MXPA00003198A - Scrub resistant latexes - Google Patents

Abstract

Latex compositions are disclosed which are polymerized from monomers having acid or anhydride functionality and wet adhesion properties. The latex compositions of the present invention can be prepared by a two stage polymerization of a first stage polymer and a second stage polymer wherein a monomer effective to enhance the wet adhesion properties of the composition is included in either the first stage polymer, the second stage polymer, or both.

Description

LAVATORY RESISTANT LATEX COMPOSITIONS FIELD OF THE INVENTION The present invention relates generally to latex polymers and more specifically refers to latex polymers having improved wet adhesion characteristics. BACKGROUND OF THE INVENTION Latex paint coatings are typically applied to substrates and dried to form continuous films for decorative purposes as well as to protect the substrate. Such paint coatings are frequently applied to interior or exterior architectural surfaces, where the coatings are sufficiently liquid to flow, form a continuous paint film, and dry at ambient temperatures. A latex paint usually comprises an organic polymeric binder, ie, latex polymer, pigments, and various paint additives. In dried paint films, the polymeric binder functions as a binder for the pigments and provides the adhesion of the dried paint film on the substrate. The pigments can be organic or inorganic pigments and functionally contribute to opacity and color as well as contributing to durability and hardness, although some paints contain few or no opacity pigments and are described as clear coatings. The manufacture of paint includes the preparation of a polymeric binder, the mixing of the components, the grinding of the pigments in a dispersing medium, and the dilution to commercial standards. Latexes produced for interior or exterior architectural surfaces frequently require the property of wet adhesion. Wet adhesion is typically tested by applying a 7 mil wet film of a latex paint on a glossy (oil-based) paint film that was allowed to dry for at least 3 weeks but not longer than 6 weeks. The latex paint is left to dry for 24 hours, and then the film is scratched, placed in water for 30 minutes, and then removed from the water and placed in a washing machine. The striped section is washed for 500 cycles using a 5% lava soap solution and a standard washing brush. The optimum values of wet grip are obtained when no part of the paint film is removed during the test. The percentage of film that remains is recorded. Essentially, this property allows paints to adhere on surfaces previously painted with alkyd paints. A latex polymer commonly used in latex paints that require wet adhesion contains acrylic monomers or styrene / acrylic monomers. There are numerous methods to produce latex from these types of monomers. A particular method employs a generic reaction scheme that produces latex in two stages. The first stage consists of monomers and chain transfer agents, polymerized in the presence of water and optionally surfactants to produce a latex polymer soluble in water or slightly soluble in water. A second stage is then polymerized in the presence of the first stage to produce a more hydrophobic polymer. The resulting polymer is known in the art as a latex composed with a second hydrophobic internal stage and a first external stage soluble in water or slightly water soluble / swellable. In a variation of this procedure, the water-soluble / water-swellable polymer is added concurrently with the second stage. EP 0 587 333 A2 discloses water-resistant multistage polymers having an insoluble polymer under alkaline conditions and a polymer soluble in alkaline conditions which are prepared by the sequential emulsion polymerization of a monomer mixture having an acid functionality in the stage soluble in alkaline conditions and an insoluble polymer under alkaline conditions having, optionally, an amine functionality to bind the first stage polymer to the second stage polymer.

