MXPA00011144A - Protonated amines for controlled crosslinking of latex polymers - Google Patents

Abstract

The latex polymer compositions of the present invention exhibit latent crosslinking properties. Latent crosslinking in the polymers takes advantage of the fast reaction that occurs between amine-reactive carbonyl groups in the polymer component and carbonyl-reactive amine nitrogens in the crosslinking component, but controls the rate of crosslinking by protonating the amines with a volatile acid. Once the latex is coated onto a substrate, the volatile acid evaporates and the carbonyl reactive amine nitrogens react with the amine reactive carbonyl groups to form a crosslinked coating.

Description

AMEBAS PROTONADAS FOR THE RETICULATION OF LATEX POLYES DESCRIPTION OF THE INVENTION This invention belongs to the field of emulsion chemistry. In particular, it relates to latex polymer compositions containing protonated amines for the controlled crosslinking. Latexes are useful in a variety of coating formulations. In a growing number of industries, aqueous coating compositions continue to replace traditional coating compositions based on organic solvents. Aqueous compositions are now formulated with paints, inks, sealants, and adhesives, for example, previously formulated with organic solvents. This reduces the potentially harmful exposure to volatile organic compounds (VOCs) commonly found in solvent-based compositions. While the movement of compositions based on organic to aqueous solvents 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 an offset on the characteristics and properties of the waterborne polymer compositions used in the aqueous coating compositions.

Waterborne polymers having various functional groups have been used to impart and achieve desired properties in a particular coating composition. For example, a coating composition must have good film formation, resistance to printing and blocking, as well as adhesion and tension properties. Polymers having acetoacetyl functional groups represent an example of waterborne polymers having such properties, they can carry different functional groups, and they are used in aqueous coating compositions. The latex industry has long had a goal to develop cross-linking systems of an effective package. The ideal system would allow the formation of films before a substantial cross-linking takes place. This type of chemistry must be non-reactive (or very slow to react) in the wet state but very reactive (at room temperature) in the dry state; hereinafter referred to as latent lattice. The result of the latent reticulation would be a latex of good film formation with excellent strength and solvent hardness. Several patents have been granted on various chemistries in a package, including many based on epoxides (glycidyl methacrylate), silanes, isocyanates, and carbonyls (including acetoxyethyl methacrylate, AAEM). Most of these patents have indicated the presence of crosslinking by demonstrating improved solvent resistance. However, the same results could be expected if the reaction takes place in the wet state prior to film formation, and there is no reason to believe that these systems react through the latent lattice. To increase the time to harden within the container of the compositions containing acetoacetate and amine groups it has been proposed to block the amine groups of the polyamine with a ketone or aldehyde to form the corresponding compounds of ketimine or aldimine before mixing them with a functional polymer of acetoacetate. Examples of such non-aqueous compositions are described in US Patent No. , 772, 680. Although improved stability can be achieved by specific aromatic aldimines, volatile by-products are still formed and the compositions have no application in waterborne coatings and are restricted to coatings that use organic solvents as the carrier. WO 95/09209 discloses a crosslinked coating composition comprising a dispersion forming aqueous film of addition polymer comprising acetoacetate functional groups and an essentially non-volatile polyamine having at least two primary amine groups and wherein the mol ratio of acetoacetate to primary amine groups is between 1: 4 to 40: 1. The EP 555, 774 and WO 96/16998 describe the use of carboxylated latexes of acetoacetoxyethyl methacrylate mixed with multifunctional amines (such as diethylenetriamine) for a stable one-component system on the shelf. In EP 555,774, the system is stabilized using vinyl acid polymerized with AAEM and the latex is "neutralized" with a polyamine. The patent teaches that the carboxyl groups should be 70 to 96 mol% relative to the acetoacetoxy groups. WO 96/16998 similarly describes a polymerization process with vinyl acid and AAEM being polymerized in the first stage. EP 744,450 discloses aqueous coating compositions containing acetoacetate functional polymers with an average molecular weight of 100,000 or greater and which contains functional acetoacetate groups and acid functional groups, and multifunctional amine. EP 778,317 discloses an aqueous self-crosslinked polymer dispersion comprising a polymer component (a relatively hydrophobic polymer having a Hansch number.1.5, at least 5% of the functional carbanyl groups capable of reacting with a nitrogen portion, and at least 1% of the non-acid functional group having hydrogen-bondable portions); and a crosslinking agent comprising a nitrogen-containing compound having at least two functional nitrogen groups capable of reacting as a functional carbonyl moiety. Again it is reported that gelation has not taken place after 10 days at 60 ° C. U.S. Patent 5,498,659 discloses a single pack aqueous polymer formulation consisting essentially of an evaporable aqueous carrier, at least one polymer ingredient having functional acidic slopes capable of forming stable enamine structures, a polyfunctional nonpolymeric amine having at least two aminofunctional portions, and an effective amount of base to inhibit gelation. It is stated in the patent that at least some of the crosslinking of the composition can take place in the liquid phase, possibly within one to four hours of adding the polyfunctional nonpolymeric amine. It is postulated that the addition of base to the contents of the reactor competes with the amino functional portions in the presence of acetoacetoxy-like functional portions, thereby reducing the degree of crosslinking and / or increasing the colloidal stability of the polymer dispersion that is formed when the crosslinking reaction takes place. Geurink, et al., "Analytical Aspects and Film Properties of Two-Pack Acetoacetate Functional Latexes", Progress in Organic Coatings 27 (1996) 73-78, reports that the crosslinking of functional acetoacetate latexes with polyamine compounds is very rapid, and that this crosslinking is hardly prevented by the existing enamines. It is further established that there are very strong indications that the crosslinking takes place rapidly in the wet state, at or to the surface of the particles just after mixing the components. They conclude that as a result of the crosslinking in the particles, the process that forms the film is impeded. In the patents and articles described above, the time to harden within the useful container of the latex formulations is demonstrated by the lack of gel formation. It is quite possible, however, that the crosslinking is taking place within each particle without causing the latex or gel to coagulate (e.g. loss of colloidal stability). This type of intraparticle crosslinking (before drying) limits the capacity of the latex to form a film on drying. This in turn reduces the integrity of the film and the operation of the polymer. Therefore, there is still a need for true latent lattice systems to those in which the intraparticle lattice is inhibited until after the formation of the film. In particular, there is a need for latent lattice systems of a package that is useful in a wide range of latex applications. These would include decorative and protective coatings, adhesives, non-woven binders, textiles, paper coatings, grooves, etc. In each case, the advantage would be a soft, ductile polymer that becomes a harder resistant latex film after drying. The present invention relates to latex polymer compositions containing a polymer component having amine-reactive carbonyl groups, a cross-linked component having carbonyl reactive amine nitrogens capable of protonation by an acid, and an acidic volatile component . The latex polymer compositions of the present invention exhibit latent crosslinking properties. The latent lattice in the polymer takes advantage of the rapid reaction occurring between the amine-reactive carbonyl groups in the polymer component and the carbonyl-reactive amine nitrogens in the component that is recirculated, but controls the rate of crosslinking by protonating them. amines with volatile acid. Once the latex is coated on a substrate, the volatile acid evaporates and the nitrogens of. amine reactive with carbonyl react with the reactive amine carbonyl groups to form a crosslinked coating.

