MXPA00001337A - Acrylic modified waterborne sulfonated alkyd dispersions - Google Patents

Abstract

A water-based latex of an acrylic-modified waterborne alkyd dispersion in water is described. The acrylic-modified waterborne alkyd is a hybrid resin prepared by the polymerization of at least one ethylenically unsaturated monomer in the presence of a waterborne alkyd having at least one pendant sulfonate functionality. Theethylenically unsaturated monomer may also be a latent oxidatively functional (LOF) acrylic monomer. Preparation of the latexes may be achieved by emulsion polymerization of at least one ethylenically unsaturated monomer in the presence of a waterborne alkyd having at least one pendant sulfonate functionality. Preparation of hybrid latexes which contain latent oxidative functional (LOF) acrylic monomers may also be achieved by emulsion polymerization of at least one LOF acrylic monomer in the presence of a waterborne alkyd having at least one pendant sulfonate functionality whereby the latent oxidative functionality of the acrylic polymer survives polymerization. Such acrylic-modified waterborne alkyds are useful in a variety of coating compositions.

Description

DISPERSIONS D? SULFONATED TRANSPORTED ALQUID? N MODIFIED WATERS WITH ACRYLIC DESCRIPTION OF THE INVENTION The invention relates to a water-based latex of an alkyd dispersion transported in water modified with acrylic in water. Such acrylic-modified water-borne alkyds are useful in a variety of coating compositions. In recent years, considerable effort has been invested by the coating industry to develop low or zero VOC containing coating formulations. The regulations that limit the amount of VOC content of industrial coatings have motivated research and development to explore new technologies aimed at reducing solvent emissions from coating operations based on industrial solvent such as automotive, household appliances, metal in general , furniture, and the like. One technology involves the replacement of organic solvents with water and is of particular interest for obvious reasons of availability, cost, and environmental acceptability. However, while the movement of the organic solvent-based compositions for the aqueous compositions brings health and safety benefits, the aqueous coating compositions must meet or exceed the expected performance standards of the solvent-based compositions.

The need to meet or exceed such performance standards places a premium on the characteristics and polymer dispersion properties carried in water used in aqueous coating compositions. Polymer dispersions transported in water have been prepared from each of the three primary industrial films that form the polymer types: polyesters, acrylics and alkyds. Of the three types of polymer, alkyd resins transported in water exhibit significantly higher storage stability and coating stability than polyester carried in water or acrylic resins. In addition, the alkyd resins, due to their low molecular weight, show the ability to form the exceptional film which results in very high gloss in the final coating film. Resistance properties are developed, such as with alkyds that carry traditional solvent, by autooxidative crosslinking of the alkyd film. However, while the alkyd polymers have shown, and continue to show promise, they have relatively slow "dry" cure times and / or, particularly at ambient temperatures. In an effort to address such a subject, hybrids of water-borne alkyds and relatively high-molecular-weight acrylic polymers have received considerable attention. U.S. Patent 4,413,073 describes the preparation of an aqueous dispersion of particles of a film forming polymer comprising a preformed polymer and at least one polymer formed in situ ("multipolymer particles"). The dispersion is prepared in the presence of an amphipathic stabilization compound having an HLB of at least 8 and whose lipophilic portion comprises at least one unsaturated ethylenic. The aqueous dispersion is useful as a film-forming component of the coating compositions. U.S. Patent 4,451,596 discloses water-dilutable acrylic and alkyd resins for use in water-dilutable lacquer systems. A method for the preparation of water-dilutable resin preparations based on alkyd resins and acrylate are also described. . European Patent Application 0 555 903 describes a water-dispersible hybrid polymer of an unsaturated fatty acid-functionalized polyester. In addition, the aqueous dispersions of such a hybrid polymer for use in aqueous coating compositions with a high solids content and films produced by the use of such coating compositions are described. PCT Application WO 95/02019 describes an emulsion of an air-dried resin dispersed in water and the preparation of such emulsions. It also describes hybrid emulsions of an alkyd resin and an acrylate resin.