The functionality has also been incorporated in latex to allow crosslinking with other resins. U.S. Patent No. 5,326,843 discloses a latex in which hydroxyethyl acrylate is added to the set of polymerizable monomers to provide reactive functionality. The hydroxyl functionality can react with aminoplasts and polyisocyanates to form a cured film. Crosslinkable latexes are also presented in WO 95/29963 as well as in WO 95/29944. Compositions of latex polymers comprising mixtures of latex polymers with wet tack properties are presented in U.S. Patent No. 5,208,285. However, patent holders have relatively small amounts of carboxylic acid-containing monomers that are often desirable in latex compositions. Accordingly, latex polymer compositions polymerized from monomers having an acid or anhydride functionality and wet adhesion properties, ie, wash resistance, are desired. SUMMARY OF THE INVENTION Throughout the present invention, latex polymer compositions polymerized from monomers having an acid or anhydride functionality and wet tack functionality are provided. The process of the present invention allows the preparation of a first stage polymer which, when a base is added, swells, partially dissolves or substantially dissolves the polymer thus providing a means for a second stage polymerization of an insoluble polymer under alkaline conditions, providing stability for the insoluble polymer under alkaline conditions. The polymer latexes of the present invention contain acid up to 10% or more based on the total weight of the polymer containing the acid or anhydride functionality. Surprisingly, when wet wetting functionality is added, it has been found that latex polymers of this type offer excellent wet tack when used in coating formulations despite the presence of acid or anhydride functionality. The present invention offers polymers which may be useful in compositions such as for example architectural coatings, industrial and automotive coatings, sealants, adhesives, paper coating compositions, inks, varnishes, and the like. DETAILED DESCRIPTION OF THE INVENTION The latex compositions of the present invention can be prepared through a two step polymerization of a first stage polymer and a second stage polymer. The first stage polymer is an emulsion polymerization of a monomer mixture comprising at least one carboxylic acid or anhydride or monomer functional monomer that provides an alkaline sensitivity to the first stage polymer, which reacts with various comonomers, optionally in the presence of a wet adhesion promoter. Suitable acid or anhydride functional monomers include acrylic acid, methacrylic acid, ethacrylic acid, alpha-chloroacrylic acid, crotonic acid, citraconic acid, mesaconic acid, itaconic acid, maleic acid, fumaric acid, 3-acrylamido-3-methylbutanoic acid, acrylic anhydride, methacrylic anhydride, ethacrylic anhydride, protonic anhydride, citraconic anhydride, mesaconic anhydride, itaconic anhydride, maleic anhydride, fumaric anhydride, p-styrenecarboxylic acid, p-styrenesulfonic acids, vinylsulfonic acid, 2-sulfoethyl methacrylate, 3-sulfopropyl methacrylate, acrylate of 3-sulfopropyl, 2-acrylamido-2-methylpropanesulfonic acid, and the like, including mixtures thereof. In one embodiment of the present invention, the preferred acid monomer is selected from the group consisting of acrylic acid and methacrylic acid. The amount of acid or anhydride functionality present in the first stage emulsion polymerization determines the degree of solubility of the first stage when a base is added. A minimum amount of acid or anhydride functionality is required to solubilize the polymer according to the hydrophobicity of the comonomers, molecular weight of the polymer, chemical nature of the acid or anhydride monomer and distribution of monomer sequences in the polymers. Polymers modified by acid or anhydride can improve or degrade adhesion, depending on the paint system and the substrate. When used in excess, the acid or anhydride groups render the paint sensitive to water, and therefore affect wet adhesion. Based on the above criteria, the preferred weight of the acid or anhydride functionality monomers present in the first stage polymerization is at least about 2% by weight, preferably at least 3% by weight, more preferably, about 5% by weight to 50% by weight; with even greater preference, from about 8 to 30% by weight, and especially from about 10 to 20% by weight, based on the total weight of the monomers charged in the first stage reaction. Exemplary comonomers useful in the first stage polymerization are monomers such as for example methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, methacrylate hydroxyethyl, hydroxypropyl methacrylate, styrene, substituted styrene such as, for example, alphamethylstyrene, acrylonitrile, vinyl acetate, and other hydroxyalkyl acrylates and methacrylates or C 1 -C 2 alkyl, 2-ethylhexanoate, vinyl propionate, vinyl neodecanoate , vinyl neononanoate, vinyl versatate, vinyl pivalate and the like, and / or mixtures thereof.