The invention further relates to a method for making a latent crosslinked polymer composition by polymerizing a vinyl monomer having amine reactive carbonyl groups to form a polymer; adding a crosslinking agent having at least two amine nitrogens reactive with carbonyl capable of being protonated by an acid, and adding a volatile acid. In another embodiment, invention relates to a crosslinked coating of the polymer composition described above. The present invention provides latex polymer compositions. The latex polymer compositions of the present invention typically include, but are not limited to, latexes, dispersions, microemulsions, or suspensions. The latex polymer compositions of the present invention can be stored at room temperature moderately above room temperature (eg, about 50 to 60 ° C) and provide adhesion and crosslinking in film formation when applied to a substrate. A film or coating formed with the polymers of the present invention can be cured at room temperature (ambient cure) or at elevated temperature (thermal cure). The polymers used to prepare the waterborne polymer composition of the present invention are generally prepared as particles. The particles can be structures or non-structures. The particle structures include, but are not limited to, core / shell particles and gradient particles. The average particle size of the polymer can vary from about 25 to about 600 mm. The polymer particles generally have a spherical shape. In one embodiment, the spherical polymer particle can generally have a core portion and a cover portion. The core / shell polymer particles can also be prepared in a multi-lobed, peanut-shell, acorn-shaped, or raspberry-shaped form. It is further preferred in such particles that the core portion comprises about 20 to about 80 of the total weight of the particle and the shell portion comprises about 80 total weight of the particle and the shell portion comprises about 80 to about 20"of the total weight of the particle. weight of total particle volume Component of ~ Polymer Polymers having repeating units of amine-reactive carbonyl groups represent a type of polymer useful in the practice of the invention Examples of amine-reactive carbonyl functional groups include, but are not limited to ethylenically unsaturated monomers, ketone or functional aldehydes such as acetoacetyl type monomers, diacetone acrylamide, (meth) acryloxyalkylbenzophenone, (meth) acrolein, croton-aldehyde, 2-butanone (meth) acrylate and the like and mixtures of A preferred class of amine-reactive carbonyl groups are those which They have acetoacetyl functionality. Although other amine-reactive carbonyl functional groups can be used, the following description will be limited to a discussion of acetoacetyl functional polymers for simplicity. The term (meth) acrylate as used throughout the specification includes acrylates and methacrylates. Polymers having repeating units derived from acetoacetyl functional groups can be prepared by free radical emulsion polymerization of vinyl monomers having an acetoacetyl functionality, such as those of Formula (I) below, alone or with other vinyl monomers. This monomer combination provides the water-based dispersion of polymer particles wherein the polymer has outstanding acetoacetyl groups. As used herein, a "vinyl" monomer is an ethylenically unsaturated monomer. An outstanding acetoacetyl group is not strictly limited to those at the end of the polymer. The pendant acetoacetyl groups also include groups attached to the backbone of the polymer and are available for further reaction. Acetoacetyl functional monomers may be represented as shown in Formula (I): R 1 -CH = C (R 2) C (0) -X 1 -X 2 -X 3 -C 0) -CH 2 -C (0) -RJ (I ) For an acetoacetyl type monomer of Formula (I) R1 is a hydrogen or halogen, R2 is hydrogen, halogen, alkylthio group of C? -C6. R3 is an alkyl group of C! -C6. X1 and X3 are independently O, S, or a group of the formula -N (RT) - / where R 'is an alkyl group of C? -C6. X2 is an alkylene group of C2-C12 or a cycloalkylene group of C3-C12. The alkyl and alkylene groups described herein and throughout the specification may be linear or branched groups. Preferred monomers of formula (I) are acetoacetoxy-ethyl (meth) acrylate, acetoacetoxymethylethyl (meth) acrylate, allylacetoacetate, acetoacetamido-ethyl-meth) acrylate, acetoacetoxybutyl (meth) acrylate, acetoacetoxyethyl (meth) acrylamide, acetoacetamido (meth) ) acrylamide, and mixtures thereof. Acetoacetoxyethyl methacrylate (AAEM) represents a particularly preferred monomer of Formula (I). Other suitable vinyl monomers that can be reacted with the vinyl monomers have acetoacetyl functionality include, but are not limited to, methyl (meth) acrylate; ethyl (meth) acrylate; butyl (meth) acrylate; isobutyl (meth) acrylate; ethylhexyl (meth) acrylate; octyl (meth) -acrylate; styrene; α-methylstyrene; glycidyl methacrylate; carbodiimide (meth) acrylate; U-Ciß alkyl crotonates; di-n-butylmaleate; dioctylmaleate; allyl (meth) acrylate; di-allylmaleate; di-allylmalonate; methoxybutenyl (meth) acrylate; isobornyl (meth) acrylate; hydroxybutenyl (meth) acrylate; hydroxymethyl (meth) acrylate; hydroxypropyl (meth) acrylate; acrylonitrile; vinyl chloride; ethylene; (meth) acrylamide; butyl (meth) acrylamide; ethyl (meth) acrylamide; vinyl (meth) acrylamide; isopropenyl (meth) acrylate; cycloaliphatic epoxy (meth) acrylates; and ethylformamide. Such monomers are