Previous alkyd / acrylic hybrids have been prepared using alkyds that do not contain metal sulphonate groups. In addition, the acrylic polymers of these above hybrids are either non-reactive groups or possessing radicals (eg, hydroxyl groups) that react, as similar groups present in the alkyd resin, with aminoplasts such as melamine formaldehyde resins. and only at elevated temperatures. One aspect of the invention is a water-based latex of an alkyd resin carried in water modified with acrylic. The alkyd resin transported in water modified with acrylic is a hybrid resin which is the result of the polymerization of at least one ethylenically unsaturated monomer in the presence of an alkyd transported in water having at least one pending sulfonate functionality, i.e. an alkyd transported in sulfonated water. The invention also provides a method for preparing such water-based latexes by the polymerization of a hybrid resin resulting from the polymerization of at least one ethylenically unsaturated monomer in the presence of an alkyd carried in sulfonated water. The invention further provides coating compositions containing water-based latex of the invention. The invention provides a water-based latex of an alkyd resin carried in water modified with acrylic. In one embodiment, the latex provides a stable emulsion of a hybrid resin resulting from the polymerization of at least one ethylenically unsaturated monomer in the presence of an alkyd carried in water having at least one pending sulfonate functionality, i.e. Alkyd transported in sulfonated water. In another embodiment, the latex provides a stable emulsion of a hybrid resin resulting from the polymerization of at least one acrylic monomer of latent oxidative functionality (FOL) in the presence of an alkyd transported in water having a functionality of at least one The sulfonate is such that the acrylic monomer retains a sufficient amount of FOL groups for further reaction with other FOL groups or alkyd functionality after or in film formation. The latexes of the invention are stable when stored at temperatures at or slightly above ambient temperatures. The latex of the invention is capable of affecting crosslinking in film formation. Such films or latex coatings can be cured at room temperature, thermally or photochemically. In the water-based latexes of the invention, the alkyd resin carried in water modified with acrylic generally exists as particles dispersed in water. The particles are generally spherical in shape. The particles can be structured or not structured. Structured particles include, but are not limited to, core / shell particles and pending particles. The core / shell polymer particles can also be prepared in a multilobe form, peanut shell, beilot form, or raspberry form. It is further preferred in such particles that the center portion comprises about 20 to about 80% by weight of the total weight of the particle and the portion of the shell comprising about 80 to about 20% by weight of the total weight of the particle. The average particle size of the hybrid latex can range from about 25 to about 500 nm. Preferred particle sizes average from about 50 to about 300 nm, more preferably from about 100 to 250 nm. The late? Hybrid particles usually have a spherical shape. The glass transition temperature (T) of the acrylic portion of the hybrid resin according to the invention can be above about 100 ° C. In a preferred embodiment of the invention, where latex film formation at room temperature is desirable, that the vitreous transition temperature may be preferably below about 70 ° C, and preferably between about 0-60 ° C. The alkyd resins transported in water modified with acrylics of the invention are prepared by polymerization of at least one ethylenically unsaturated monomer in the presence of an alkyd transported in sulphonated water. If at least one of the ethylenically unsaturated monomers is an oxidatively latent functional acrylic monomer (FOL), as described in the following, the alkyd resins transported in water modified with acrylics of the invention will be prepared in the presence of an alkyd transported in water. sulfonated such that sufficient latent oxidative functionality of the acrylic monomer survives the polymerization process to cross-link the hybrid resin. Any polymerization process known in the art can be used. Preferably an emulsion polymerization process is used since the emulsion polymerization allows the preparation of low viscosity high molecular weight polymers. The polymerization can take place as a single phase or multi-phase feed. If a multi-phase food is used, one or more phases may contain an FOL acrylic monomer or FOL acrylic monomer mixtures. Different FOL monomers can be used in different phases. The copolymers can be used as the acrylic portion of the modified alkyd and other ethylenically unsaturated monomers can be prepared by copolymerization with the FOL acrylic monomer. The preparation of the emulsion polymers of alkyd resins transported in water modified with acrylics containing latent oxidative functionality is a possible solution for a coating composition which cross-links under a variety of cure conditions, for example environmental, thermal, and photochemical. Alkyd Resin Transported in Sulfonated Water An alkyd resin transported in sulfonated water for use in the water-based latex of the invention can be any alkyd resin carried in water having a pending sulfonate functionality at least known in the art and can include any alkyd resin dissipable in water, dispersible in water or reducible in water (ie able to enter water). Examples of such alkyd resins are described in US Pat. 5,378,757 and 5,530,059 both of which are incorporated herein by reference. Generally the alkali resins transported in sulfonated water can be prepared by reacting a monobasic fatty acid, fatty ester or naturally saponified oil that occurs partially; a glycol or polyol; a polycarboxylic acid; and a sulfomonomer or sulfomonomer adduct containing at least one sulfomonomer group. The monobasic fatty acid, fatty fatty ester, or naturally occurs partially the saponified oil is preferably selected from the formula (I), (II), and (III): where the group R is an alkyl group of C8-C-: ü. More preferably, the group R is one of the following: LINOLESCO LYMPHENIC R OLEICO The monobasic ester acid, fatty ester or naturally occurring saponified oil is preferably prepared by reacting a fatty acid or oil with a polyol. Examples of suitable oils include, but are not limited to, sunflower oil, canola oil, dehydrated castor oil, coconut oil, corn oil, cottonseed oil, fish oil, linseed oil, oil oiticica, soybean oil, and tung oil, animal fat, castor oil, lard, palm kernel oil, peanut oil, goat oil, safflower oil, tallow oil, walnut oil, and the like. Suitable examples of fatty acids alone or as oil components include, but are not limited to, tallow acid, soy acid, myristic acid, linseed acid, crotonic acid, versatic acid, coconut acid, liquid resin fatty acid , resin acid, neodecanoic acid, neopentanoic acid, isostearic acid, 12-hydroxystearic acid, cottonseed acid, and the like. The glycol or the polyol is preferably selected from and aliphatic, alicyclic and arylalkyl glycols. Suitable examples of the glycols include, but are not limited to, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, hexaethylene glycol, heptaethylene glycol, octaethylene glycol, nonaethylene glycol, decaethylene glycol, 1,3-propanediol, 2,4-ll. dimethyl-2-ethylhexane-l, 3-diol, 2,2-dimethyl-l, 2-propanediol, 2-ethyl-2-butyl-l, 3-propanediol, 2-ethyl-2-isobutyl-1, 3-propanocylol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2,2-tetramethyl-1,6-hexanediol, thiodiethanol, 1,2-cyclohexanedimethanol, 1 , 3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2,2,4-trimethyl-1,3-pentanediol, 2,2,4-tetramethyl-1,3-cyclobutanediol, p-xylenediol, hydroxypivalyl hydroxypivalate, 1, 10 -decanodol, hydrogenated bisphenol A, trimethylolpropane, trimethylolethane, pentaerythritol, erythritol, treitol, dipentaerythritol, sorbitol, glycerin, trimellitic anhydride, pyromellitic dianhydride, dimethylolpropiconic acid, and the like. The polycarboxylic acid is preferably selected from the group consisting of isophthalic acid, terephthalic acid, (acid) phthalic anhydride, adipic acid, tetrachlorophilic anhydride, tetrahydrophthalic anhydride, dodecanedioic acid, sebacic acid, azelaic acid, 1,4-cyclohexanedicarboxylic acid, 1, 3-cyclohexetnodicarboxylic acid, maleic anhydride, fumaric acid, (acid) succinic anhydride, 2,6-naphthalenedicarboxylic acid, glutaric acid and esters thereof. The alkali resins transported in sulfonated water useful in the invention preferably has a K value, defined as the total number of moles (Mt) of each reagent divided by the total equivalents of acid functionality (Ert), from about 1.0 to about 1.5, more preferably from about 1.0 to about 1.25, and a value of R, defined as the total equivalents of hydroxyl functionality (E0H) divided by the total equivalents of acid functionality (Ea), from about 1.0 to about 2.0, more preferably from about 1.0 to approximately 1.5. The K value is a measure of the molecular weight of a resin that increases as the K value decreases to 1.00. Subsequently the higher molecular weight resins are better, the K values that are more intimate at 1.00 are most preferred. The value of R is proportional to the equivalents of the excess hydroxyl functionality used in the synthesis of the resin. An excess of hydroxyl functionality is preferred, however this excess should not be too high to give the resulting sensitive water coating. The sulfomonomer of the sulfomonomer adduct is either a difunctional monomer or a monofunctional monomer containing an -S03M group attached to an aromatic nucleus where M is hydrogen or a metal ion such as, for example, Na +, Li ', iX, Ca'1, Cu-1, Fe2h, or Fe3 +. The sulfomonomer as a difunctional monomer component may be a dicarboxylic acid (or a derivative thereof) which contains a -S03M group where M is as defined above. Suitable examples of the aromatic nucleus to which the S03M group can be attached include, but are not limited to, benzene, naphthalene, anthracene, diphenyl, oxydiphenyl, sulfonyl-diphenyl, and methylenediphenyl. Especially good results are obtained when the difunctional monomer is a sodium salt of a sulfoisophthalic acid, a sulfoterephthalic acid, a sulfophthalic acid, 4-sulfo-naphthalene-2,7-dicarboxylic acid or a derivative thereof. More preferably, the difunctional monomer is 5-sodiosulfoisophthalic acid or a derivative such as dimethyl-5-sodiosulfoisophthalate. Other preferred difunctional monomers are 5-sulfoisophthalic lithium acid, dimethyl lithium 5-sulfoisophthalate, potassium 5-sulfoisophthalic acid, and 5-sulfoisophthalate dimethyl potassium. Other effective difunctional monomers containing an S03M Group attached to an aromatic nucleus include metal salts of aromatic sulfonic acids or their respective esters of the formula (IV): wherein X is a trivalent aromatic hydrocarbon radical, Y is a divalefin aromatic hydrocarbon radical, R 'is hydrogen or an alkyl group of four carbon atoms, M 'is hydrogen Na +, Li +, or K +. Examples of preferred monomers of formula (IV) include, but are not limited to, 4-sodiosulfofenil-3, 5-dicarbometoxibenzensulfonato, 4-litiosul-fofenilo, 3, 5-dicarbometoxibenzensulfonato and 6-sodiosulfo-2-naphthyl-3 , 5-dicarbomethoxy-benzensulfonate. Still other effective difunctional monomers containing an S03M group attached to an aromatic nucleus include metal salts of dicarboxylic acids sulfodiphenyl ether or esters thereof of the formula (V): wherein R "is hydrogen, an alkyl group of eight carbon atoms, or phenyl and M" is hydrogen, K +, Na 'or Li'. Examples of preferred monomers include, but are not limited to, 5- [4 ~ (sodiosul fo) phenoxy] isophthala to dimethyl or, 5- [4- (sodiosulfo) phenoxy] terephthalate dimethyl, and 5- [4- ( sodiosulfo) phenoxy] isophthalic. Additional examples of such monomers are described in U.S. Patent No. 3,734,874, incorporated herein by reference. The type and amount of metal sulfonate selected for water dispersibility may be varied to obtain alkyd resins containing useful ion. As small as 2 mole percent based on the total carboxylic acid content that will impart a significant degree of water miscibility, however, at least 3 percent are preferred. The water soluble polyesters can be formulated with as much as 20 mole percent of the metal sulfonate. However, a practical upper limit based on the amount of intermediate introduced branch required to neutralize the effects of water sensitivity is 9 percent, preferably 6 percent. The metal sulfonates that are most preferred include-sodiosulfoisophthalic 5, 5-sodiosulfoisophthalate, 5-sulfoisophthalic acid, lithium 5-sulfoisophthalate dimethyl lithium 5-sulfoisophthalic acid, potassium 5-sulfoisophthalate dimethyl potassium, acid-sodiosulfobenzoico acid Similar. Optionally, the sulfomonomer containing a sulfonate group which can react with a polyol to produce a polyol at least (eg a diol) the adduct of the sulfomonomer can be a monofunctional sulfomonomer containing a sulfonate group which can react with a polyol containing three hydroxylol groups at least. The monofunctional sulfomonomer is preferably selected from the following group of sulfomonomers: where X 'is CH2, S02, or O and M' '' is an alkaline earth metal. When the polyol sulfomonomer adduct is prepared by reacting a di functional functional sulfomonomer with a polyol, the polyol is preferably a diol. Suitable examples of diols include those described above with the following diols being more preferred: ethylene glycol, diethylene glycol, 2, 2, 4-trimethyl-l, 3-pentanediol, 1,4-cyclo-hexanodimetanol, 1, 3-cyclohexanedimethanol , hydroxypivalyl hydroxypivalate, dipropylene glycol, 1,6-hexanediol, 1,10-decanediol, 1,3-butanediol, hydrogenated bisphenol A, 1,4-butanediol and neope glycol. In addition to the polyol amount reacted with the fatty acid, fatty ester or naturally saponified oil partially occurs according to the preferred step, and in addition to the polyol used in the preparation of the sulfomonomer adduct of a monofunctional sulfomonomer, an additional amount of a polyol or other branched agent such as a polycarboxylic acid can be used to increase the molecular weight and the branching of the alkyd resin carried in water. These branched surfactants are preferably selected from trimethylolethane, pentaerythritol, erythritol, threitol, dipentaerythritol, sorbitol, glycerine, trimellitic anhydride, pyromellitic dianhydride, dimethylolpropionic acid, and trimethylolpropane.