The first stage polymer can have several molecular weights. The molecular weight is controlled by the addition of a suitable chain transfer agent as is known in the art. Examples of suitable chain transfer agents include, for example, alkyl ercaptans such as octylmercaptan and decylmercaptan, esters of mercaptoacetic acid, such as, for example, mercaptoacetic acid ethyl ester and mercaptoacetic acid 2-ethylhexyl ester, and mercaptopropionic acid esters , such as, for example, iso-octyl ester of mercaptopropionic acid. In a preferred embodiment, the chain transfer agent can be selected from the group consisting of 2-ethylhexylmercaptopropionate and iso-octylmercaptopropionate or mixtures thereof. The average molecular weight index Mn obtained is typically located within a range of 500 to 100,000. A wet adhesion promoter is optionally incorporated in the first stage alkaline soluble polymerization to promote wet adhesion properties to the first stage polymer and final latex product. Preferably, the wet adhesion promoter comprises a monomer having an effective nitrogen functionality to increase the wet adhesion properties of the latex composition. Preferred wet adhesion promoters include compounds having an amino, ureido, or N-heterocyclic group such as for example dialkylaminoalkyl esters, and dialkylaminoalkyl amides of acrylic or methacrylic acid, and particularly those having 1 to 5 carbon atoms in the alkyl groups, polymerizable free-radical compounds of urea, ethyleneurea, or propyleneurea, as well as polymerizable imidazolidinones having a -NC (0) N- group as part of a five-membered ring-ring structure. Examples of wet adhesion promoters that provide the desired wet tack properties include dimethylaminoethyl acrylate, diethylamino acrylate, dimethylaminopropyl acrylate, 3-dimethylamino-2,2-dimethylpropyl-1-acrylate, 2-N-acrylate. morpholinoethyl, 2-N-piperi-dinoethyl acrylate, N- (3-dimethylaminopropylacrylamide (as used herein includes methacrylamide), N- (3-dimethylamino-2,2-dimethyl-propyl) acrylamide, N-dimethylaminomethylacrylamide, N- (4-morfo-linomethyl) acrylamide, N- (2-methacryloyloxyethyl) ethyleneurea, methacrylaminoethylethyleneurea, N- (2-methacryloxyacetamidoethyl-N, N, N ', N'-ethyleneurea, allylkylethyleneurea, N-methacrylamido methylurea, N -metacryloylurea, N- [3- (1, 3-diazacyclohexane-2-on-propyl)] methacrylamide, 2- (1-imid-azolyl) ethyl methacrylate, 2- (1-imidazolidin-2-on) methacrylate ethyl, vinylimidazole, vinylpyrrolidone, and 3-allyl-4,5-methoxy-2-imidazolidinone Preferred wet adhesion promoters include N- (2- tachyloyloxyethyl) ethyleneurea, and methacrylamidoethylethyleneurea. In addition, it has been found that propyleneimine can subsequently react with the soluble polymer in alkaline conditions of the first stage to provide wet adhesion properties and act as a base to neutralize the soluble polymer in the alkaline condition of the first stage. It can also react with the polymer of the first stage after the formation of the polymer of the second stage. The amount of wet adhesion promoter present in the emulsion polymerization process of the first stage is typically within a range of from about 0.1 to 20% by weight, more preferably from about 1 to 10% by weight, and especially from about 1.9 to 5% by weight, based on the total weight of the monomer composition of the first stage filler. In carrying out the emulsion polymerization, at least one initiator or catalyst is used in a sufficient concentration to initiate or catalyze the polymerization reaction. The concentration of initiator and / or catalyst varies according to the weight of the charged monomers. The particular concentration used in any case will depend on the specific mixture of monomers subjected to reaction and the specific initiator used; as is well known to those skilled in the art, it is frequently from about 0.01 to 3% by weight; more preferably from about 0.05 to 2% by weight, and especially from about 0.1 to 1% by weight based on the weight of the charged monomers. It is also known that traces of metal ions can be added as activators in order to improve the speed of polymerization, if desired. Illustrative examples of suitable initiators are hydrogen peroxide, peracetic acid, t-butyl hydroperoxide, ammonium persulfate, potassium persulfate, sodium persulfate, as well as any other known initiators. Also useful are redox catalyst systems such as sodium persulphate-sodium sulfoxylate formaldehyde, cumene hydroperoxide-sodium metabisulfite, hydrogen peroxide-ascorbic acid, and other known redox systems. The polymerizable compositions fed may also contain any of the other conventionally known additives used in the emulsion polymerization processes in the usual known amounts, such as crosslinkers, dispersion aids, emulsifiers, photosensitizers, colorants, bactericides, fungicides, etc.

