonly available under trade names such as, for example, Pluronic ™ (or Pluronic ™ R, a reverse Pluronic structure) from BASF Corporation. More preferably, the The polyoxypropylene blog is also linked to a second polyoxyethylene block (or the polyoxyethylene blog is linked to a second polyoxypropylene blog). Particularly useful block polymers include adhesives, for example, comprising a central blog having from about 20 to about 55 propylenoxy portions and blogs on each side of the central blog and each having from about 5 to about 130 ethyleneoxy moieties. Other particularly useful blog polymers include those comprising a core block having from about 15 to 165 portions of ethyleneoxy and blogs on each side of the central blog having from about 5 to about 25 portions of propyleneoxy. Other preferred alkyloxyxy portions are agueilles derived from polyethylene glycols having a molecular weight from about 200 to 10,000. Commercially available polyethylene glycols which are suitable for use in the invention include, for example, Carbowax ™ (available from Union Carbide). The acrylate portion of the fluoroguimic additive comprises portions of acrylate and / or methacrylate. The acrylate and / or methacrylate portions form part of the starting monomers, as well as the final polyacrylate products. For example, the nonafluorobutanesulfonamido acrylate can be copolymerized with a polyalkylenoxy moiety to form surface active agents. In this way, the fluorochemical acrylic polymer additives used in the paint composition of the invention can be prepared, for example, by free radical initiated copolymerization of an acrylate containing nonafluorobutanesulfonamido radicals with a polyalkyleneoxy acrylate such as, for example, monoacrylate, diacrylate or mixtures thereof. The molecular weight of the polyacrylate copolymer can be controlled by adjusting the concentration and activity of the initiator, concentration of monomers, and temperature, or by chain transfer agents. The preparation of such starting nonafluorobutanesulfonamide polyacrylates and acrylates is known in the art (see, for example, U.S. Patent Nos. 3,787,351 (Olson) and 2,803,615 (Ahlbrecht et al.) Respectively. Polyalkylenoxy acrylates can be prepared from commercially available hydroxypolyether or hydroxy polyoxyalkylene compounds such as, for example, Pluronic ™ or Carbowax ™ polymers Such hydroxy materials are reacted with acrylic acid, acrylic chloride or acrylic anhydride using methods known in the art.