For the alkyd resin to serve as a reactive film aid (by oxidative coupling) in a hybrid latex and incorporated into the crosslinked polymer film, it is preferred that the alkyd have a bit of length - of finite oil - long, medium or short. The length of finite oil or the oil content is generally between about 20% by weight and about 90% by weight in the alkyd composition based on the total weight of the alkyd resin. A "long" alkylated oil has an oil length or oil content of about 60-90% by weight based on the total weight of the alkyd resin. A "medium" oil alkyd has an oil content of about 40-60% by weight based on the total weight of the alkyd resin. A "short" oil alkyd has an oil length or oil content of about 20-407. by weight based on the total weight of the alkyd resin. Ethylenically unsaturated monomer The acrylic portion of the alkyd resin transported in acrylic modified water can be prepared by free radical polymerization of at least one ethylenically unsaturated monomer in the presence of an alkyd transported in sulfonated water as described above. Examples of suitable ethylenically unsaturated monomers include, but are not limited to, styrenic monomers such as styrene, α-methyl styrene, vinyl naphthalene, vinyl toluene, chloromethyl styrene and the like; ethylenically unsaturated species such as, for example, methyl acrylate, acrylic acid, methacrylic acid, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, sodium acrylate, ethylhexyl, ethylhexyl methacrylate, octyl acrylate, octyl methacrylate, glycidyl methacrylate, carbodiimide methacrylate, alkyl crotonates, vinyl acetate, di-n-butyl maleate, di-octyl maleate, and the like; and nitrogen containing monomers including t-butylaminoethyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, N, N-dimethylaminopropyl methacrylamide, 2-t-butylaminoethyl methacrylate, N, N-dimethylaminoethyl acrylate, N- (2-methacryloyloxy-ethyl) ethylene urea, and methacrylamidoethylethylene urea. Other examples of suitable ethylenically unsaturated monomers include, but are not limited to, ethylenically unsaturated monomers that possess at least one latent oxidative functionality (FOL). Preferably, at least one of the ethylenically unsaturated monomers polymerized with the alkyd transported in sulfonated water having latent oxidative functionality (FOL). The FOL group can be any pending portion that is capable of (i) surviving the polymerization process and (ii) participating in or crosslinking the oxidative promotion of the modified alkyde. After the polymerization of the FOL acrylic monomer, a modified alkyd of the invention possesses sufficient FOL groups to increase or normally amplify the degree of crosslinking normally found in the acrylic-modified water-transported alkyd resins containing no FOL group. In other words, the rest of the FOL groups increase or reinforce the effective crosslinker of the hybrid resin. The presence of a FOL group in the modified alkade makes crosslinking possible on or after the formation of the film. With a modified alkyde of the invention, the crosslinking agents can occur between the FOL groups of the acrylic monomer (s), between a FOL group of an acrylic monomer and an ethylenically unsaturated alkyd functionality, or between the ethylenically unsaturated functionalities of alkyd. Able to undergo an oxidative reaction, the FOL group participates in or promotes the oxidative crosslinker as a source of free radicals to generate a free radical flow. Preferably the FOL group is an ethylenic unsaturation such as, but is not limited to, allyl and vinyl groups. The FOL group can also preferably be a portion of acetoacetyl or an enamine moiety. The preparation of enamines of the acetoacetyl groups is described in US Patents 5,296,530, 5,494,975, and 5,525,662 which is incorporated herein by reference.

Examples of acrylic monomers having latent oxidative functionality (FOL) groups include, but are not limited to, allyl methacrylate, vinyl methacrylate, acetoacetoxyethyl methacrylate, hydroxyl butenyl methacrylate, allyl or maleic diallyl ester, poly (allyl glycether) and similar. Water-based Latex A water-based latex of the invention was prepared by the polymerization of at least one ethylenically unsaturated monomer in the presence of an aqueous dispersion of an alkyd carried in water having a pending sulfonate functionality. A water-based latex of the invention is stable at the same pH (pH > 7) as latex prepared from alkyd transported in traditional water. However, the hybrid latexes other than traditional water-borne alkyds, the alkyd transported in sulfonated water based on hybrid latexes of the invention is also stable at pH < 1, as well as a. pR of 4.0-4.5. In the water-based coating of the invention, the modified alkyd generally exists as particles in water. As discussed above, if the monomers containing FOL groups are included in the acrylic portion of the hybrid resin, sufficient FOL groups remain after the polymerization process to strengthen the oxidative crosslinker of the alkyd latex forming films based on resulting water. Since the functions of the FOL group increase the effective crosslinker of the alkylate, the post-polymerization survival of the sufficient FOL groups not only allows their nucleoactivity with other FOL groups and / or alkyd functionality carried in water in or after the formation of the film but can also promote similar oxidative crosslinker between the functionalities of alkyd transported in water. As a result of such co-activity between the FOL group and / or the alky functionalities, the properties of the film such as, for example, the strength of the solvent can be improved. As discussed above, the ethylenically unsaturated monomer can be added as a mixture of at least one ethylenically unsaturated monomer or as a mixture of at least one ethylenically unsaturated monomer and an acrylic FOL comonomer. The addition of an ethylenically unsaturated monomer is directed in a single-phase or multi-phase process (e.g. core-shell). Preferably, the ethylenically unsaturated monomer is added in a one-phase process. In cases where a FOL acrylic monomer is desired, the addition of the FOL acrylic monomer or monomers in a one phase process results in a homogeneous acrylic monomer (ie, simple terpolymer) which contains a sufficient number of FOL groups (eg allyl , vinyl) capable of reacting with other FOL groups or functionality, alkylated in or after the film formation or promoting the reaction between the functionalities in the alkyde. The addition of the FOL acrylic monomer in a multiple phase process produces a heterogeneous acrylic monomer. For example, in a two-phase process, the first phase of the addition can produce a core polymer of preferably an acrylic monomer or styrene / acrylic polymer that is often pre-crosslinked with a multi-functional monomer such as trimethylolpropane triacrylate. . The second phase of the addition produces a shell polymer preferably a styrene / acrylic polymer containing a high level of FOL groups, such as reactive allyl and / or vinyl moieties. The monomers for use in one or more phases of the polymerization process are described in US Pat. No. 5,539,073 incorporated herein by reference. The FOL groups can be located at the end of the polymer as well as along the base column of the polymer. As discussed above, preferably the water-based latex of the invention has been prepared under the conditions of emulsion polymerization. In general, in the polymerization of the FOL emulsion the acrylic monomer compositions, is mainly the portion of ethylenic unsaturation of the acrylic undergoing the polymerization and not the FOL group. If the FOL group participates in the polymerization, the polymerization conditions are such that sufficient FOL groups survive in order to oxidatively crosslink with another FOL Group and / or functionality of the alkyde carried in water and / or to increase the oxidative crosslinker between Liquid functionalities transported in water on or after film formation. The survival of the FOL groups, such as the allyl or vinyl portions, in the polymerization can be achieved by manipulating the differences in the reactivity of the ethylenically unsaturated groups. For example, the ethylenically unsaturated acrylic portion of an allyl or vinyl functionalized acrylic monomer has greater reactivity in styrenic monomer polymerization than the allyl or vinyl FOL moiety. As a result, the resulting polymer contains FOL groups. A description of the handling of the allyl functionalized acrylic monomer compositions to promote survival of the allyl portion in the polymerization of the emulsion can be found in U.S. Patent 5,539,073 which is incorporated herein by reference. The functionalized vinyl acrylic monomer compositions can be handled in a manner similar to that applied to the allyl functionalized acrylic monomer compositions. When the FOL group of the acrylic monomer gives an acetoacetoxy moiety, under polymerization conditions of the emulsion it is the ethylenically unsaturated moiety that polymerizes. The acetoacetoxy portion is not effected by, and thus survives, the polymerization process.