At the end of the first stage polymerization, a neutralizing agent or base is added to the soluble polymer in first stage alkaline conditions in order to swell, partially dissolve, or substantially dissolve the polymer. Suitable bases include ammonia, triethylamine, monoethanolamine, dimethylaminoethanol, ammonium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide and all other hydroxides of Group I A and group II A and the like. In accordance with the above, a propyleneimine can also be effective for the neutralization of the soluble polymer in first stage alkaline conditions, while at the same time providing wet adhesion properties to the final product. Based on equivalents of acid in the soluble polymer in alkaline conditions, typically 0.01 to 1.5 equivalents of base are added to the soluble polymer in alkaline conditions to swell, partially dissolve, or substantially dissolve the soluble polymer under alkaline conditions in order to form a stabilized dispersing medium for the second stage polymerization. In one aspect of the invention, the first stage latex polymer, in accordance with the preparation, can be stored for subsequent neutralization. In another aspect of the invention, the first stage polymer can be neutralized and used as a dispersion medium for other latex polymers including the second stage emulsion polymerization process of the present invention. By using the first stage polymer as a means for a second stage emulsion polymerization of insoluble monomers under alkaline conditions, it has been found that the final product exhibited improved film-forming properties, improved wet adhesion properties as well as other characteristics. The monomers useful for polymerization in the second tea include any monomer insoluble under alkaline conditions, ie monomers substantially free of anhydride or carboxylic acid functionality, such as, for example, those having an acrylic, styrenic, vinyl or versatile functionality . As used herein, the term "substantially free" means less than about 10% by weight, preferably less than about 2% by weight, and more preferably less than about 2% by weight, based on the total weight of the polymer . Illustrative examples of such monomers are esters of acrylate and methacrylate, styrene, alkylstyrenes, vinyltoluene, vinyl acetate, vinyl alcohol, acrylonitrile, vinylidene chloride, and vinyl ketones. Other illustrative monomers useful in this invention include, for example, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, n-amyl methacrylate, sec-amino methacrylate, hexyl methacrylate, lauryl methacrylate, stearyl methacrylate, methacrylate ethylhexyl, crotyl methacrylate, cinnamyl methacrylate, oleyl methacrylate, ricinoleyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, vinyl propionate, vinyl butyrate, vinyl tert-butyrate, vinyl caprate, vinyl stearate, laurate vinyl, vinyl oleate, vinyl methyl ether, vinyl ethyl ether, vinyl n-propyl ether, vinyl isopropyl ether, vinyl n-butyl ether, vinyl isobutyl ether, vinyl isoetyl ether, vinyl phenyl ether, a-chloro vinyl phenyl ether, vinyl naphthyl ether, methacrylonitrile, acrylamide, methacrylamide, N-alkyl acrylamides, N-arylacrylamides, N-vinylpyrrolidone, N-vinyl-3-morpholinones, N-vinyl-oxazolidone, N-vinyl imidazole and the like, including blending s of them. Optional ingredients that may be included in the second stage polymerization of the insoluble polymers under alkaline conditions include, for example, other monomers such as vinyl ester, acid and / or anhydride functional monomers, crosslinkers, chain transfer agents, and others as is known in the art. The average molecular weight index can be within a range of 500 to 500,000 or more up to infinity if appropriate chain transfer or cross-linking agents are employed. The wet adhesion promoter is also optionally incorporated in the second stage polymerization in order to provide wet adhesion properties to the final latex product; provided, however, that it is incorporated into at least one of the first stage polymer or second stage polymer.