described in "The Brandon Wordwide Monomer Reference Guide and Sourcebook" Second Edition, 1992, Brandon Associates, Merrimack, New Hampshire; and in "Polymers and Monomers," the 1996-1997 Catalog from Polyscience, Inc., Warrington, Pennsylvania. The vinyl esters of Formula (II) represent additional examples of other useful vinyl monomers: RCH = CH-0-C (0) -C (R) 3 (II) In Formula (II), R is independently hydrogen or an alkyl group of up to 12 carbon atoms. Particular monomers of formula (II) include. CH2 = CH-0-C (O) -CH3, CH2 = CH-0-0) -C (CH3) 3, CH2 = CH-0-C (0) - (C2H5) (C4H9), and CH2 = CH -0-C (O) -CH2-CH3. The vinyl ester monomers also include vinyl alcohol vinyl esters such as the VEOVA series available from Shell Chemical Company as VEOVA 5, VEOVA 9, VEOVA 10 and VEOVA 11 products. See O.W. M.J. Collins, P.S. Martin and D.R. Bassett, Prog Org. Coatings 22, 19 (1993). Optional monomers that can be incorporated into the polymer include methylstyrene, vinyltoluene, (meth) acrylonitrile, vinyl acetate, and vinyl esters of acids other than acetic acid, itaconic anhydride, maleic anhydride, vinyl formate, and 2-sulfoethyl (meth) acrylate salts . In one embodiment, the functional acetoacetyl polymer can also incorporate vinyl monomers containing nitrogen, known to promote wet adhesion. Examples of moisture adhesion monomers include, for example, t-butylaminoethyl methacrylate; dimethylaminoethylmethacrylate; diethylaminoethyl methacrylate; N, N-dimethylaminopropylmethacrylate; 2-t-butylaminoethyl methacrylate; N, N-dimethylaminoethylacrylate; . N- (2-methacrylamido-ethyl) ethylene urea; and N- (2-methacryloyloxy-ethyl) ethylene urea. The N- (2-methacryloyloxyethyl) ethylene urea is available from RohmTech as a 50% solution in water under the tradename Rohamere 6852-0 and as a 25% solution in water under the tradename Rohamere 6844. The urea N- (2-methacrylamidoethyl) ethylene is available from Rhone-Poulenc under the trade name WAM. Small amounts of acidic vinyl monomers can also be used to prepare acetoacetoxy emulsion polymers according to the invention. Such acid vinyl monomers include, for example, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, tiglic acid, maleic acid, fumaric acid, and 2-acrylamido-2-methyl-1-propanesulfonic acid (sodium, potassium, or ammonium salts). Generally these monomers are used in small amounts. Preferably, the amount of acidic vinyl monomers may vary, for example from 0 to 5 phr. Larger amounts of acidic vinyl monomers can be used to achieve a desired effect, such as increased viscosity. Functional acetoacetyl type polymers preferably contain about 0.5 to about 99.5% by weight of vinyl monomers having acetoacetyl functionality such as those of Formula (I), and about 99.5 to about 0.05 weight percent of other vinyl monomers, preferably alkyl (meth) acrylates having 1 to 18 carbons. Acetoacetyl functional polymers are also useful as 100 percent of the polymer composition. The weight percentage is based on the total amount of monomers in the composition. More preferably, the functional acetoacetyl polymer has about 10 to about 50 weight percent acetoacetyl monomers, and about 90 to about 50 weight percent other vinyl monomers The acetoacetyl functional polymers of the present invention can be prepared using Emulsion polymerization known in the art Acetoacetyl polymer can be prepared using free radical emulsion polymerization techniques which produce structured or unstructured particles As discussed above, the structured particles include, for example, core / shell particles, particles Raspberry, and gradient particles Chain transfer agents, initiators, reducing agents, catalysts, and surfactants known in the emulsion polymerization art can be used to prepare the polymers. optionally added, in an amount of about 5 weight percent based on the total monomer content, to control the molecular weight of the polymer. The use of chain transfer agents can be preferred when it is desired to obtain low molecular weight polymers. Examples of chain transfer agents are butylmercaptan, mercaptopropionic acid, 2-ethylhexyl mercaptopropionate, dodecyl mercaptran, n-butylmercaptopropionate, octylmercaptan, isodecyl ercaptan, octadecyl mercaptan, mercaptoacetic acid, allylmercaptopropionate, allylmercaptoacetate, propylmercaptopropionate, crotylmercaptoacetate, and blood transfer agents. Reactive chain taught in U.S. Patent No. 5,247,040, incorporated herein by reference. Typical initiators include hydrogen peroxide, sodium, potassium or ammonium peroxodisulfate, dibenzoyl peroxide, lauryl peroxide, di-tertiary butylperoxide, 2,2'-azobisisobutyronitrile, t-butylhydroxyperoxide, benzoyl peroxide, and the like. Suitable reducing agents are those which increase the polymerization rate and include, for example, sodium bisulfite, sodium hydrosulfite, sodium formaldehyde sulfoxylate, ascorbic acid, isoascorbic acid, and mixtures thereof. Polymerization catalysts are those compounds that increase the polymerization rate and which, in combination with the reducing agents described above, can promote the decomposition of the polymerization initiator under the reaction conditions. Suitable catalysts include transition metal compounds such as, for example, ferrous sulfate heptahydrate, ferrous chloride, cupric sulfate, cupric chloride, cobalt acetate, cobaltous sulfate, and mixtures thereof. Redox peroxide, sulfite and peroxide-iron catalysts can also be used.