The polymerization process by which hybrid latexes are made may also require an initiate, a reducing agent, or a catalyst. Suitable initiators include conventional initiators such as ammonium persulfate, ammonium carbonate, hydrogen peroxide, t-butylhydroperoxide, ammonium or alkali sulfate, di-benzoyl peroxide, lauryl peroxide, di-tertiary butyl peroxide, 2,2'-azobisisobutaronitrile , benzoyl peroxide, and the like. Suitable reducing agents are those which increase the percentage of polymerization and include, for example, sodium bisulfite, sodium hydrosulfite, sodium formaldehyde sulfoxylate, ascorbic acid, isoascorbic acid, and mixtures thereof. Suitable catalysts are those compounds that promote the decomposition of the polymerization initiator under the polymerization reaction conditions whereby the percentage of polymerization increases. Suitable catalysts include transition metal compounds and dryers. Examples of such catalysts include, but are not limited to, ferrous sulfate heptahydrate, ferrous chloride, cupric sulfate, cupric chloride, cobalt acetate, cobalt sulfate, and mixtures thereof. Optionally, a conventional surfactant or combination of surfactants can be used as a co-stabilizer or cosurfactant, such as an anionic or non-ionic emulsifier, in the suspension or emulsion polymerization preparation of a hybrid latex of the invention. Examples of preferred surfactants include, but are not limited to, alkali or ammonium alkyl sulfate, alkylsulfonic acid, or fatty acid, oxyethylated alkylphenol, or any combination of anionic or nonionic surfactant. A more preferred surfactant monomer is HITENOL HS-20 (which is a polyoxyethylene alkylphenyl ether ammonium sulfate available from DKS International, Inc. of Japan). A list of suitable surfactants is available in the treatise: McCutcheon's Emulsifiers & Detergents, North American Edition and International Edition, MC Publishing Co., Glen Rock, NJ, 1993. Preferably, a conventional surfactant or combination of surfactants is used when the alkid portion of the hybrid resin represents above about 35% by weight, generally about 5-20? > by weight of the total solids of the latex. If the resulting hybrid latex is formulated with drying salts typically used in alkyd casings and FOL portions are presented in the acrylic portion of the hybrid, the significant improvements, among other properties, the fraction of latex gel and the expansion ratio (LGF and LSR) , respectively) and the resistance of the solvent is observed. While the alkyd portion of the hybrid latex plays an important role in stabilizing the latex and improving the formation of the film, it is the presence of the FOL acrylic portion of the hybrid which can improve certain physical and mechanical film properties. The improved properties are typically those that are related to the high crosslinking density than those observed for the hybrid resins containing acrylics without FOL. In general, the alkyd portion of the hybrid latex represents approximately 5-60? -. by weight, preferably about 10-50% by weight, more preferably about 20-40% by weight of the total solids of the latex while the acrylic portion of the hybrid latex represents about 30-90% by weight, preferably about 50-80% by weight. weight, more preferably about 60-80% by weight of the total solids of the latex. Such hybrid latexes can be used beyond coating compositions. A coating composition of the invention contains a latex of an alkyd dispersion carried in water modified with acrylic of the invention and can be prepared by techniques known in the art, for example as described in US Patent Nos. 4., 698,391, 4,737,551, and 3,345,313 each of which are incorporated herein by reference in their entirety. Examples of such coating compositions include, for example, architectural coatings, maintenance coatings, industrial coatings, automotive coatings, textile coatings, liners, adhesives, and layers for paper, wood, and plastics. The coating compositions of the invention contain significantly less solvent, less than 25"by weight to as low as 17, by weight and even zero VOC content.The alkyd portion carried in water of the hybrid resin which retains the desirable properties of an alkyd while the acrylic portion of the resin improves the hardness and durability of the hybrid alkyd resin When a FOL acrylic monomer is used, the FOL portion of the acrylic resin fulfills or enhances the oxidative crosslinking ability of the hybrid alkyd resin At room temperature, the coating compositions of the invention produce coatings having high gloss, fast curing, and good acid and caustic resistance.The coating composition can be coated on a substrate and cured using techniques known in the art (for example by spray by applying 3 to 4 mils of wet coating on a metal panel, and heating in a forced air oven at 150 ° C for 30 minutes). The substrates can be any common substrate such as paper, polyester film such as polyethylene and polypropylene, metals such as aluminum and steel, glass, urethane elastomers and substrates (painted) primers, and the like. The coating composition of the invention can be cured at ambient temperature (environmental cure), at elevated temperatures (thermal cure), or photochemically cured. A coating composition of the invention may also contain coating additives. Examples of such coating additives include, but are not limited to, one or more leveling, rheology, and flow control agents such as silicones, fluorocarbons or celluloses.; the spreaders; reactive coalescence aids tai such as those described in U.S. Patent No. 5,349,026, incorporated herein by reference; plasticizers; crushing agents; moisture of pigment and dispersing agents and surfactants; ultraviolet absorbers (UV); UV light stabilizers; staining pigments; colorants; deformation and anti-formation agents; anti-establishment agents, anti-sinking agents and bodily agents; .good anti-skinners; anti-sinking and anti-flotation agents; biocides, fungicides and mildiucides; corrosion inhibitors; thickening agents; or coalescence agents. Specific examples of such additives can be found in Raw Materials Index, published by National Paint & Coatings Association, 1500 Rhode Island Avenue, N.W., Washington, D.C. 20005. Additional examples of such additives and emulsion polymerization methodology can be found in U.S. Patent No. 5,371,148, incorporated herein by reference. Examples of flattened agents include, but not 3o are limited to, synthetic silica, available from the Davison Chemical Division of W. R. Grace & Company under the trade name SYLOIDO; polypropylene, available from Hercules Inc. under the trade name HERCOFLAT ©; and the synthetic silicate, available from J. M. Huber Corporation under the trade name ZEOLEX®. Examples of dispersing agents and surfactants include, but are not limited to, sodium bis (tridecyl) sulfosuccinate, sodium di (2-ethylhexyl) sulfosuccinate, sodium dihexylsul-phosuccinate, sodium dicyclohexyl sulfosuccinate, sodium diammon sulfosuccinate, sodium diisobutyl sulfosuccinate, iso-decyl sulfosuccinate disodium, ethoxylated alcohol diisocyl ester of sulfosuccinic acid, amido polyethoxy sulfosuccinate alkyl amido, N- (1,2-dicarboxyethyl) -N-octadecyl sulfosuccinamate tetra-sodium, N-octasulfosuccinamate disodium , sulfated ethoxylated nonylphenol, 2-amino-2-methyl-1-propanol, and the like. Examples of viscosity, suspension, and flow control agents include, but are not limited to, polyaminoamide phosphate, high molecular weight carboxylic acid salts of the acid salts polyamine amides, and alkylene amine salts of an unsaturated fatty acid. , all available from BYK Chemie USA under the trade name ANTI TERRA .. Additional examples include copolymers of polysiloxane, polyacrylate solution, cellulose esters, hydroxyl ethyl cellulose, hydrophobically modified hydroxyethyl cellulose, hydroxylpropyl cellulose, polyamide wax, polyolefin wax, carboxymethyl cellulose, ammonium polyacrylate , sodium polyacrylate, hydroxylpropyl methyl cellulose, ethyl hydroxyl ethyl cellulose, polyethylene oxide, guar gum and the like. Other examples of thickeners include the associated methylene oxide / ethylene thickeners and water soluble carboxylated thickeners such as, for example, UCAR P0LIFPH0BEO by Union Carbide. Various proprietary antifoam agents are commercially available and include, for example, Buveman from Buckman Laboratories Inc., BYK © from BYK Chemie, U.S.A., FOAMASTER © and NOPCO © from Henkel Corp. / Coating Chemicals, DREWPLUS © of the Drew Industrial Division of Ashland Chemical Company, TRYSOL © and TROYKYD © of Troy Chemical Corporation, and SAG © of Union Carbide Corporation. Examples of fungicides, mildewis, and biocides include, but are not limited to, 4-dimethyl azolidine, 3,4,4-trimethyloxazolidine, modified barium metaborate, potassium N-hydroxy-methyl-N-methyldithiocarbamate, 2- ( ticiano-methylthio) benzothiazole, potassium dimethyl dithiocarbamate, adamantane, N- (trichloromethylthio) phthalimide, 2,4,5,6-tetrachloro-isophthalonitrile, orthophenyl phenol, 2,4,5-trichlorophenol, dehydroacetic acid, copper naphthenate, copper octoate, organic arsenic, tributyl tin oxide, zinc naphthenate, and copper 8-quinoline. Examples of U.V. and light stabilizers U.V. they include among others substituted benzophenone, substituted benzotriazoles, hindered amines, and hindered benzoates, available from American Cyanamid Company under the tradename CYASORB UV ©, and diethyl-3-acetyl-4-hydroxy-benzyl-phosphonate, benzophenone from 4-dodecyloxy- 2-hydroxy, and resorcinol monobenzoate. Examples of solvents and coalescing agents are well known and include but are not limited to ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, isobutanol, ethylene glycol monobutyl ether, propylene glycol n-butyl ether, propylene glycol methyl ether, propylene glycol monopropyl ether, dipropylene glycol methyl ether, diethylene glycol monobutyl ether, trimethylpentanediol monoisobutyrate, ethylene glycol monooctyl ether, diacetone alcohol, TEXANOL alcohol ester © (Eastman Chemical Company), and the like. Such solvents and coalescence aids may also include reactive solvents and the coalescence aids such as diallyl phthalate, polyglycidyl allyl ether SANTOLINK XI-100 © of Monsanto, and others as described in US Pat. Nos. 5,349,026 and 5,371,148, incorporated herein. by reference. Pigments suitable for use in the coating compositions provided by the invention are the typical organic and inorganic pigments, well known to one of the ordinary experts in the surface layer technique, especially those established by the Color Index, 3d Ed. , 2d Rev., 1982, published by the Society of Dryers and Colourists in association with the American Association of Textile Chemists and Colorists. Examples include, but are not limited to, the following: titanium dioxide, barytes, clay, or calcium carbonate, Pigment Cl White 6 (titanium dioxide); Pigment Cl Red 101 (red ferric oxide); Yellow Pigment 42; Pigment Cl Blue 15, 15: 1, 15: 2, 15: 3, 15: 4 (copper phthalocyanines); Red Cl Pigment 49: 1; and Red Cl Pigment 57: 1. Dyes such as phthalocyanine blue, molybdate orange, or carbon black are also suitable for the coating compositions of the invention. The following examples are given to illustrate the invention. It should be understood, however, that the invention will not be limited to the specific conditions or details described in these examples. Examples of various coating compositions of the invention use the following materials not described above: Associative thickener ACRYSOL 1020 sold by Rohm and Haas, Philadelphia, PA Accelerator ACTIV 8 sold by R.T. Vanderbilt, - Inc., Norwalk, CT dehydrators AQUACAT and MAGNACAT sold by Ultra Additive, Paterson, New Jersey Dispersant BYK-024 sold by BYK-Chemie, Cleveland, Ohio Dehydrator COBALT HYDROCURE II, dehydrator ZIRCONXUM HYDROCEM, and DRI-RX-HF accelerator sold by OMG, Cleveland, Ohio Plasticida dibutyl phthalate sold by Eastman Chemical Company, Kingsport, TN Coalescents EASTMAN EB and EASTMAN DB [co-solvent] sold by Eastman Chemical Company, Kingsport, Tennessee FASCAT 4100 an esterification catalyst, sold by M &T Chemicals, Rahway, New Jersey Co-solvent HEXYL CARBITOL sold by Union Carbide Corporation, Danbury, Connecticut, Reduced Water Alkali KELSOL 3960-B2G-75 sold by Reichhold Chemical, Research Triangle Park , North Carolina PAMOLYN 200 tallow fatty acid, sold by Hercules Incorporated, Wilmington, Delaware PATCOTE 519 and 577 defoamers sold by American Ingredients Company, Kansas City, Missouri Latex RHOPLEX WL-51 sold by Rohm & Haas, Philadelphia, PA SURFYNOL 104, 104PA and 465 surfactants sold by Air Products and Chemicals, Inc., Allentown, Pennsylvania.