The desired ratio for the polymerization of the second stage monomer fed into the first stage polymer medium covers a wide range according to the desired properties of the final latex composition, and the level of acid in each stage. For example, the amount of first stage polymer that is incorporated in the second stage polymerization can be small when a more highly carboxylated material is employed [eg, 10 parts per hundred resin, i.e., first stage plus second stage ( "phr") of the first stage resin containing 20% methacrylic acid] or larger amounts when a less carboxylated material is used [eg 20 phr of the first stage resin containing 10% methacrylic acid]. Suitable ranges include from about 1:99 to about 99: 1. Preferably, the weight ratio of the second stage monomer fed is from about 5:95 to 95: 5, and more preferably from about 10:80 to 80:10. The resulting latex latex compositions can be used, for example, as binders for architectural coatings, industrial and automotive coatings, sealants, adhesives, paper coating compositions, inks, varnishes and the like. In paint formulations, the insoluble polymers in alkaline conditions dispersed in the first stage neutralized polymer can be employed at levels based on the weight of solids, within a range of about 5% to about 90% of the total weight of the formulation of painting. Paint formulations prepared with these unique polymers exhibit excellent wet tack, high gloss and improved block strength. The paint formation can, in addition to the polymers of this invention, contain conventional additives such as, for example, pigments, fillers, dispersants, wetting agents, coalescents, rheology modifiers, drying retardants, biocides, antifoaming agents and the like. The following description is a general description of an emulsion polymerization process for preparing insoluble polymers in alkaline conditions dispersed in a soluble polymer under dissolved alkaline conditions. In a typical reaction, the mixture of acrylic or methacrylic acids, acrylate or methacrylate esters, and / or styrenic monomers, wet adhesion monomer, and other optional ingredients are fed to a reactor where they are emulsion polymerized in the presence of a chain transfer agent and an initiator. Typically, the polymerization is carried out using a surfactant or emulsifying agent in an aqueous medium. The temperature can vary from about 35 ° C to about 90 ° C or more; the preferred temperature is from about 70 ° C to about 85 ° C. Pressure is not a critical factor and depends on the nature of the monomers used, usually gaseous monomers that require superatmospheric pressures. Upon completion of the first stage monomer feed, the reaction is maintained at the reaction temperature until the level of residual monomers is less than about 5000 ppm, followed by addition of the desired neutralizing agent until the first stage polymer is swollen. , partially dissolved, or substantially dissolved. The second stage monomers, including optional ingredients such as wet adhesion monomers, are then fed into the first stage polymer medium at the temperatures described above. Upon completion of the second stage monomer feed, the reactor is maintained at temperatures for about one (1) hour, cooled, and the latex product is collected. Optionally, the latex can be further neutralized at this time.

EXAMPLES The following examples are for the purpose of further illustrating the present invention and should not be construed in any way as limiting the scope of the present invention. Example A: Synthesis of acrylic styrene polymer A monomer mixture was prepared by charging 100 grams of styrene, 70 grams of methyl methacrylate (Aldrich), 30 grams of methacrylic acid (Aldrich), and 7 grams of 2-ethylhexylmercaptopropionate (Hampshire Chemicals) to a 1 liter monomer feed cylinder. A second mixture of monomers was prepared by loading 210 grams of styrene, 250 grams of methyl methacrylate (Aldrich), 330 grams of butyl acrylate (Union Carbide), and 50 grams of N- (2-methylacryloyloxyethyl) at 25% in methyl methacrylate (ROHAMERE 6844-0) (Rohm Tech) in a second feed cylinder one liter monomers. A two-liter encased resin bottle equipped with a four-bladed stainless steel mechanical stirrer, a Claisen connection tube, a Friedrichs water condenser, a nitrogen sprayer and a bubble trap, a thermometer, as well as addition inputs monomers were used to load 925 grams of water, 2.5 grams of GR-9M (Union Carbide). An initial solution of oxidant, prepared by dissolving 2.5 grams of ammonium persulfate in 20 grams of water, was prepared in a separate vessel. A retardant oxidant solution, prepared by dissolving 5 grams of ammonium persulfate in 100 grams of water, was also prepared in a separate vessel. Under nitrogen purge, the reactor was heated to a temperature of 80 ° C by circulating water at a controlled temperature through the reactor jacket. After the temperature of the reactor charge had reached 80 ° C, the initial oxidant solution was added to the reactor. Two minutes later, the monomer feed was brought to the reaction vessel in a period of 40 minutes through FMI pumps using a 1/8"Teflon tubing with continuous stirring while maintaining the reaction temperature at a level comprised between 79 and 81 ° C. The reaction proceeded at 80 ° C. for an additional fifteen minutes after the end of the monomer feed.To