The crosslinked agents may optionally be added, in an amount of about 2 weight percent, based on the total monomer content, to control the molecular weight of the polymer. The use of crosslinking agents may be preferred when it is desired to obtain high molecular weight polymers. Useful crosslinkers include trimethylolpropane tri (meth) acrylate, 1,6-hexanediol di (meth) acrylate, allyl methacrylate and the like. Any convention polymerization surfactant can be used to form the polymers of the present invention. The use of surfactants includes, but is not limited to, ionic and nonionic surfactants such as alkyl polyglycol ethers; alkylphenol polyglycol ethers; alkali metal salts of alkyl ammonium, aryl or alkylarylsulfonates, sulfates, complex ester acids of organic phosphates, phosphates, and the like, and reactive anionic or nonionic surfactants having styrene or allyl groups. Surfactants containing sulfonates such as dodecyl diphenyloxide. Sodium disulfonate, sodium dodecylbenzenesulfonate, sodium dodecyl sulfate, and the diesters of sodium sulfosuccinic acid such as sodium dioctyl sulfosuccinate, and alpha olefin sulphonates, and the like, are suitable. When the persulfate catalysts are used, the oligomers generated in situ with terminal sulfate groups can also act as surfactants.

The type and amount of surfactant used in the polymerization process depends on the specific composition, reaction conditions, and the desired final particle size, as is known in the art. Water-dispersible and water-soluble polymers can also be employed as surfactants / stabilizers in the water-based latexes of the invention. Examples of such polymer stabilizers include water dispersible polyesters as described in U.S. Patent No. 4,946,932 and 4,939,233; water dispersible polyurethanes as described in U.S. Patent Nos. 4,927,876 and 5,137,961; alkali-soluble acrylic resins as described in U.S. Patent No. 4,839,413; and hydroxyethylcellulose, as described in U.S. Patent No. 3,876,596 and British Patent 1,155,275. Crosslinking Component The crosslinking component in the present invention can be any nitrogen-containing compound having at least two amine nitrogens reactive with carbonyl group. Such compounds can be aliphatic or aromatic, polymeric or non-polymeric, and can be used alone or in combination. The carbonyl reactive amines useful in the practice of the invention include polyfunctional amines, hydrazine, alkyldihydrazines, alkylene diols and dihydrazides of dicarboxylic acids. Preferably, the amines reactive with carbonyl are polyfunctional amines having at least two primary amine groups capable of being protonated by an acid. Preferred amines include, but are not limited to, ethylenediamine, propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehaxamine, polyethyleneimine, polypropyleneimine, ethylene or propylene oxide adducts (eg, triethyleneglycoldiamine or JEFFAMINES®), cyclohexane diamine. , xylylenediamine, inotrimethylcyclohexanamine, 2,2,4-trimethylhexandiamine, 2,2-dimethylpropanediamine, triaminonone-no, triaminoethylamine, diaminoethanolamine, diaminomethylcyclohexane and mixtures thereof. Volatile Acid Compound The volatile acids useful in the practice of the present invention can be defined as organic acids having a boiling point of less than 250 ° C. Useful volatile acids include carboxylic acids, such as formic, acetic, propionic, butanoic, pentanoic, hexanoic, heptanoic, snoenoic and their respective isomers; cyclohexane and benzoic; carbonic acid; carbonate and bicarbonate salts such as carbonate or aminium or sodium bicarbonate; and mixtures thereof. The carbonic acid can be provided in the form of gas, solid (for example dry ice) or a salt that releases carbon dioxide gas. The preferred volatile acids are carbonic acid (carbon dioxide) and acetic acid. Method for Making a Latent Cross-linked Polymer The order for mixing the above-described components of the latex polymer composition can vary. In some cases, it may be easier to mix the acetoacetylfunctional latex polymer with a volatile acid component before adding the crosslinking amine. In other cases, such as when CO 2 is used, the amine and CO 2 can be mixed first to form an amine salt and then added to the functional acetoacetyl latex polymer. The addition of the acid or the acid salt of the amine may, in some cases, cause coagulation or gelation of the latex. In those cases, additional stability can be provided by adding surfactants, preferably nonionic surfactants, stabilizing comonomers, preferably acrylamide. It is believed that the stabilization when using acrylamide monomers is due to the formation of a water soluble polymer layer around the particles of latex which increases stability. The level of functional acetoacetoxy polymer in the latex polymer composition can vary from about 0.5 to 100%. The amount of carbonyl reactive amine is typically present at about 0.5 to about 1.5 molar equivalent to the acetoacetoxy groups present in the polymer. The level of volatile acid must be sufficient to protonate a significant fraction of the amine and is typically present at about 0.5 to about 1.5 equivalents of the amine level. The latex polymer compositions of the present invention may vary in properties, depending on the end use application. In general, the polymer component can have a second cycle of glass transition temperature (Tg) of -50 to + 100 ° C, more preferably -20 to + 50 ° C. However, the final cross-linked latex polymer composition can have a Tg of up to about 150 ° C. The average molecular weight weight of the latex polymer compositions may vary from about 5,000 to 5,000,000 daltons; more preferably from 20,000 to 2,000,000 and more preferably from 50,000 to 1,000,000. Molecular weight variation can be controlled by the reaction conditions, as is known in the art, or by the use of a chain transfer agent or lattice, as discussed above. Since the polymers of the present invention become highly crosslinked upon drying, there is no substantial disadvantage in starting with low molecular weight polymers. Low molecular weight polymers can offer advantages in film formation and in the interdiffusion of the polymer chain. The method for making a latent crosslinked polymer using the method of the present invention may have application in other chemistries that are using crosslinking amines. Such systems include, but are not limited to epoxide (glycidyl methacrylate), silanes, isocyanates, and other carbonyls. A polymer composition carried in water can be prepared using the latex polymer composition of the present invention together with other known additives and can use another emulsion polymerization methodology. U.S. Patent No. 5,371,148 provides a good description of the possible additives and is incorporated herein by reference. The following examples illustrate the preparation of latex polymers and polymer compositions carried in water according to the invention. Latexes or other waterborne compositions containing polymers of small particle size, those ranging from about 25 to about 700 mm, preferably from about 50 to about 500 mm and more preferably from about 75 to about 300 mm, represent a mode preferred of the invention.