Dispersants TAMOL 165 and TRITÓN CF-10 sold by Rohm & Haas, Philadelphia, PA Surfactant TERGITOL 15-S-40 sold by Union Carbide Chemical and Plastics Co., Danbury, CT Pigments TIPURE R-706 and Aqueous Subsidence R-746 sold by DuPont Chemicals, Wilmington, Delaware, The following methods were used for evaluating the coatings and films prepared according to the invention. FRACTION OF FILM GEL / PERCENTAGE OF SHEATH: The proportions of film expansion (FSR) were obtained by determining the percentage of the weight fraction of the insoluble polymer inflated in acetone (by weight) for the dry weight of the weight fraction insoluble in a sample of dry film. The procedure used is as follows: for each determination of the sample, a steel screen of 4"x 4" 325 meshes and a heavy metal canister are baked in the oven, cooled and weighed for 30 minutes (Wl and W2, respectively ). After the latex film is dried and maintained for the required number of days at room temperature, a piece of the film is cut, weighed (W3), placed in an aluminum pan, and separated. Another sample of the film is cut, weighed (W4) and placed in a screw cap jar with excess solvent in a stirring bath for 16 hours at constant temperature. The film gel is recovered by pouring the solution plus the wet solids through the screen and weighing the screen more withholding the wet solids (W5). At this point on the screen plus the solids and the film sample were dried in the aluminum canister in a vacuum oven at 80 ° C to the constant weight and the weight for the screen plus the dry solids (W6) and the sample of Film on the aluminum boat (W7) was held. The calculations are shown in the following. FGF = (W6-W1) / [W4 * ((W7-W2) / W3)] FSR = (W5-W1) / (W6-W1) VISCOSITY OF PAINTING: The viscosity of paint (in Krebs Units) SP measured after 24 hours of using a Krebs-Stormer viscometer. RESISTANCE METHYL ETHYL KETONE: Methyl Ethyl Ketone (MEK) resistance was reported as MEK double rubbing (a side-to-side play). The MEK rubs were measured by securing the multiple layers of blankets on the round head of a 16-oz. Ball-pin hammer. The hammer is then attached to a mechanical device that moves the hammer from one side to the other. The blanket is saturated with MEK, the panel is rubbed with the soaked cloth to the point of the first escape from the substrate. PENDULUM HARDNESS: The hardness of the pendulum was measured using a Gardner Pendulum Hardness Tester.

TUKON HARDNESS: Tukon Hardness was determined according to ASTM D1474-92. SURFACE ADHESIVITY: Surface Adhesivity was determined by applying firm finger pressure for 10 seconds. Valuations are as follows: 0 - not released 3 - sticky 4 - adhesiveness 5 - without adhesiveness Example 1: Preparation and Dispersion of Sulfonated Alkyd Resin Dispersible in Water Stage 1: An adduct of neopentyl glycol (NPG) and 5-sodiosulfoisophthalic acid (SIP) was first prepared by reacting NPG (2483.5 g, 23.88 mol); SIP (93.37) (1608.5g, 5.6 mol); distilled water (276. Og); and the catalyst, FASCAT 4100 (3.3g) in a three-necked, round bottom flask equipped with a mechanical stirrer, a steam-wrapped partial condenser, a Dean-Stark trap, a nitrogen inlet, and a water condenser. The reaction temperature was increased gradually from 130 ° C to 190 ° C in a period of five hours and the condensate (water) collected in a Dean-Stark trap. The reaction was allowed to continue until an acid number of 3. A portion of the resulting product was used in the next step.