Alternatively, a polyalkylenoxy diacrylate can be copolymerized with the nonafluorobutanesulfonamido acrylate to obtain a polyacrylate copolymer of the invention. The luorochemical additives described above may optionally comprise a polar water-solubilizing group, which may be anionic, non-ionic, cationic or amphoteric. Preferably, the water solubilizing polar group is anionic. More preferably, it is selected from the group consisting of sulfonates, sulfates and carboxylates (for example, -S03M, -OS03M, and -C (= 0) 0M wherein M is hydrogen, a metal cation such as an alkali or alkali metal cation earth (for example, sodium, potassium, calcium or magnesium and the like), or a nitrogen-based cation, such as, for example, protonated or ammonium tertiary amine (for example, (H0CH2CH2) 2NTHC3)). The luorochemical additives used in the composition of the paint of the invention include those that can be represented by the following general formula: Formula I where ww ww. represents a bond in a polymeric or polymerizable chain; R, R and R2 are each independently, hydrogen or alkyl of 1 to 4 carbon atoms; R3 is at least one or more straight or branched alkyleneoxy groups, bonded together and having 2 to 6 carbon atoms, or a straight or branched alkylene group, having 12 to 20 carbon atoms; n is an integer from 2 to 10; and x, y, and z are integers of at least 1. Preferred fluorochemical additives of Formula I include those in which R, Ri and R2 are each independently hydrogen or methyl and those in which n is 2. Another preferred embodiment is wherein R3 is a polyalkylene oxide group selected from those represented by formula A or formula B: Formula A Formula B (EO) p- (PO) q- (EO) p (PO) q- (EO) p- (PO) q where EO is an ethyleneoxy moiety, PO is a propyleneoxy moiety, p is a number integer from 1 to about 165, and q is an integer from 0 'to about 55. Preferably, when R3 is a polyalkylene oxide group of Formula A, p is an integer from about 5 to about 130 and q is a whole number from about 20 to about 55. More preferably, p is about 11 and q is about 21. Even more preferably, p is about 11, q is about 21, and R is methyl. Preferably, when R3 is a polyalkylene oxide group of Formula B, q is an integer from about 5 to about 25 and p is an integer from about 10 to about 165. The fluorochemical additives employed in the paint composition of the invention , also include the reaction products of the following monomers or oligomers: (i) a compound represented by the following general formula: CH2 (ii) a compound selected from the group consisting of and mixtures thereof; and (iii) a compound represented by the following general formula: wherein R, Rlf R2, R 'are hydrogen or alkyl of 1 to 4 carbon atoms, EO is a portion of ethyleneoxy, PO is a propyleneoxy portion, p is an integer from 1 to about 130, q is a number integer from 0 to about 55, n is an integer from 2 to about 10, n 'is an integer from 1 to about 10, and M is hydrogen, a cation, or a protonated tertiary amine. Preferably, (iii) is a compound represented by the following general formula: wherein R2 is hydrogen or methyl and M is hydrogen, potassium, ammonium, lithium or a protonated tertiary amine. In a particularly useful embodiment, the fluorochemical additive comprises the reaction product of (i), (ii), (iii) and (iv), wherein (iv) is a compound represented by the general formula AOC (= 0) C (R2) = CH2; wherein A is a group containing amine or an alkyl of 12 to 20 carbon atoms. The fluorochemical additives employed in the paint composition of the invention also include the reaction products of the following: (i) a compound represented by the following general formula: (ii) a compound selected from the group consisting of: HO (EO) p- (PO) q- H2 HO (PO) q- (EO) p CH2 R-i- "(EO) - and mixtures thereof, and (iii) a compound represented by the following general formula: M-O-C (= O) -C (R2) = CH2 wherein R, Ri, R2 and R 'are independently hydrogen or alkyl of 1 to 4 carbon atoms, n is an integer from 2 to about 10, EO is an ethyleneoxy portion, PO is a propyleneoxy moiety, p is a number integer from 1 to approximately 130, q is an integer from 0 to approximately 55, and M is H, potassium, sodium, ammonium or protonated tertiary amine. Preferably, M is H or ammonium. In a particularly useful embodiment, the fluoroguimic additive comprises the reaction product of (i), (ii), (iii) and (iv), wherein (iv) is a compound represented by the general formula AOC (= 0) C (R2) = CH2; wherein A is a group containing amine or an alkyl of 12 to 20 carbon atoms. In some embodiments, the additive may contain an alkylene group interrupted by a carboxy ester moiety, for example, a caprolactone acrylate, instead of or in combination with the polyoxyalkylene block materials described above. For example, SR495, a caprolactone acrylate from Sartomer and having the formula HO (CH2) 5C (O) O (CH2) 5C (O) 0 (CH2) 2? COCH = CH2 | , it can be used in accordance with the present invention.

The fluorochemical additives used in the paint compositions of the invention also contain at least one water solubilizing polar group, which may be anionic, nonionic, cationic or amphoteric. Preferred anionic groups include, but are not limited to, sulfonates (e.g., -S03M), sulfates (e.g., -OSO3M, and carboxylates (e.g., -C (= 0) 0M.) M is hydrogen, a cation metal such as an alkaline earth metal or alkali cation (eg, sodium, potassium, calcium or magnesium and the like), or a nitrogen-based cation, such as, for example, ammonium or a protonated tertiary amine (eg, ( HOCH2CH2) 2NTHCH3) The polar sulfonate groups are used as oligomers or polymers including polyacrylates and polyacrylamides A particularly useful monomer or oligomer employed in the present invention is a polyacrylamide sulfonate of the formula: wherein R2 and R are as defined above; R 'is hydrogen, or alkyl of 1-4 carbon atoms, especially methyl; n 'is an integer from 1 to 10, and M is hydrogen, a metal cation, or a protonated tertiary amine. A preferred anionic group is 2-acrylamido-2-methyl-l-propanesulfonic acid (AMPS) or the potassium salt itself. Useful representative cationic water solubilizing groups include, for example, ammonium or quaternary ammonium salts. Preferred monomers that provide cationic water solubilizing groups, include, dimethylaminoethyl methacrylate, dimethylaminoethyl acrylate and the like. For example, the surfactant can be made by incorporating compounds of the formula A-O-C (= 0) C (R2) = CH2, wherein A is an amine-containing group. In pure form, the fluorochemical additives employed in the paint compositions of the invention are typically viscous liquids or glassy solids. They are soluble in polar synthetic resinous compositions and have from about 5 to about 30 weight percent of fluorine bonded to carbon, based on the total weight of the fluorochemical additive (preferably, about 10 to about 25 weight percent). The present invention comprises at least about 0.01 weight percent by volume of the fluorochemical additive and typically contains up to about 3 weight percent by volume of the additive Typically, a preferred range is between about 0.2 and about 0.3 weight percent. of volume of an optimal balance of operation and cost.Further fluorochemical additive (up to about 10 weight percent by volume) can be used, but the use of high concentrations, typically at some point, will become prohibitively expensive.