The polymers and waterborne polymer compositions of the invention are used in a variety of coating formulations such as architectural coatings, metal coatings, wood coatings, plastic coatings, textile coatings, similar coatings, paper coatings, inks. , and adhesives. Examples of such coating formulations adapted for particular uses include, but are not limited to, corrosion inhibitors, concrete coatings, maintenance coatings, latex paints, industrial coatings, automotive coatings, textile undercoats, surface printing inks and laminating inks. . Accordingly, the present invention relates to such coating formulations containing a water-borne polymer composition of the invention, preferably a water-based latex. The polymers and waterborne polymer compositions of the invention can be incorporated in those coating formulations in the same way to the known polymer latexes and are used with the conventional components and / or additives of such compositions. The coating formulations may be clear or pigmented. With their crosslinking ability, adhesion properties, and strength properties, the water-based latexes of the invention impart new and / or improved properties to the various coating formulations. Under formulation, a coating formulation containing a latex polymer or a waterborne polymer composition of the invention can then be applied to a variety of surfaces, substrates, or articles, eg, paper, plastic, steel, aluminum, wood, gypsum slabs. , concrete, brick, masonry, or galvanized coating (primed or unprimed). The type of surface, substrate or article to be coated generally determines the type of coating formulation used. The coating formulation can be applied using means known in the art. For example, a coating formulation can be applied by spraying or coating a substrate. In general, the coating can be dried by heating but preferably dried in air. Advantageously, a coating employing a polymer of the invention can be cured thermally or environmentally. As a further aspect, the present invention relates to a shaped or shaped article which has been cured with coating formulations of the present invention. A polymer composition carried in water according to the invention may additionally comprise water, together with a solvent, a pigment (organic or inorganic) and / or other additives and fillers known in the art, and listed below. When a solvent is used, water-miscible solvents are preferred. A latex paint composition of the invention may comprise a waterborne polymer composition of the invention, a pigment and one or more additives or fillers used in latex paints. The additives or fillers used in the coating formulations include, but are not limited to, leveling agents, rheology and flow control, such as silicones, fluorocarbons, urethanes, or cellulosics; extenders; curing agents such as multifunctional isocyanates, multifunctional carbonates, multifunctional epoxides or multifunctional acrylates; reactive coalescent auxiliaries such as those described in U.S. Patent No. 5,349,026; varnishes; pigments, wetting and dispersing agents and surfactants; ultraviolet (UV) absorbers; UV light stabilizers; coloring pigments; extenders; defoaming and defoaming agents; anti-sedimentation, anticorrosion and incorporation agents; anti-skid agents; anti-flood and anti-flotation agents; mohesides and fungicide; corrosion inhibitors; thickening agents; plasticizers; reactive plasticizers; drying agents; catalysts; crosslinking agents; or coalescing agents. Specific examples of such adhesives can be found in Raw Materials Index, published by National Paint & Coatings Association, 1500 Rhode Island Avenue, NW, Washigton, D.C. 20005. A polymer or waterborne polymer composition of the present invention may be used alone or in conjunction with other conventional waterborne polymers. Such polymers include, but are not limited to, water-dispersible polymers such as those consisting of polyesters, polyester-amides, cellulose esters, alkyds, polyurethanes, epoxies, polyamides, acrylics, vinyl polymers, polymers having allyl groups pendant such as those described in U.S. Patent No. 5,539,073, styrene-butadiene polymers, vinylacetate-ethylene copolymers, and the like. The following examples are intended to illustrate, without limiting the invention: EXAMPLES Methods of Test MEK rubs An aluminum test panel was coated with latex to give a dry film of 1 mil. The sky blanket was secured on the round head of a 16 - QZ ball point hammer. The hammer is attached to a mechanical device, which moves the hammer back and forth when in operation. The machine was equipped with a counter. The sky blanket was saturated with methyl ethyl ketone (MEK), and each panel is rubbed with the soaked cloth until the film is removed from the central portion of the substrate. The values reported are the number of "double rubs" or passes back and forth through the film. Pendulum Hardness A glass test panel was coated with latex to give a dry film of 2-3 mil. The hardness of each sample was measured using a Gardner Pendulum Hardness Tester. The sample is placed under the pendulum of the instrument. The pendulum swings back and forth. The movement of the pendulum is damped by the film. The harder, the longer the pendulum swings. The values reported are the number of pendulum swings. Glass Transition Temperature (Tg) The glass transition temperatures (Tg) were measured using a DuPont 2200 differential scanning calorimeter with a heating rate of 20 ° C / min. The reported value is the midpoint of Tg. Water Absorbance Samples were prepared by melting a 4 mil wet film on a pre-weighted aluminum panel. The films were then dried and reweighed to determine the dry weight of the polymer. The plates were immersed in water for 24 hours, then dried and reweighed. The weight gained after soaking divided by the dry weight of the polymer provides the weight percent gain. Fraction Film Gel (FGF) and Film Swelling Ratio (FSR): The dried film was removed from a glass panel with a shaving blade, weighed (original film weight ~ 0.5 g), and placed in a 200 ml glass jar. The jar was filled with tetrahydrofuran (THF) (~ 100g), then placed on a shaker for ~ 24 hours. After 24 hours, the THF / film was filtered through a preweighed piece of 100 mesh metal wire screen. The metal mesh containing the wet film was bent and shaken to remove all excess THF. The mesh / film wire is then weighed immediately (wet film weight). The wire / film mesh was placed in a forced air oven at 80 ° C for 6 hours to dryness. Once dry, the samples were removed, allowed to cool to room temperature, and the wire / film mesh was weighted (dry film weight), the "swelling index was calculated by the following equation: (weight of wet film - sieve) / (dry film weight - sieve weight) The "% Gel" was calculated by the following equation: (dry film weight - sieve weight) / original film weight x 100. Hardness of Tukon A glass test panel was coated with latex to give a film of 2-3 mil. The hardness of each sample was measured using a Wilson®Tukon® Series 200 instrument. The hardness was determined by the size of an indentation made by a probe pressing on the film under a fixed load. The reported values are in units of knoops. Minimum Resistance Temperature for Film Formation: The minimum resistance temperature for forming film (MFFT resistance) was determined by melting a wet latex film with a 1-mil applicator cube on a MFFT bar set at a temperature range in which the film coalesces during drying, pushing the end of a bronze spatula blade through the film from the cold end to the hot end on the MFFT bar after 30 minutes and recording the temperature at which the film offers significant resistance to the spatula. Surfactants The surfactant Tergitol® 15-S-40, available from Union Carbide, is a secondary alcohol of C11-C15 ethoxylated with an HLB of 18.0. The Rhodofac®-610 surfactant, available from Rhone-Poulenc, is an acid of an organic phosphate complex ester. The Dowfax®2Al surfactant, available from Dow Chemical, is a sodium dodecyldiphenyloxide disulfonate. The Igepal® C0887 surfactant, available from Rhone-Poulenc, is a nonylphenol ethoxylated with an HLB of 17.2.