Stage 2: In a three-necked round bottom flask (3L) equipped with the same configuration as in the above, the NPG / SIP adduct was charged (497.0 g); phthalic anhydride (PA) (357.4g, 2.42 mol); pentaerythritol (PE) (233.8g, 1.72 mol); PAMOLYN 200 (talo fatty acid) (985.9g, 3.40 mol); and FASCAT 4100 (1.54g). The reaction temperature was gradually increased to 230 ° C in one hour. The reaction was allowed to continue for approximately three more hours until an acid number of 8. The resulting resin was allowed to cool and subsequently isolate. The Aqueous Dispersion Preparation: The viscous resin from Step 2 was heated to 80 ° C in a furnace and subsequently charged (100g) in a flask equipped with a water condenser. The resin was heated to 120 ° C and stirred under a nitrogen atmosphere. The melting of the resulting resin was allowed to cool to 80 ° C and the distilled water (100g) was added dropwise. During the dispersion process, the temperature was further reduced to 50 ° C when a homogenous resin solution was obtained. Stirring was allowed to continue and additional water (22g) was added to give an aqueous resin with 45% solids. Examples 2-9: The Preparation of Latexes by Emulsion Polymerization of Alkyl / Heterogeneous Acrylic Hybrid Resins For each of Examples 2-9, in a 1000 mL resin kettle equipped with a condenser, the nitrogen purge, and an underlying food tube was added water and alkyd dispersion of Example 1, (Table 1). A nitrogen purge was started, then the contents of the reactor were brought above 80 ° C, a charge of the initiator composed of 0.15 g of ammonium persulfate dissolved in 5.0 g of water was added to the reactor. The food of the core composition or the first acrylic phase monomer was then initiated and fed more than about 70 mins. Simultaneously, an initiator food composed of 0.51 g of ammonium persulfate and 0.66 g of ammonium carbonate dissolved in 33.0 g of water was started and fed at 0.22 g / min. After the first monomer feed stage was complete, the reaction was maintained for 30 mins at 80 ° C with continued addition of the starter solution. After the holding period, the shell composition feed or the second acrylic monomer phase was started and fed more than about 50 mins. After all the food was completed, heating to 80 ° C was continued for 60-90 mins. The emulsion was then cooled, filtered through a screen of 100 mesh wire, and the solids filtered or collected in pieces. The particle size, viscosity and pH of the resulting acrylic / heterogeneous acrylic hybrid resin latexes were determined and summarized in Table 1. Example 10: Preparation of Latexes by Emulsion Polymerization of Alkyl Acrylic Hybrid Resin / Homogenea-Control In a 1000 mL resin kettle equipped with a condenser, the nitrogen purge was added, and an underlying food tube was added to 122.1 g of water and 204.4 g of the alkyd dispersion of Example 1. A nitrogen purge was start, then the contents of the reactor were brought to 80 ° C at 300 rpm. Then an initiator charge composed of 0.15 g of ammonium persulfate dissolved in 5.0 g of water was added to the reactor. A monomer feed compound of 38.5 g of 2-ethylhexylacrylate, 61.3 g of styrene, and 30.7 g of methyl methacrylate was started and fed over about 135 mins. Simultaneously, an initiator feed compound of 0.51 g of ammonium persulfate and 0.66 g of ammonium carbonate dissolved in 33. Og of water was started and fed at 0.22 g / min. After all the food was completed, the heated 80 ° C was continued for 60-90 mins. The emulsion was then cooled and filtered through a screen of 100 mesh wire. The particle size, the viscosity and the resulting hybrid latex Ph were determined and summarized in Table 1. Example 11: Cure studies in the movies Claras that use a Cobalt / Zirconium Dryer Pack as Reticulating Catalyst. For each latex of Examples 2-10, to 30 grams of latex was added 4.3g of water (to reduce solids to 35%), 0.24g of Cobalt HIDROCURE II and 0.50g of Zirconium Hydrochem.