Other Ingredients Latex paint films are formed by the coalescence of the binding polymer to form a bonding matrix at room temperature of paint application to form a hard, tack-free film. The coalescing solvents help the coalescence of the binder that forms the film, decreasing the film formation temperature. The latex paints of the invention preferably contain a coalescing solvent. Representative examples of suitable coalescing solvents include 2-phenoxyethanol, diethylene glycol butyl ether, dibutyl phthalate, diethylene glycol, 2, 2, 4-trimethyl-1,3-pentanediol monoisobutyrate and combinations thereof. Preferably, the coalescing solvent is diethylene glycol butyl ether (butyl carbitol) (available from Sigma-Aldrich, Milwaukee, WI) or 2, 2,4-trimethyl-1,3-pentanediol monoisobutyrate (available from Eastman Chemical Co. , Kingsport, TN, such as Texanol ™), or combinations thereof. The coalescing solvent is preferably used at a level between approximately 12 to 60 grams (preferably about 40 grams) of coalescing solvent per liter of latex paint or to about 20 to 30 weight percent, based on the weight of the solid polymers in the paint. The paints can be manufactured to have a desired degree of brightness or brilliance. The paint gloss is defined using an ASTM Test Method D523"Standard Test Method for Specular Brightness". The brightness ratings for this test method are obtained by comparing the reflectance of the specimen (at an angle of 20 °, 60 ° or 85 ° measured from the vertical) with that from a polished gloss standard. 20 ° brightness ratings describe the "depth" of brightness and are typically only used to describe gloss or semi-gloss paints. 60 ° gloss ratings are used to describe most paints, except for completely smooth paints. The 85 ° brightness ratings describe the "reflection" of smooth, egg-shell and glossy paints. Typically, paints are categorized by their brightness values. For example, the Main Institute of Painting (MPI), categorizes the paintings as follows: Type of 20 ° brightness 60 ° 1 brightness 85 ° brightness paint Brilliant 20-90 70-85 + - Semi- 5-45 35-75 glossy Satin - 20-35 Min. 35 Cascara 10-25 10-35 smooth egg / mate "0-10 Max. 35 The latex paints of the invention preferably have a brightness of 85 ° less than or equal to about 20 and could therefore typically be considered plain or egg shell paints. Smoother paints can be produced using various procedures. One method is to increase the pigment volume concentration (ie, the volume ratio of all the pigments in the paint to total non-volatiles) (PVC) of the paint above its critical pigment volume concentration (CPVC). At the CPVC, many physical and optical properties of the paint change abruptly and the paint changes from a semi-glossy paint to a smooth paint. Typically, although paints of high PVC plants exhibit less durability than flat paints of lower PVC, all of these are the same, because these flat paints have less binder available per unit of pigment. Alternatively, a smooth paint can be produced by adding a flattening agent, (that is, a material which reduces the gloss of a paint film). Flaking agents introduce micro-roughness to the surface, causing light to be reflected in a diffuse manner, which reduces the apparent brightness. This last procedure generally produces a better paint film. Therefore, the smooth paints of the present invention have a PVC of at least 20% and less of their CPVC, but preferably they contain a flattening agent. Preferably, the PVC is below about 54%; more preferably, below about 52%.

Suitable plating agents include silicas of various types, such as, for example, Novacite ™ Silica. (available from Mrn Minerals, Hot Springs National Park, AR). The paints of this invention may further comprise conventional materials used in paints such as, for example, plasticizer, anti-foam agent, pigment extender, pH adjuster, color staining and biocides. Such typical ingredients are listed, for example, in TECHNOLOGY OF PAINTS, VARNISHES AND LACQUERS, edited by C.R. Martens, R. E. Kreiger Publishing Co. , p. 515 (1974). Paints are commonly formulated with "functional extenders" to increase coverage, reduce costs, achieve durability, altered appearance, rheology control and influence other desirable properties. Examples of functional extenders include, for example, barium sulfate, calcium carbonate, clay, gypsum, silica and talc. The most common functional extenders for interior smooth paints are clays. Clays have a number of properties that make them desirable. Cheap calcined clays, for example, are useful for controlling low cut viscosity and have a large internal surface area, which contributes to "dry skin". But, this surface area is also available to catch spots. Due to its tendency to absorb stains, it is preferable that the calcined clays be used in the paints of the invention only in small amounts required for rheology control, for example, typically as less than about half the total extender pigment, or not. they are all used. Preferred extenders for use in the paints of the invention are calcium carbonates; more preferred are ultra fine ground calcium carbonates, such as, for example, Opacimite ™ (available from ECC International, Sylacauga, AL), Supermite ™ (available from Imerys, Roswell, GA), or others having a particle size of approximately 1.0 to 1.2 microns. Ultrafine calcium carbonate, helps to separate titanium dioxide optimally by skin (see for example, KA Haagenson, "The effect of extending particle size on the hing properties of an interior latex fíat paint", American Paint &Coatings Journal , April 14, 1988, pp. 89-84).