Polyester Seed Létex The water dispersible polyester resin containing a sulfonate group used in the latex synthesis examples is described in US Patent No. 4,946,932, incorporated herein by reference. Synthesis of Carbonate Salts The carbonate salts of the multifunctional amines were prepared by adding excess solid carbon dioxide (dry ice) to 25% aqueous solutions of the amines with stirring until no additional carbon dioxide was consumed (i.e. constant weight). For example, 50.0 g of triethylene glycol diamine was dissolved in 150 g of deionized water. Dry ice was added with stirring for a period of 1 hour, resulting in a total weight gain of 11.5 g and a pH of 8.6. Example 1 - Latex Synthesis Within a 2-liter, 3-neck glass reactor equipped with a stirrer, a reflux condenser and a nitrogen inlet was charged to a solution consisting of 616.6 g of deionized water and 12.8 g of a dispersion of polyester in 33% water. An aqueous solution containing 4.2 g of ammonium persulfate and 28.2 g of surfactant (a 15% solution of the ammonium salt of Rhodafac® RE-610) was prepared in 73.9 g of deionized water. A monomer mixture containing 275.3 g of butyl acrylate, 262.6 g of methyl methacrylate, 296.5 g of acetoacetoxyethyl methacrylate, and 4.2 g of 2-ethylhexyl-3-mercaptopropionate was prepared. An aqueous monomer mixture containing 25.4 g of 50% acrylamide was made in 200.1 g of deionized water. After the reactor charge was heated to 82 ° C under a nitrogen atmosphere, the aqueous and monomer mixtures were pumped into the reactor. The aqueous solution was added at a rate of 0.39 g / min for 270 min. The monomer mixture was added at a rate of 0.93 g / min for 45 min and then at 3.49 g / min for 225 min. The aqueous acrylamide mixture was added at a rate of 0.25 g / min for 45 min then at 0.95 g / min for 225 minutes. After completing the salinizations, the reactor was maintained at 82 ° C for 1 hour, then cooled to room temperature. The product was a latex polymer having a pH of 2.6, a solids content of 46.8%, a solids content of 46.8%, a particle size of 95 nm, and a glass transition temperature (Tg) of 20.1 ° C. Example 2 50 gram portions of the above latexes were formulated with 2.0 g of Tergitol® 15-S-40 surfactant (35% active9, then with diamine acid as shown in Table 1.