the product was added 20 grams of a 15% ammonium hydroxide solution.After fifteen additional minutes, the second monomer mixture was fed to the reactor concurrently with the oxidant solution delayed by 2 hours.The product was kept at 80 for 1 hour.To the resulting product an additional 20 grams of a 15% by weight ammonium hydroxide solution was added. The product was then cooled to room temperature - The latex with a solids content of 48% resulting in a pH of 8, and an average diameter of p 252 nanometer ("nm") particle in accordance with that measured with a Microtrac particle size analyzer (Leeds-Northrop). Three samples were made according to the procedure described above with styrene contents of 30% by weight (Al), 10% by weight (A2), and 20% (A3). Example B: Production of paint A pigment grind was prepared by mixing the following ingredients in sequence: 30 grams of water, 40 grams of propylene glycol, 9.0 grams of Tamol dispersant 165 (Rohm and Haas), 2.5 grams of Triton® surfactant CF-10 (Union Carbide Corp.), 1.5 grams of Strodex PK-90, (Dexter), 1.0 grams of AMP-95 (Angus), 2.0 grams of Nuosept 145 preservative (Huís), 2.0 grams of foam remover Foamaster AP (Henkel), and 225 grams of titanium dioxide TiONA RCL-535 (SCM). The mixture was milled in a high speed disperser for 20 minutes to provide a grinding figure of 6+ on the Hegman scale. A paint was prepared by mixing, under moderate agitation, the following ingredients, in the order: 550 grams of latex from Example A, 313 grams of the pigment grinding elaborated above, 26 grams of Texanol coalescing solvent (Eastman), 10.5 grams of Polyphase P.20.T (Troy) mohocide, 13.0 grams of Acrysol RM-2020 (Rohm &Haas), 10 grams of Butyl Carbitol solvent (Union Carbide Corp.), and 134 grams of water. Example C: Wet adhesion test Wet adhesion was tested by applying a 7 mil wet film of the latex paint on a glossy (oil-based) alkyd paint film that had been allowed to dry for at least 3 weeks but not more than 6 weeks. The latex paint was allowed to dry for 24 hours, and then the film was scratched, placed in water for 30 minutes, and then removed from the water and placed in a washing machine. The striped section was washed for 500 cycles using a 5% lava soap solution and a standard washing brush. The results appear in Table A below. Table A Example C Coonntteenniiddoo of wet adhesion to styrene 24 hours% remaining 30% 100% A2 10% 100% A3 20% 15% * Wet adhesion monomer was omitted. Preferably, in accordance with the present invention, the wet adhesion value at 24 hours is at least 90%, more preferably 95%, and especially 100%. Although the invention has been described in relation to specific aspects, those skilled in the art will recognize that the description is not intended to limit the scope of the following claims.

Claims (1)

1. CLAIMS l.A latex composition comprising: (i) a first polymer polymerized from at least one monomer with acid or anhydride functionality; and (ii) a second polymer polymerized from monomers substantially free of acid or anhydride functionality: characterized in that at least one of said first polymer or said second polymer is polymerized from a monomer having an effective nitrogen functionality to increase the wet adhesion properties of films formed from the latex composition. The latex composition according to claim 1 wherein said first polymer comprises at least 2.0% by weight of the monomer with acid or anhydride functionality based on the total weight of said first polymer. 3. The latex composition according to claim 1 wherein said first polymer comprises at least 5.0% by weight of the monomer with acid or anhydride functionality based on the total weight of said first polymer. 4. The latex composition according to claim 1 wherein said first polymer comprises at least 10.0% by weight of the monomer with acid or anhydride functionality based on the total weight of said first polymer. The latex composition according to claim 1 wherein said first polymer is in the form of a solution. The latex composition according to claim 1 wherein said first polymer is in swollen or partially dissolved form. The latex composition according to claim 1 wherein said first polymer is in the form of particles. The latex composition according to claim 1 wherein said first polymer and said second polymer are at least partially copolymerized. The latex composition according to claim 1 wherein said acid or anhydride functional monomer is selected from the group consisting of acrylic acid, methacrylic acid, ethacrylic acid, alpha-chloroacrylic acid, crotonic acid, citraconic acid, mesaconic acid, itaconic acid, maleic acid, fumaric acid, 3-acrylamido-3-methylbutanoic acid, acrylic