Preparation of the Paint Composition The latex paints of the invention can be prepared using conventional techniques. For example, some of the ingredients of the paint are generally combined together under high cut to form a mixture commonly referred to as "milled" by paint formulators. The consistency of this mixture is comparable to that of sediments, which is desirable to efficiently disperse the ingredients with a high cut agitator. During the preparation of the ground, the high cut energy is used to break apart agglomerated pigment particles. The ingredients not included in the milling are commonly referred to as "the descending". The descending is usually much less viscous than the ground and is usually used to dilute the grind to obtain a final paint with the proper consistency. The final mixing of the ground with the descending, is typically carried out with low-cut mixing.

Most polymer latexes are not stable to cutting, and therefore, are not used as a component of grinding. The incorporation of unstable latexes to the cut in the grinding, can result in coagulation of the latex, providing a lumpy paint in no or little capacity of film formation. Consequently, the paints are generally prepared by adding the latex polymer downward. However, the preferred paints of this invention contain latex polymers that are generally stable to cutting. Therefore, the latex paints of the invention can be prepared by incorporating some or all of the latex polymers in the mill. Preferably, at least some of the latex polymer is put into the mill.

Method for Imparting Stain and Fouling Resistance The luorochemical acrylic polymer additives described above can be used to impart improved stain and fouling resistance to latex paint compositions having a pigment volume concentration of at least 20% and the same ao greater than its critical concentration of pigment volume and comprising: (a) a polymer having interpolymerized units comprising units derived from styrene, methylstyrene, vinyl, or combinations thereof and units derived from one or more acrylates, methacrylates, acrylonitrile, or combinations thereof, (b) opaque pigment, and (c) non-cellulosic thickener. Preferably, the interpolymerized units of the polymer comprise at least 10 percent mole of units derived from styrene, methylstyrene, or combinations thereof and at least 10 percent mole units derived from one or more acrylates, methacrylates, acrylonitrile or combinations thereof. A latex paint coating with improved stain and dirt resistance can be obtained by providing such a latex paint composition, adding at least 0.05 weight percent volume of fluorochemical acrylic polymer additive, applying the resng composition to a surface of substrate, and allowing the resng composition to dry, such that a coating with a fluorine enriched surface is formed on the surface of the substrate. The fluorochemical additive may be added to the latex paint composition at any point during or after its formulation (eg, during grinding or lowering or after all the ingredients have been combined). Preferably, the luorochemical additive is added during the descent. The resng latex paint composition can be applied to various substrate surfaces, such as, for example, architectural surfaces such as walls, ceilings, articles such as furniture and boxes, or any other surface that is normally painted. The resng composition should be allowed to dry in a manner that allows the lumochemical additive to migrate to the surface of the coating as it dries, so that the resng dry coating has a surface enriched in fluorine. Preferably, the composition is allowed to dry on the surface of the substrate under typical interior temperature conditions (about 10 ° C (50 ° F) to about 40 ° C (100 ° F) and humidity (about 20% to about 90% relative humidity).

EXAMPLES The invention will now be further explained by the following illustrative examples which are proposed to be non-limiting.

Glossary Table Description and availability of the paintings used in the "REGAL" tests: Benjamin Moore Regal Base Cake 221 IB, available from Benjamin Moore Paint Co, Montvale, NJ "SIGNATURE": American Tradition Signature Base 1 (45321), Valspar Corp, Minneapolis, MN. "RALPH LAUREN": Brilliant White Ralph Lauren (RL-1191), Glidden, Cleveland OH. "COLORPLACE": Wal-Mart Color Place, available from Wal-Mart, Bentonville, AR.