* Control ** Ethylenediamine In samples # 2-6, ethylenediamine (EDA) was an equivalent to AAEM. In samples 3, 4, and 6, the acid is equivalent to the amine. In sample 5, the acid is 0.5 equivalent to the amine. Table 2 shows that samples 3-6 have better made film properties than comparative # 1 which includes higher Tg, lower swelling index, and higher hardness. This indicates extensive reticulation. Samples 3-6 also have a film formation temperature much lower than control # 2. This suggests that the # 2 crosslinking occurs undesirably in the wet state (prior to film formation), while the crosslinked 3-6 occurs after the formation of the film.

? ? ** Tg measured by DSC after drying at 22 * C for one week *** Solvent Dilution Index and Gel Percentage in THF films, drying at 22 ° C, 2 hrs, before testing **** Sample # 2 Control does not form a film Example 3 - Latex Synthesis A solution consisting of 533 g of deionized water and 7.7 g of a dispersion was charged into a 2-liter 3-neck glass reactor equipped with a stirrer, a reflux condenser and a nitrogen inlet. of polyester in 33% water. An aqueous solution containing 4.6 g of ammonium persulfate and 30.8 g of surfactant (a 15% solution of the ammonium salt of Rhodafac® RE-610) was prepared in 68.3 g of deionized water. A monomer mixture containing 300.4 g of butyl acrylate was prepared, 286.6 g of methyl methacrylate, and 323.6 g of acetoacetoxyethyl methacrylate. An aqueous monomer mixture containing 27.7 g of 50% aqueous acrylamide in 217.2 g of deionized water was made. After the reactor charge was heated to 82 ° C under a nitrogen atmosphere, the aqueous and monomer mixtures were pumped into the reactor. The aqueous solution was added at a rate of 0.38 g / min for 270 min. The monomer mixture was added at a rate of 1.01 g / min for 45 minutes then at 3.84 g / min for 225 min. The aqueous acrylamide mixture was added at a rate of 0.27 g / min for 45 min, then at 1.03 g / min for 225 min. After completing the feeds, the reactor was maintained at 82 ° C for 1 hour, then cooled to room temperature. The product was a latex polymer having a pH of 2.7, a solids content of 50.8%, a particle size of 167 nm, and a glass transition temperature (Tg) of 22.2 ° C. Example 4 Portions of 50 grams of the above latex were formulated 1.4 g of Tergitol® 15-S-40 surfactant (35% solution in water), then with diamine acid as shown in Table 3.

Table 3. Amounts of amine salts added In samples 8-10 the amine is an equivalent to the AAEM. Again, they achieved excellent film properties for samples 8-10, using 3 different amines as shown in Table 4.

Soaking 24 hours in water Example 5 - Latex synthesis In a 3-liter 2-liter glass reactor, equipped with a stirrer, a reflux condenser and a nitrogen inlet, a solution consisting of 860.11 g of deionized water and 12.5 g of a dispersion in water of 33% polyester. An aqueous solution containing 4.1 g of sodium persulfate, 1.7 g of sodium bicarbonate and 18.4 g of surfactant (a 45% solution of Dowfax® 2A1) was prepared in 75.4 g of deionized water. A monomer mixture was prepared containing 413.9 g of butylacrylate, 393.2 g of methyl methacrylate, and 20.7 g of acetoacetoxyethyl ethyl methacrylate. An aqueous monomer mixture containing 25.4 g of 50% aqueous acrylamide in 200.1 g of deionized water was made. After the reactor charge was heated to 82 ° C under a nitrogen atmosphere, the aqueous and monomer mixtures were pumped into the reactor. The aqueous solution was added at a rate of 0.37 g / min for 270 min. The monomer mixture was added at a rate of 0.92 g / min for 45 min then at 3.49 g / min for 225 min. After completing the feeds, the reactor was maintained at 82 ° C for 1 hour, then cooled to room temperature. The product was a latex polymer having a pH of 6.8, a solids content of 46.7%, a particle size of 110 mm and a glass transition temperature (Tg) of 17. 6C . Example 6 Portions of 50 grams of latex were formulated with 3. 9 g of Igepal® C0887 surfactant (30% active), then with diamine acid as shown in Table 5. Table 5. Amounts of amine salts added In samples 12 and 13, the amine is an equivalent to the AAEM. Even at low levels of AAEM there is still a significant difference in the rate of dilation and the percentage of gel, with a minimal effect on Tg. It is usually expected to see an elevation of 1 to 1.5 ° C in the Tg for every 1% by weight of AAEM in the latex. Table 6 Movie Properties * Samples were dried at 22 ° C for 3 days Example 7 - Latex Synthesis A solution consisting of a solution consisting of a 3-neck 2-liter glass reactor equipped with a stirrer, a reflux condenser and a nitrogen inlet was loaded into a glass reactor. 865.1 g of deionized water and 12.6 g of a dispersion in water of 33% polyester. An aqueous solution containing 4.1 g of sodium persulfate, 1.7 g of sodium bicarbonate and 1.2 g of surfactant (a 45% solution of Dowfax® 2A1) was prepared in 75.4 g of deionized water. The monomer feed contains 831.9 g of acetoxyethylmethacrylate. After the reactor charge was heated to 82 ° C, under a nitrogen atmosphere, the aqueous and monomer mixtures were pumped into the reactor. The aqueous solution was added at a rate of 0.33 g / min for 270 min. The monomer feed was added at a rate of 0.92 g / min for 45 min then at 3.51 g / min for 225 min. After completing the feeds, the reactor was maintained at 82 ° C for 1 hour, then cooled to room temperature. The product was a latex polymer having a pH of 4.5, a solids content of 44.4%, a particle size of 290 nm, and a glass transition temperature (Tg) of 3.2 ° C. EXAMPLE 8 Portions of fifty grams of early latex were formulated with 3.7 g of Igepal® surfactant (30% active), then with diamine acid as shown in Table 7 Table 7. Amounts of amine salts added In samples 15 and 16, the amine is an equivalent to the AAEM. At this high level of AAEM there is a significant increase in the Tg after crosslinking, as shown in Table 8.