anhydride, methacrylic anhydride, ethacrylic anhydride, protonic anhydride, citraconic anhydride, mesaconic anhydride, itaconic anhydride, maleic anhydride, fumaric anhydride, p-styrenecarboxylic acid, p-styrenesulfonic acids, vinylsulfonic acid, 2-sulfoethyl methacrylate, 3-sulfopropyl methacrylate, 3-sulfopropylate, 2-acrylamido-2-methylpropanesulfonic acid, and mixtures thereof. . The latex composition according to claim 1 wherein at least one of said first polymer and said second polymer is polymerized from at least one comonomer selected from the group consisting of methyl acrylate, ethyl acrylate, butyl acrylate. , 2-ethylhexyl acrylate, decyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, styrene, substituted styrene such as for example alphamethylstyrene, acrylonitrile, vinyl acetate, acrylates and methacrylates of C? -C? 2 alkyl, or hydroxyalkyl, vinyl 2-ethylhexanoate, vinyl propionate, vinyl neodecanoate, vinyl neononanoate, vinyl versatate, vinyl pivalate, and mixtures thereof. The latex composition according to claim 1 wherein said monomer has a wet adhesion functionality is selected from the group consisting of dimethylaminoethyl acrylate, diethylamino acrylate, dimethylaminopropyl acrylate, 3-dimethyl-amino-2,2-dimethylpropyl. -l-acrylate, 2-N-morpholinoethyl acrylate, 2-N-piperi-dinoethyl acrylate, N- (3-dimethylaminopropyl) acrylamide (as used herein includes methacrylamide), N- (3-dimethylamino-2) , 2-dimethyl-propyl) acrylamide, N-dimethylaminomethylacrylamide, N- (4-morfo-linomethyl) acrylamide, N- (2-methacryloyloxyethyl) ethyleneurea, methacrylaminoethylethylene urea, N- (2-methacryloxyacetamidoethyl-N, N, N ', N' -ethyleneurea, allylkylethylene-urea, N-methacrylamido-methylurea, N-methacryloylurea, N- [3- (1 , 3-diazacyclohexan-2-on-propyl)] methacrylamide, 2- (l-imid-azolyl) ethyl methacrylate, 2- (l-imidazolidin-2-on) ethyl methacrylate, vinylimidazole, vinylpyrrolidone, and 3-allyl -4,5-methoxy-2-imidazolidinone The latex composition according to claim 11 wherein said monomer having a nitrogen functionality is selected from the group consisting of N- (2-methacryloyl-oxyethyl) ethyleneurea and methacrylaminoethylethyleneurea The latex composition according to claim 1 further comprising a neutralizing agent selected from the group consisting of ammonia, triethylamine, monoethanolamine, dimethylaminoethanol, ammonium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide as well as as propyleneimine. The latex composition according to claim 1 wherein said monomer substantially free of acid or anhydride functionality is selected from the group consisting of propyl methacrylate, isopropyl methacrylate, butyl methacrylate, butyl acrylate, methyl methacrylate , methyl acrylate, ethylhexyl acrylate, n-amyl methacrylate, sec-amyl methacrylate, hexyl methacrylate, lauryl methacrylate, stearyl methacrylate, ethylhexyl methacrylate, crotyl methacrylate, cinnamyl methacrylate, oleyl methacrylate, methacrylate of ricinoleyl, hydroxyethyl methacrylate, hydroxypropyl methacrylate, vinyl propionate, vinyl butyrate, vinyl tert-butyrate, styrene, alphamethylstyrene, alkylstyrene, acrylonitrile, vinyltoluene, vinyl acetate, vinyl caprate, vinyl stearate, vinyl laurate , vinyl oleate, vinyl methyl ether, vinyl ethyl ether, vinyl n-propyl ether, vinyl isopropyl ether, vinyl n-butyl ether ter, vinyl isobutylether, vinyl isooctyl ether, vinyl phenyl ether, a-chloro vinyl phenyl ether, vinyl naphthyl ether, methacrylonitrile, acrylamide, methacrylamide, N-alkyl acrylamides, N-arylacrylamides, N-vinylpyrrolidone, N-vinyl-3-morpholinones, N-vinyl-oxazolidone, N-vinyl- imidazole and mixtures thereof. . The latex composition according to claim 1 wherein said second step comprises less than about 5% by weight of monomers with acid or anhydride functionality based on the total weight of the second polymer. . The latex composition according to claim 1 wherein the first polymer is polymerized from methacrylic acid, butyl acrylate, and methyl methacrylate, and optionally methacrylamidoethylethyleneurea. . The latex composition according to claim 1 wherein the second polymer is polymerized from butyl acrylate and butyl methacrylate and optionally methacrylamidoethylethyleneurea. . The latex composition according to claim 1 wherein the first polymer is polymerized from methacrylic acid, styrene, and methyl methacrylate, butyl acrylate, and optionally methacrylamidoethylethyleneurea. The latex composition according to claim 1 wherein the second polymer is polymerized from butyl acrylate, styrene, and methyl methacrylate and optionally methacrylamidoethylethyleneurea. A paint composition comprising water, pigment, and the latex composition according to claim 1.