Preparation 1: Synthesis of MeFBSEA Ethoxylation of MeFBSEA with Ethylene Carbonate REACTION: C4F9S02NHCH3 + (CH20) 2C = O + Na2C03 (catalyst)? C4F9S02N (CH3) CH2CH2OH + C02 LOADS: A. 100 g of MeFBSA (C4F9S02NHCH3, MW = 313, 0.32 moles) B. 2.8 g of Na2C03 (0.026 moles) DI. 8 g of ethylene carbonate (MW = 88) (available from Sigma-Aldrich, Milwaukee, MI) fused in an oven at 50 ° C D2. 8 g of ethylene carbonate D3. 8 g of ethylene carbonate D4. 10 g of ethylene carbonate (total weight = 34 g, 0.38 mol) E. 300 ml of water F. 300 ml of water G. 300 ml, 3% by weight of sulfuric acid H. 300 ml of water I. 300 ml of water J. 300 ml of water PROCEDURE: 1. Loads A, B and C were placed in a 3 liter necked flask, with an upper stirrer, thermocoupler, addition funnel and reflux condenser. 2. The batch was heated to 60 ° C (140 ° F) to a point at which the batch was merged and agitation was started. The settling pinto was increased to 120 ° C (248 ° F). 3. When the batch reached 120 ° C, the DI Load was removed from the furnace and transferred to the addition funnel. The DI Load was then added slowly over a period of 10 minutes. Gas evolution (carbon dioxide) was observed. Thirty minutes elapsed until the valuation of gas evolution, was notable for having decreased. 4. Charge D2 was then transferred to the addition funnel and added over a period of 5 minutes.

After 25 minutes, the gas evolution valuation has decreased and the D3 Load was added over a period of 5 minutes. After 30 minutes, the D4 Load was removed from the furnace, added to the addition funnel and added to the batch for a period of 5 minutes. 5. The settling point was reduced to 110 ° C (230 ° F) and allowed to stir overnight 6. In the morning, the batch was cooled to 90 ° C (194 ° F) and the batch was sampled Gas chromatographic analysis (GC) showed the material to be 96.1% of the desired product and did not contain amide, Charge E. The batch was stirred for 30 minutes, the phase was left to divide and the upper aqueous phase was decanted. The operation was repeated for F Load at 63 ° C (145 ° F) 7. After the water washes, the batch was stirred with the Load G for 30 minutes at 63 ° C (145 ° F) , then the phase was divided and decanted in vacuo The pH of the aqueous layer was tested and found to be less than 2. 8. After washing with acid, the batch was washed with water charges H, I, and J successively at 63 ° C (145 ° F) 9. The batch was fused and poured from the flask into a bottle and allowed to solidify.A small amount of water in the upper part of the resulting solid was poured, and The remaining solid material in the jar was found weighing 124 g.

. The solid material was fused in a 500 ml two-necked flask. The melting point was found to be 57 ° C (135 ° F). 11. The resulting liquid material (113 g) was distilled at 667-933 Pa (5-7 torr Hg). 104 g was distilled (92% undistilled material) at a main temperature of 130-137 ° C (266-279 ° F) and at a crucible temperature of 136-152 ° C (277-306 ° F). In addition, the increase in crucible temperature to 170 ° C (338 ° F), did not result in additional material being distilled.

Preparation of MeFBSEA (N-methyl-perfluorobutane sulfonylethylacrylate) REACTION: C4F9S02N (CH3) CH2CH20H + CH2 = CHC02H + triflic acid (CF3S03H) catalyst - »C4F9S02N (CH3) CH2CH2OC (= 0) CH = CH2 + H20 + CF3S03H LOADS: A. 112 g of MeFBSE alcohol (C4F9S02N (CH3) CH2CH2OH, 0 313 moles) B. 0 07 g of phenothiazine (available from Sigma-Aldrich, Milwaukee, Wl) C. 0 11 g of methoxyhydroxyquinone (MEHQ) (available from Sigma-Aldrich, Milwaukee, Wl) D. 100 g of heptane E. 27.5 g of acrylic acid (0.38 mol) F. 1 g of anhydrous triflic acid (trifluoromethanesulfonic acid) (available as FC -24 from 3M, Maplewood, MN) G. 300 g of water H. 300 g of water PROCEDURE: 1. Loads A, B, C, D, E and F were added to a 3-neck flask equipped with a decanter assembly, top agitator and a thermocoupler under positive hydrogen pressure. 2. The flask was heated to 60 ° C and stirring was started. The batch was stirred at reflux, which was initially at 96 ° C and rose to 102 ° C at the end of the reaction. The theoretical water that must be collected in the decanter was 6.3 ml. After 15 minutes of reflux, 2 ml were collected. After 1 hour and 15 minutes, the reflux temperature was 99 ° C and 5 ml were collected. After 5 hours and 15 minutes, the reflux temperature was 102 ° C and 5.4 ml were collected. A sample was removed from the batch and the GC analysis showed no alcohol that has reacted, 92.6% of the desired product and 7.4% of high boiler which is probably the Michael adduct with acrylic acid. 3. The batch was removed atmospherically to the decanter at 103 ° C until no more heptane was collected in it. 4. The batch was cooled to 64 ° C and pushed slowly under vacuum. More heptane was removed at 5 torr, until no more liquid was observed to be distilled. 5. The vacuum was interrupted and Charge G. The batch was stirred at 64 ° C for 15 minutes, the phase was allowed to divide and the top layer was subjected to vacuum. 6. This operation was repeated with Load H and then the batch was allowed to cool to room temperature at a point where the product was a solid. The remaining water was poured and the product material was fused from the container in a jar. The weight of the product was 125 g (theoretical 129 g). The GC analysis showed the material to be 92.64% of the desired acrylate and 7.36% of the acrylic acid Michael adduct.