Table 8. Movie Properties * The samples were dried at 22 ° C for 3 days. Example 9 - Latex Synthesis A solution consisting of 574.7 g of deionized water and 7.4 g of a dispersion was charged into a 2-liter 3-neck glass reactor equipped with a stirrer, a reflux condenser and a nitrogen inlet. in 33% polyester water. An aqueous solution containing 4 »4 g of ammonium persulfate, 1.59 g of 28% amino hydroxide and 29.6 g of surfactant (a 15% solution of the ammonium salt of Rhodafac® RE-610) was prepared in 71.1 g of deionized water. A monomer mixture was prepared containing 288.9 g of butylacrylate, 253.3 g of methyl methacrylate, 311.1 g of acetoacetoxyethyl methacrylate, and 22.2 g of methacrylic acid. An aqueous monomer mixture containing 26.7 g of 50% aqueous acrylamide in 208.9 g of deionized water was made. After the reactor charge was heated to 82 ° C under a nitrogen atmosphere, the aqueous and monomer mixtures were pumped into the reactor. The aqueous solution was added at a rate of 0.40 g / min for 270 min. The monomer mixture was added at a rate of 0.97 g / min for 45 min then at 3.70 g / min for 225 min. The aqueous acrylamide mixture was added at a rate of 0.26 g / min for 45 min then at 0.99 g / min for 225 minutes. After completing the feeds, the reactor was maintained at 82 ° C for 1 hour, then cooled to room temperature. The product was a latex polymer having a pH of 4.9, a solids content of 48.6%, a particle size of 171 nm, and a glass transition temperature (Tg) of 25.9 ° C.

EXAMPLE 10 Portions of fifty grams of early latex were formulated with acids and amines as shown in Table 9.

Table 9. Amounts of amine salts added * Control In samples 18 and 21, the amine is an equivalent to the AAEM Samples 19 and 21 form films at much lower temperatures than the control 18 and . Sample 19 also has much better film properties than comparative sample 17. Table 10 Control The films were cured at 82 * C for 1 hour before the test. They did not form a film at room temperature.

The invention has been described in detail with particular reference to the preferred embodiments thereof, but it will be understood that various variations and modifications may be made within the spirit and scope of the invention.

Claims (9)

1. CLAIMS 1. A latex polymer composition characterized in that it comprises: a. a polymer component having repeating units of amine-reactive carbonyl groups; b. a crosslinking component comprising nitrogen containing compounds having at least two amine nitrogens with the carbonyl group capable of being protonated by an acid; and c. a volatile acid component comprising an organic acid having a boiling point of less than 250 ° C.
2. 2. The composition of latex polymer according to claim 1, wherein the polymer component is selected from the group consisting of acetoacetyl monomer type, diacetone acrylamide, (meth) acriloxialquilbenzofenona, (meth) acrolein, crotonal-dehyde, 2 -butanone (meth) acrylate and mixtures thereof.
3. 3. The composition of latex polymer according to claim 1, wherein the crosslinking component is selected from the group consisting of ethylenediamine, propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylene haxamina, polyethyleneimine, polypropyleneimine , ethylene oxide adducts, propylene oxide adducts, cyclohexanediamine, xylylenediamine, aminotrimethylcyclohexaneamine, 2,2,4-trimethylhexanediamine, 2,2-dimethylpropane diane, triaminononane, triaminoethylamine, diamino-ethanolamine, diaminomethylcyclohexane and mixtures of the same.
4. The latex polymer composition according to claim 1, characterized in that the volatile acid component is selected from the group consisting of formic acid, acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, acid octanoic and their respective isomers; cyclohexane acid, benzoic acid, carbonic acid carbonate and bicarbonate salts; and mixtures thereof.
5. 5. The latex polymer composition according to claim 1, characterized in that the polymer component additionally comprises other vinyl monomers.
6. 6. A polymer composition carried in water characterized in that it comprises: a. the latex polymer of claim 1; and b. Water.
7. 7. A coating formulation selected from an architectural coating, a metal coating, a wood coating, a plastic coating, a textile coating, a cement coating, a paper coating, an ink, and an adhesive, comprising the water-transported polymer composition of claim 6 and at least one additive selected from a solvent, a pigment, a regulator, a leveling agent, a reslógico agent, a curing agent, a flow control agent, an extender, a auxiliary coalescing reagent, a flattening agent, a wetting agent pigment, a dispersing agent, a surfactant, an ultraviolet absorber (UV) stabilizer UV light, a defoaming agent, an antifoaming agent, an anti-settling, agent anti-corrosion, an incorporation agent, an anti-skid agent, an anti-flooding agent, in antiflotation agent, a fungicide, a fungicide, an inhibitor corrosion agent, a thickening agent, a plasticizer, a reactive plasticizer, a drying agent, a catalyst, a crosslinking agent, and a coalescing agent.
8. A crosslinked coating according to claims 1, 6 or 7.
9. 9. A method for manufacturing a latent crosslinked polymer composition characterized in that it comprises adding a crosslinking component and a volatile acid component to a polymer component.