The samples were shaken overnight, in addition to casting on released paper (humidity 15 mils) and air drying at room temperature. Example 11: Cure Studies in Clear Films Using a Cobalt / Zirconium Dryer Package as Reticulating Catalysts. For each latex of Examples 2-10, to 30 grams of latex was added 4.3g of water (to reduce solids to 35%), 0.24g of Cobalt HIDROCURE II and 0.50g of Zirconium Hydrochem. The samples were shaken overnight, in addition to casting on released paper (humidity 15 mils) and air drying at room temperature. Film gel fractions (FGF) were obtained by determining the insoluble weight fraction of polymer in a dry film sample. The average values were determined from triplicate measures and summarized in Table 2. Both of the non-functional control (Example 10) and those hybrid latexes that contain either allylic or vinyl functionality in the shell (Examples 2-8) seem to reach a high plateau in gel film fraction of 75-80% in 21 days. It is believed that this apparent independence of the ultimate gel fraction in the acrylic composition is in fact related to the composition of the alkyd - specifically to the relatively low level of tallow fatty acid (TOFA) in the alkyd. At the lower levels of TOFA, the average number of reactive groups per the alkylated molecule can be so low that statically, there are alkyd molecules that are essentially non-reactive and are not made, therefore, become part of the cross-linked matrix. However, the allyl / vinyl functional latexes of this invention offer significant improvements in the film gel fraction at shorter cure times (for example 7 days). In fact, the average of the 7 day film gel fraction of the allyl / vinyl functional hybrids is 76.2 ± 2.1% - considerably higher than the 62.4% observed in non-functional Example 10. The proportions of dilatation of the film indicate that although some fraction of the hybrid latex (perhaps the alkyd as described above) is not incorporated in the crosslinked film, that fraction that continues to crosslink with time - resulting in a continuous decrease in the relationship of the dilation of the film. In addition, the proportions of film dilation determined by the functional allyl / vinyl latexes are significantly lower on days 7 and 21 than those determined by the non-functional control. This further suggests the importance of functionality in the acrylic portion of an alkyd / acrylic hybrid. The comparison of the film expansion percentages for Examples 1, 3 and 4 demonstrate the effect of the alkyd content on the percentage of the hybrid oxidative alky / acrylic crosslinker of the hybrid films. While the film gel fractions are quite similar for these three hybrids, the percentages of the final film dilation and perhaps more important the percent change in the film dilation percentages of 7 to 21 days indicates the LOW levels of the film. denser alkyd yield and / or the films crosslinked rapidly. This demonstrates that it has a latent oxidative functionality (FOL) acrylic as a component of the alkyd / acrylic hybrid can significantly reach the percentage / crosslinking extent of the hybrid film. Example 9 is not and strictly speaking, an allyl / vinyl functional alky / acrylic hybrid. The reactive monomer in this latex is acetoacetoxyethyl methacrylate (AAEM), as opposed to allyl methacrylate (ALMA) or vinyl methacrylate (VMA). It is well known that neutralized amine pH of this latex (pH <; 8.0), the acetoacetoxy functionality will form oxidatively reactive enamine groups that could be either ALMA or VMA, reacting the oxidative functionality of the alkyd dispersion. In fact, the film gel fraction and percent expansion measurements indicate that the enamine functionality associated with the AAEM crosslinkers much more rapidly than either the ALMA or VMA chemistry. Advantageously, the survival of AAEM functionality in the polymerization process does not T3 CD ü)? li rf O P- CD O li C o I-1 Table 1 J £ U 3 ti ÍU The density of the core composition (% by weight) shell composition (% by weight) t core / shell Size of Particle Vise Quantity 3 3 fD CD MA / S / EHA / TMPTA S EHA ALMA / VMA / AAEM 'Percentage 3 ( nm) (cps) (gm) PH 3 rf rt (D CD CD O 2 35 0.0 / 70.0 / 29.5 / 0.5 55.8 / 23.6 / 14.3 / 0/0 1.70 195 48 0.08 8.2 H O 3 35 35 ¡3 3 .0 / 35.0 / 29.5 / 0.5 55.8 / 23.6 / 14.3 / 0/0 1.70 298 628 0.06 8.1 4 35 70.0 / 0.0 / 29.5 / 0.5 55.8 / 23.6 / 14.3 / 0/0 1.70 246 90 0.22 8.1 20 35.0 / 35.0 / 29.5 / 0.5 55.8 / 23.6 / 14.3 / 0/0 1.70 296 17 2.04 8.3 6 50 35.0 / 35.0 / 29.5 / 0.6 55.8 / 23.6 / 14.3 / 0/0 1.70 152 204 0.09 • 8.0 7 35 35.0 / 35.0 / 29.5 / 0.7 55.8 / 23.6 / 0 / 14.3 / 0 1.70 341 6410 0.00 8.2 8 35 35.0 / 35.0 / 29.5 / 0.8 55.8 / 23.6 / 7.2 / 7.1 / 0 1.70 338 5110 0.00 8.2 9 35 35.0 /35.0/29.5/0.9 55.8 / 23.6 / 0/0 / 14.3 1.70 371 - 0.00 8.1 10 35 47.0 / 23.5 / 29.5 * 146 625 0.06 8.0 * corresponds to the total composition of the core / shell latex in Examples 2 -9 without the LOF monomer (s) and all the shell compositions contain 6.3% by weight of N, 1-dimethylamide methacrylate all latexes prepared in 40% solids MMA-methyl methacrylate; S-styrene; EHA = ethylhexyl acrylate; TMPTA Triacrylpropane Triacrylate; ALMA = allyl methacrylate; VMA- METACRIALÑTO DE VINILO; AAEM - acetoacetoxyethyl methacrylate Table 2 Ex 7- day 21- day% 7- dif to 21- day% FGF FGF Increase FSR FSR Decrease year in FGS in FSR 2 0.762 0.800 5.0 3.494 2.026 42.0 3 0.754 0.761 0.9 3.198 2.523 21.1 4 0.766 0.765 -0.1 3.904 3.229 17.3 5 0.785 0.817 4.1 4.322 2.608 39.7 6 0.719 0.731 1.7 3.454 3.397 1.7 7 0.781 - ~ 3.512 - - 8 0.766 0.782 2.1 3.662 3.321 9.3 9 0.898 __ - 2.623 - 10 0.624 0.769 23.2 5.383 4.156 22.8 FGF - Film Gel Fraction; FSR - Movie Scattering Percentage Example 12: Preparation of Dispersible Sulfonated Alkyl Resins Following the procedure described in Example 1, two of the other sulfonated alkyd resins dispersible in water were prepared whose content, respectively, 0.63 and 1.29 times the amount of tallow fatty acid (PAMOLYN 200) as used in Example 1. Example 1 was designated and these two materials were designated short, medium and long oil alkyds, respectively. The process of alkyd dispersion A and for these three samples it was slightly modified to include the addition of 12% carbitol hexyl based on the weight of the alkyd) the previous alkyd resin of the water addition. Examples 13-23: Preparation of Latex Containing Alkyd / Acrylic Hybrids Using the alkyd dispersions prepared in Example 12, a series of latexes containing alkyd / acrylic hybrids was prepared with different types of FOL groups, different types of levels of the alkyd resins, and acrylic T's different Tg. A general procedure for the preparation of these materials is as follows: To a 500 mL ~ reactor, the appropriate amounts of demineralized water and alkyd dispersion were added. These reactor contents were heated to 80 ° C, at which time an initiator charge consisted of ammonium persulfate 0.22 g in 5.0 g were added to the reactor. A mixture of the monomers, as described in Table 3 below for each sample, was then fed into the reactor over a period of three hours while simultaneously feeding a solution of 0.22 g ammonium persulfate and 0.31 g ammonium carbonate. in 30 g water. Following the addition of all reactor components, 40% solids latex was maintained at 80 ° C for one hour, cooling to room temperature, and filtering.

Table 3 Sample% by weight length of acrylic oil styrene 2BH? monomer3% by weight alkyd1 alkyd T 2 ° C% by weight% by weight acrylic FOLIO 13 35 short 10 46 44 SOUL 10 14 40 short 30 58 32 VMA 10 45 cut 50 70 20 AAEM 10 16 50 short 70 85 15 none - 17 35 rpedia 30 59 31 AAEM 10 18 45 average 70 78 12 SOUL 10 19 35 long 50 75 25 none - 40 long 70 79 1 1 AAEM 10 21 45 long 10 46 44 VMA 10 22 40 average 10 53 47 none ~ 23 50 long 30 58 32 SOUL 10 1% by weight based on the total polymer solids 2 Tg calculated from the Fox-Flory equation 3 ALMA = allyl methacrylate; VMA = vinyl methacrylate; AAEM = acetoacetoxyethyl methacrylate; Example 24: Preparation of the Coating Compositions The latexes of Examples 13-23 were formulated as follows: latex 43.8 g, water 2.7 g, and 3.5 g of a catalyst mixture. This catalyst mixture was comprised of EASTMAN EB 63.2 parts, Cobalt HIDROCURE II 17.7 parts, SURFYNOL 465 6.4 parts, and SURFYNOL 104PA 12.7 g. The samples were allowed to remain overnight, at which time they were applied to the glass at a moisture thickness of 6 thousand. The resulting films were cured under ambient conditions (50% RH and 70 ° F) for 14 days. Half of the total available samples were then baked at 150 ° C for 30 min to affect the last cure. Both of the environmental cure and high temperature films were evaluated for solvent resistance (methyl ethyl ketone or double friction MEK), pendulum hardness, and surface adhesion. The results are presented in Table 4. 1 S short oil alkyd; M - mean oil alkyd; Long oil alkyd ~ measured using a Gardner J Pendulum Hardness Tester determined by steady finger pressure for 10 seconds, evaluations are 0- not releasing; 3-adhesive; 4-lightweight adhesive; 5-without adhesion.

Example 25: Binding Resistance of Examples 13-23 The formulated samples of Examples 13-23 were covered in a oriented polypropylene film (Mobil 100 LBW) with a # 3 RD rod. Another piece of the same film was placed immediately above the coating, and the two films were pressed together for three seconds using a Sentinel Heat Sealer (no heat, 40 psi clutch pressure). The bond strength between the films was measured after 18 hours using an Instron Stress Tester. The results are presented in Table 5. Table 5 Example 26: Bonding Strength of Examples 16-17, 19-20 and 23. The formulated samples of Examples 13-23 (Table 5) which show relatively low adhesiveness bond strengths were tested by extrusion lamination stress. The polypropylene film was covered as described in Example 25 and the coatings allowed to cure for 24 hours. A metallized film covered with polyethylene was then placed on the top film of the polypropylene film with the polyethylene facing the test cover. The two films were then pressed together for three seconds using a Sentinel Heat Sealer (300 F, 40 psi clutch pressure). The bond strength between the films was then measured using an Instron Stress Tester. The results are presented in Table 6. Table 6 Example 27: Latex Compositions The latex compositions added in Table 7 using the average oil alkyd of Example 12 and following the general emulsion polymerization process of Examples 13-23. 1% by weight based on solids of total polymer 2 TCJ calculated from the equation Fox-Flory 3 EHA = 2-ethylhexyl acrylate; ALMA = allyl methacrylate; MAA = methacrylic acid Example 28: Coverage yields The Example of the latex of Example 27 were formulated as follows: 26.4 g latex, 0.9 g water, 0.6 g 80/20 isopropanol / water, and 2.1 g of a mixture of L catalyst. This catalyst mixture was comprised of 63.2 parts of EASTMAN EB, 17.7 parts of Cobalt HIDROCURE II, 6.4 parts of SURFYNOL 465, and 12.7 g SURFYNOL 104PA. The samples were allowed to remain overnight at which time they were applied to the glass in 6 ml of moisture thickness. The resulting films were cured under ambient conditions (50% RH and 70 ° F) for 14 days. These environmental cure films were evaluated by solvent resistance (methyl ethyl ethyl ketone or double MEK frictions) and hardness (pendulum and Tu on). The results are presented in Table 8. Table 8 Comparative Example 1: Paint Formulations Based on Alkyd Dispersions Transported in Water with Modified Acrylic and Alkyd Resins and Commercial Waterborne Acrylics Each paint formulation AD described in, respectively, Tables 9-12, was prepared by mixing of the components with vigorous agitation in the order listed in the corresponding Table. Then, sufficient water was added to each formulation to reduce the formulation viscosity to 25-40 seconds as measured in a Laza # 2 Zahn. The films were melted to give a dry film thickness of 1.3-1.5 mils. These films were cured and tested at constant temperature and humidity (73.5 ° F +/- 3.5 ° F, 50% +/- 5% relative humidity). Table 9. Painting Formulation A Table 10. Paint Formulation B Table 11. Formulation of Paint C Table 12. Paint Formulation D Comparative example 2: Coverage yields Covers based on the paint formulations AD of Comparative Example 1 were evaluated with respect to the properties of drying time, printing resistance, pencil hardness, scratch adhesion, water immersion and specular brightness. The evaluations were conducted according to, respectively, ASTM D1640-83, ASTM D2091-88, ASTM D3363-92A, ASTM D3359-92A, ASTM D870-92, and ASTM D523-89. The results are summarized in Tables 13-16.