Preparation of FC-1; MeFBSEA / "PLURONIC" / HEA / AA; 65/31/2/2 A 3-liter flask fitted with an overhead stirrer, thermocoupler, reflux condenser and nitrogen purge tube was charged with MeFBSEA (585.0 g), "PLURONIC" (504.0 g, 55% solution) in toluene), HEA (18.0 g), AA (18.0 g) MPD (45.0 g) and ethyl acetate (1551.0 g) under a dry nitrogen purge. The temperature of this stirred mixture was raised to 70 ° C, "LUPROX 26M50" (80.0 g) was added and the assured mixture was allowed to stir for 6 hours. After this time, a plate distillation apparatus was attached to the flask and the ethyl acetate was distilled from the flask. The mixture was then cooled to 70 ° C and the toluene was removed under reduced pressure (10-20 mm Hg). The resulting solid was isolated, MeFBSEA / "PLURONIC" / HEA / AA; 65/31/2/2 (919.0 g).

Preparation of the Paint A one liter polypropylene beaker was loaded, fitted with an upper stirrer with the paint to be tested (500 g). An appropriate amount of FC-1 was added to the paint (to achieve the weight percentages listed in Table 1). The paint is stirred for 10 minutes.

Coating Method and Test Coating Method for Spot Release Testing Latex paint sample panels were prepared by coating on a dark panel for rubbing test (Form P121-10N; 16.5 cm x 43.2 cm; available from The Leneta Co., Mahwah, NJ), using a manual coater with an aperture of 6 mil (0.15 mm). The resulting latex paint coating was allowed to air dry at room temperature and humidified for 3 days.

Soiled / Cleaned Test Method "Oily dirt" was prepared by high-cut mixing of 50 parts of Lanolin (anhydrous USP), 50 parts of Petrolate, 5 parts of carbon black, 30 parts of sticky margarine, and 10 parts of mineral oil at 120 ° F (50 ° C) for approximately 15 minutes. The resulting greasy dirt was applied to the test panel coated with a 3"(7.62 cm) paint roller and allowed to settle for 1 hour.The resulting dirty panel was vigorously rubbed with a clean paper towel to remove both - the greasy dirt as possible. The panel (painted side up), was then fixed in a machine Rubner Gardner (available from Gardner Laboratories, Bethesda, Maryland). A wet, clean cellulose sponge with 5 mL of 5% DAWN dishwashing liquid in water DI (available from Procter &Gamble, Cincinnati, OH), was placed on the brush holder of the rubbing machine.

Approximately 5 ml of "DAWN" dishwashing liquid (5% in DI water), were applied to the soiled and painted surface of the rubbed test panel. The rubbing was stopped after 127 double rubs and the test panel was removed, rinsed with DI water, and air dried for at least one hour.

Residual Stain Measurement Residual stain measurements were taken using a Minolta CR200 Chroma meter (available from Minolta Corp, Osaka, Japan), with D65 illuminant. Measurements L *, a *, and b * were taken from the unstained portion of the rubbed test panel (designated with subscript ?? u "in the following formula) and the stained portion of the rubbed test panel (designated with the subscript "s in the following formula). To calculate the residual spot,? E, the following formula was used:? E = V (Z *. -L *,) * + (μ - «* 2 + (**. -b \? This value? E represents the distance in the color space L * a * b * between the unstained area and the stained area (see, for example, Richard S. Hunter, THE MEASUREMENT OF APPEARANCE, Wiley-Interscience, pp. 102-130, (1975) It is a good measurement for the difference in color as perceived by people A smaller E value is indicative of a cleaner surface.

General Preparation of Latex Paint Compositions A 1 liter beaker was charged with stainless steel with the grinding: Joncryl, Propylene Glycol, Drew, Ti-Puro, Supermite, Novacite and Attagel. The cooling water was then changed and the resulting mixture was dispersed at high speed (11,000 rpm) using a high cut Cowles mixer, equipped with a 32 mm Cowles impeller for approximately 30 minutes.

The high-cut Cowles mixer was then replaced with a low-cut marine impeller mixer running at 200 rpm and the mixture was lowered by adding the descending: Joncryl, Deionized Water (DI), Drew, Acrisol, Butyl Carbitol, fluorochemical additive (8.35 g 10% active by weight by weight in Texanol), Colortrend and Nuosept. FC-1 was then added for Examples 1-9.

Examples 1-9 and Comparative Examples C1-C3 Examples 1-9 and Comparative Examples Cl through C3, were prepared following the General Preparation procedures of the Latex Paint Compositions described above, with appropriate amounts of materials as mentioned in Tables 1 and 2.

Table 1. Examples 1-9 and Comparative Examples C1-C3 Descending Ingredients (in grams) Table 2. Examples 1-9 and Comparative Examples C1-C3 Descending ingredients (in grams) and FC-1 (%).

CN / A = without added FC-1 Table 3. Values? E for Examples 1-9 and Comparative Examples C1-C3 * N / A = without added FC-1 Additionally, several commercial paints with and without FC-1 were tested for Residual Stain (? E). For Examples 10-17, the listed percentage of FC-1 was added to the commercial paint and allowed to stir at low speed for approximately 10 minutes to "ensure complete mixing." The samples were prepared in accordance with the Coating Method described above. The resulting E values are listed in Table 4.

Table 4. Values? E for Examples 10-17 and Comparative Examples C4-C6.

* N / A = without added FC-1 Various modifications and alterations of this invention become apparent to those skd in the art without departing from the scope and spirit of this invention.

It is noted that with the relationship to this date, the best method known by the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention.

Claims (19)

CLAIMS Having described the invention as above, the content of the following claims is claimed as property.

1. Latex paint composition, characterized in that it comprises (a) a polymer having interpolymerized units comprising units derived from styrene, methylstyrene, vinyl or combinations thereof and units derived from one or more acrylates, methacrylates, acrylonitrile or combinations thereof , (b) opaque pigment, (c) non-cellulosic thickener, and (d) at least 0.01 weight percent by volume of fluorochemical acrylic polymer additive comprising: (1) at least one perfluoroalkyl portion selected from the group consisting of of portions of heptafluoropropansulfonamido, nonafluorobutanesulfonamido, undecafluoropentanesulfonamido and tridecafluorohexansulfonamido, (2) at least one polyoxyalkylene block comprising at least (a) an alkyleneoxy moiety or (b) an alkylene group interrupted by a carboxy ester moiety, and (3) at least one polar group solubilizing in water; wherein said fluorochemical acrylic polymer additive comprises about 5 to about 30 weight percent of fluorine bonded to carbon based on the total weight of said fluorochemical acrylic polymer, and said latex paint composition, having a pigment volume concentration of at least 20% and equal to or greater than its critical concentration of pigment volume.

2. Paint composition according to claim 1, characterized in that said perfluoroalkyl portion is nonafluorobutanesulfonamido.

3. Paint composition according to claim 1, characterized in that a plurality of said perfluoroalkyl portions are each linked to at least one polyoxyalkylene block by a polymer chain. .

Painting composition according to claim 1, characterized in that said alkylenoxy portion is selected from the group consisting of ethyleneoxy portions and propylenoxy portions.

5. Paint composition according to claim 1, characterized in that said fluorochemical acrylic polymer additive is selected from those represented by the following general formula: wherein "w ww represents a bond in a polymeric or polymerizable chain; R, Ri and R2 are each independently, hydrogen or alkyl of 1 to 4 carbon atoms; R3 is at least one or more straight or branched alkyleneoxy groups, bonded together and having 2 to 6 carbon atoms, or a straight or branched alkylene group, having 12 to 20 carbon atoms; n is an integer from 2 to 10; and x, y, and z are integers of at least 1.

6. Painting composition according to claim 1, characterized in that said fluorochemical acrylic polymer additive comprises the reaction product of: (i) a compound represented by the following formula general: (ii) a compound selected from the group consisting of and mixtures thereof; and (iii) a compound represented by the following general formula: wherein R, Ri, R2, R 'are hydrogen or alkyl of 1 to 4 carbon atoms, n is an integer from 2 to 10, EO is a portion of ethyleneoxy, PO is a propyleneoxy portion, p is a number integer from 1 to approximately 130, q is an integer from 0 to approximately 55, n 'is an integer from 1 to approximately 10, and m is hydrogen or a cation.