Table 13. Print Strength (ASTM D2091- Table 14. Pencil Hardness (ASTM D3363-92A) Table 15. Resistance of hot water after exposure for 2 hours of immersion in 60 ° C water.

Table 16. Drying time, Adhesion of Scratch and Shine. The Adhesion of Scratch and Shine were measured after 14 days of cure in the Environmental Conditions.

Claims (21)

1. CLAIMS 1. An acrylic modified alkyd comprising the polymerization product of at least one ethylenically unsaturated monomer in the presence of an alkyd transported in water having at least one pending sulfonate functionality. 2. alkyd modified acrylic accordance with claim 1, wherein the ethylenically unsaturated monomer is an acrylic monomer of functionality oxidatively latent and modified alkyd with resulting acrylic has sufficient sets of functionality oxidatively latent available to increase the effective crosslinking of the alkylate in the application on a substrate. 3. The acrylic modified alkyd according to claim 2, characterized in that the oxidatively latent functionality group is selected from the group consisting of allyl, vinyl, acetoacetyl and enamine. 4. The acrylic-modified alkyd according to claim 2, wherein the acrylic monomer of latent oxidatively functionality is selected from the group consisting of allyl methacrylate, vinyl methacrylate, acetoacetoxyethyl methacrylate, methacrylate hidroxilbutenilo, maleic acid allyl ester , maleic acid of diallyl ester, and poly (allyl glycidyl ether). 5. The acrylic modified alkyd according to claim 1, characterized in that the ethylenically unsaturated monomer is a mixture of at least one ethylenically unsaturated monomer and at least one acrylic monomer of oxidatively latent functionality. 6. The modified acrylic alkyd according to claim 5, wherein the ethylenically unsaturated monomer is selected from the group consisting of styrene, a-methyl naphthalene, vinyl toluene, vinyl styrene, chloromethyl methyl acrylate, acrylic acid, methacrylic acid, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, ethylhexyl acrylate, ethylhexyl methacrylate, octyl acrylate, octyl methacrylate, glycidyl methacrylate, methacrylate carbodiimide crotonate, alkyd, vinyl acetate maleate, di-n-butyl, dioctyl, metacrilßito t-butylaminoethyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylamide, N, N-dimethylaminopropyl methacrylate, 2-t-butylaminoethyl, N, N-dimethylaminoethyl acrylate, N- (2-methacryloyloxy-ethyl) ethylene urea, and methacrylamidoethylethylene urea 7. The acrylic modified alkyd according to claim 6, characterized in that the ethylenically unsaturated monomer is selected from the group consisting of styrene, α-methyl styrene, vinyl naphthalene, vinyl toluene, and chloromethyl styrene. 8. A water-based latex characterized in that it comprises water and a modified acrylic alkylate because it comprises the polymerization product of at least one ethylenically unsaturated monomer in the presence of an alkyd transported in water having at least one sulfonate functionality outstanding . 9. The latex water-based in accordance with claim 8, wherein the ethylenically unsaturated monomer is an acrylic monomer oxidatively latent functionality and the modified alkyd with resulting acrylic has sufficient sets of functionality oxidatively latent available to increase the effective crosslinking of the alkyd said in the application to a substrate. 10. The water-based latex according to claim 8, characterized in that the acrylic modified alkyd comprises about 5-60. by weight, an alkyd transported in water is based on the total solids of the latex and about 40-95% by weight of the ethylenically unsaturated monomer based on the total solids of the latex. 11. The water-based latex according to claim 8, further characterized in that it comprises a cosurfactant and wherein the alkyd resin carried in water comprises about 5-35% by weight of the total solids of the latex. The water-based latex according to claim 8, characterized in that the oxidatively latent functionality group is selected from the group consisting of allyl, vinyl, acetoacetyl, and enamine. The water-based latex according to claim 8, characterized in that the acrylic monomer of oxidatively latent functionality is selected from the group consisting of allyl methacrylate, vinyl methacrylate, acetoacetoxyethyl methacrylate, hydroxyl-butenyl methacrylate, acid maleic allyl ester, maleic acid diallyl ester, and poly (allyl glycidyl ether). The water-based latex according to claim 8, characterized in that the ethylenically unsaturated monomer is a mixture of at least one ethylenically unsaturated monomer and at least one acrylic monomer of oxidatively latent functionality. 15. The water-based latex according to claim 14, characterized in that the ethylenically unsaturated monomer is selected from the group consisting of styrene, a-methyl styrene, vinyl naphthalene, vinyl toluene, chloromethyl styrene, acrylate methyl, acrylic acid, methacrylic acid, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, ethylhexyl acrylate, ethylhexyl methacrylate, octyl acrylate, methacrylate octyl, glycidyl methacrylate, carbodiimide methacrylate, alkyl crotonate, vinyl acetate, di-n-butyl-maleate, di-octylmaleate, t-butylaminoethyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, methacrylamide of N, N- dimethylaminopropyl, 2-t-butylaminoethyl methacrylate, N, N-dimethylaminoethyl acrylate, N- (2-methacryloyloxy-ethyl) ethylene urea, and methacrylamidoethylethylene urea. 16. The coating composition characterized in that it comprises a water-based latex according to claim 8, and at least one additive selected from the group consisting of rheology and flow control agents, extenders, reactive coalescing aids, plasticizers; crushing agents; moisture of pigment and dispersing agents and surfactants; ultraviolet absorbers (UV); UV light stabilizers; staining pigments; colorants; deformation and anti-formation agents; anti-establishment agents, anti-sinking agents and bodily agents; anti-skinning agents; anti-sinking and anti-flotation agents; biocides, fungicides and mildiucides; corrosion inhibitors; thickening agents; and coalescence agents. 17. A method of preparing a water-based latex comprising the polymerization step of at least one ethylenically unsaturated monomer in the presence of an alkyd carried in water having at least one pending sulfonate functionality. 18. The method according to the claim, 17, characterized in that it further comprises the step of polymerizing at least one acrylic monomer of oxidative functionality in the presence of an aqueous dispersion of an alkyd transported in water having at least one sulfonate functionality pending under conditions sufficient for the survival of the latent oxidative functionality of the acrylic monomer. 19. The method according to claim 18, characterized in that the oxidatively latent functionality group is selected from the group consisting of allyl, vinyl, acetoacetyl, and enamine. 20. The method of compliance with the claim 18, characterized in that the acrylic monomer of oxidatively latent functionality is selected from the group consisting of allyl methacrylate, vinyl methacrylate, acetylacetoxyethyl methacrylate, hydroxylobutenyl methacrylate, maleic allyl ester of maleic acid, a diallyl ester of maleic acid, and poly ( allyl glycidyl ether 21. The method according to claim 17, characterized in that the polymerization is a polymerization of the emulsion.