7. Paint composition according to claim 1, characterized in that said fuoroquin acrylic polymer additive comprises the reaction product of: (i) a compound represented by the following general formula: (ii) a compound selected from the group consisting of: and mixtures thereof; and (iii) a compound represented by the following general formula: M-O-C (= O > C (R2) = CH2 wherein R, R, R2 and R 'are independently hydrogen or alkyl of 1 to 4 carbon atoms, n is an integer from 2 to about 10, EO is an ethyleneoxy moiety, PO is a propyleneoxy moiety, p is an integer from 1 to approximately 130, q is an integer from 0 to about 55, M is H, potassium, sodium, ammonium or protonated tertiary amine.

8. Paint composition according to claim 1, characterized in that said interpolymerized units comprise at least 40 mole percent of units derived from styrene, methyl styrene or combinations thereof and at least 10 mole percent units derived from one or more acrylates, methacrylates, acrylonitrile or combinations thereof.

9. Paint composition according to claim 1, characterized in that said polymer has a glass transition temperature between 21 ° C and 95 ° C.

10. Paint composition according to claim 1, characterized in that said opaque pigment has a refractive index above about 1.8.

11. Paint composition according to claim 1, characterized in that the thickener is an associative thickener.

12. Paint composition according to claim 1, characterized in that said latex paint further comprises a functional calcium carbonate extender.

13. Paint composition according to claim 1, characterized in that said latex paint further comprises a coalescing solvent.

14. Article, characterized in that a portion of at least one surface of said article is coated with the paint composition according to claim 1.

15. Method for imparting resistance to staining and soiling to a latex paint, characterized in that it comprises steps of: (a) providing a latex paint composition comprising: (1) a polymer having interpolymerized units comprising units derived from styrene, methylstyrene, vinyl or combinations thereof, and units derived from one or more acrylates, methacrylates, acrylonitrile or combinations thereof, (2) opaque pigment, and (3) non-cellulosic thickener; wherein said latex paint has a pigment volume concentration of at least 20% and equal to or greater than its critical concentration of pigment volume; (b) adding at least about 0.01 volume percent by weight of a fluorochemical acrylic polymer additive comprising: (1) at least one portion of perfluoroalkyl selected from the group consisting of portions of heptafluoropropanesulfonamido, nonafluorobutanesulfonamido, undecafluoropentanesulfonamido and tridecafluorohexansulfonamido, ( 2) at least one polyoxyalkylene block comprising at least (a) an alkyleneoxy moiety or (b) an alkylene group interrupted by a carboxy ester moiety, and (3) at least one polar water solubilizing moiety; wherein said fluorochemical acrylic polymer has from about 5 to about 30 weight percent of fluorine bonded to carbon, based on the total weight of said fluorochemical acrylic polymer in said latex paint composition; (c) applying the resulting composition of (b) to a substrate surface; and (d) allowing said resultant composition to dry in such a manner that a coating with a fluorine enriched surface is formed on said surface.

16. Method according to claim 15, characterized in that said polymer has a glass transition temperature between 21 ° C and 95 ° C.

Method according to claim 15, characterized in that said fluorochemical acrylic polymer additive is selected from those represented by the following general formula: where < "W VWV" represents a bond in a polymeric or polymerizable chain, R, Ri and R2 are each independently, hydrogen or alkyl of 1 to 4 carbon atoms, R3 is at least one or more straight or branched alkylenoxy groups, linked in and having 2 to 6 carbon atoms, or a straight or branched alkylene group, having 12 to 20 carbon atoms, n is an integer from 2 to 10, and x, y, and z are integers of at least 1 .

18. Method according to claim 15, characterized in that said fluorochemical acrylic polymer additive comprises the reaction product of: (i) a compound represented by the following general formula: (ii) a compound selected from the group consisting of and mixtures thereof; and (iii) a compound represented by the following general formula: wherein R, Ri, R2, Rf are hydrogen or alkyl of 1 to 4 carbon atoms, n is an integer from 2 to 10, EO is a portion of ethyleneoxy, PO is a propyleneoxy portion, p is a whole number from 1 to approximately 128, q is an integer from 0 to about 55, n 'is an integer from 1 to approximately 10. Method according to claim 15, characterized in that said acrylic polymer additive comprises the reaction product of: (i) a compound represented by the following general formula: (ii) a compound selected from the group consisting of: HO (EO) p- (PO) q- (EO) p H2 HO (PO) q- (EO) - (PO) q CH2 and mixtures thereof; and (iii) a compound represented by the following general formula: M-O-C (= O) -C (R2) = CH2 wherein R, Ri, R2 and R 'are independently hydrogen or alkyl of 1 to 4 carbon atoms, n is an integer from 2 to about 10, EO is an ethyleneoxy portion, PO is a propyleneoxy moiety, p is a number whole from 1 to approximately 130, q is an integer from 0 to about 55, M is H, potassium, sodium, ammonium or protonated tertiary amine.