MXPA96005922A - Replaceable compositions of coating that lead to - Google Patents

Abstract

Aqueous compositions of interlazable, storage stable polymers are disclosed, comprising: (a) an aqueous dispersion of a component of an acrylic polymer, containing certain functional groups including carbonyl, (b) a nitrogen-containing compound, having at least two reactive carbonyl nitrogen groups, and (c) optionally, co-solvents, pigments, fillers, dispersants, soaking agents, anti-foaming agents, UV light absorbers, antioxidants, biocides and stabilizers. These compositions are useful as coatings or binders in coating compositions, or as adhesives.

Description

INTERLOCKING COMPOSITIONS OF WATER COATING BACKGROUND OF THE INVENTION The present invention relates, generally, to crosslinkable compositions of polymers, which carry water, especially emulsions or dispersions. In particular, the present crosslinkable polymer compositions, which carry water, are useful as coatings or binders in compositions, of a package, of stable coatings in storage which have low moisture permeability.

It is well known that the durability and aesthetic value of a variety of substrates can be maintained or enhanced by the application of a polymer coating to the surface of these substrates, and that the interlacing, after application, improves coating performance ( for example, increasing the hardness and strength of the film, as well as the properties of chemical resistance). These improvements are particularly beneficial to substrates that require protection from environmental stresses, or substrates to which abrasives or organic solvents (cleaners) are frequently applied.

When dispersions of polymer particles contain carbonyl functional groups reactive with the nitrogen of the amine, it is difficult to maintain the stability of the dispersion in the presence of the polyfunctional amines. One method for obtaining a dispersion of stable polymer particles in an aqueous carrier is to incorporate functional groups of carboxy acids into the polymer backbone. It is thought that, in an aqueous carrier at a pH equal to, or greater than, the pKa of the acid group, some of the carboxy groups, placed on the surface of the polymer particles, ionize and form a double electric layer that stabilizes the dispersion, around the polymer particles. Sufficient carboxy groups must be present to effectively block the reaction between the amine nitrogen groups of the crosslinking agent and the carbonyl groups present in the dispersed polymer particles. Examples of such compositions are disclosed in patent EP 555 774 Al (Kriess ann et al.) And in WO 93/16133 (Esser), The main drawback of this method is that, although the carboxylic acid groups in the polymer skeleton stabilize the dispersion, these groups also increase the moisture permeability of the resulting coating. That is, in the resulting polymeric coating, the presence of the carboxy acid groups increases the amount of water that can pass through the coating or that is absorbed by the coating itself, thus allowing more water to attack the substrate. An alternative method of stabilizing a dispersion of polymer particles is to incorporate certain hydrophilic compounds (such as functional amine polyalkylene oxide compounds) into the dispersion. Examples of such compositions are disclosed in WO 95/09209 (Serelis et al.), Which teaches that the use of a polyoxyalkylene amine interlayer increases the storage stability of the compositions, however, these compositions have the same inconvenient as the previously described compositions, since the presence of such polyoxyalkylene amines is also known to increase the moisture permeability of such coatings.

The problem of storage stability is addressed in the aforementioned references, but at the expense of coating performance - through the incorporation of high amounts of carboxylic acid into the polymer backbone or the use of hydrophilic crosslinkers, which stabilize the dispersion, such as polyoxyalkyldiamines. What is desired, then, is a stable storage composition, of a package, where the performance of the coating (i.e. water resistance) is not sacrificed.

EXPOSITION OF THE INVENTION The coating compositions of the present invention comprise: (a) a polymeric component, which includes an aqueous dispersion of latex polymer particles, neutralized to a pH of not less than 6, the polymer has a Hansch value of 1.5 or more, an acid number of 0 to 25, at least 5 percent in weight (% by weight) of a carbonyl functional group, capable of reacting with a part of nitrogen, and at least 1% by weight of a non-acid functional group, having hydrogen-bondable portions; and (b) an interlacing agent, comprising a nitrogen-containing compound, with at least two nitrogen functional groups, capable of reacting with a functional part of carbonyl, wherein the ratio of molar equivalents of such a coating agent to the parts of reactive carbonyl, is at least 0.25: 1.

DETAILED DESCRIPTION OF THE INVENTION As used in this specification, the following terms have the following definitions, unless the context clearly dictates otherwise. "Interlacing" and "interlacing" refer to the formation of new chemical bonds between the existing chains of the polymer, and "cure" refers to the interlacing polymers after application to the substrate. "Stable to storage" refers to a coating composition in which the reactive components do not substantially intertwine within the storage container itself, even after prolonged storage. "Pot life" or "shelf life" refers to the period of time that a composition is stable in storage. "Two packs" or "two components" refers to coating compositions (or systems) in which the components are stored separately, then mixed together, just before use; on the other hand, "a package" or "a component" refers to coating compositions in which the components are stored in a container. The specified intervals should be interpreted including the values mentioned, unless specifically identified otherwise.

The multi-component package stable storage compositions according to the present invention include at least 5% by weight of the carbonyl functional group solids, containing the polymer component, based on the weight total of the final composition. It is preferred that the compositions of the present invention preferably include from 5 to 70% by weight solids of the carbonyl functional group, which contains the polymer component, and more preferably from 10 to 50% by weight. The polymer component of the present invention can be prepared by emulsion polymerization or dispersion (aqueous) polymerization techniques known to those skilled in the art. The ethylenically unsaturated monomers can be used to prepare the emulsion or dispersion polymers, which constitute the polymer component of this invention. Examples of suitable monomers include ethylenically unsaturated monomers, such as, for example, acrylic ester monomers, which include methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, methacrylate methyl, ethyl methacrylate, butyl methacrylate, lauryl (meth) acrylate, isobornyl (meth) acrylate, isodecyl (meth) acrylate, oleyl (meth) acrylate, palm (methyl) methacrylate, (meth) acrylate stearyl, hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate; acrylamide or substituted acrylamides; styrene or substituted styrenes; butadiene, ethylene; vinyl acetate; vinyl ester of the "Versatic" acid (a tertiary monocarboxylic acid having a chain length of C9, C10 and C ??, the vinyl ester is also known as "vinyl versatate") or other vinyl esters; vinyl monomers, such as, for example, vinyl chloride, vinylidene chloride, vinyl pyridine, N-vinyl pyrrolidone; non-reactive amino monomers, such as, for example, N, N'-dimethylamino (meth) acrylate, chloroprene and acrylonitrile or methacrylonitrile. In addition, polyfunctional ethylenically unsaturated monomers can be incorporated, which include the allyl, vinyl and crotyl esters of acrylic, methacrylic, maleic and fumaric acids, their di- and tri- (meth) acrylate derivatives, divinylbenzene, diallyphthalate, triallylcyanurate and polyvinyl ethers of glycols and glycerols. Suitable monomers of ethylenically unsaturated, copolymerizable acids include, but are not limited to, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid, maleic acid, monomethyl itaconate, monomethyl fumarate, monobutyl fumarate, maleic anhydride , 2-acrylamido-2-methyl-l-propanesulfonic acid, sodium vinyl sulfonate and phosphoethyl methacrylate.

The polymer component will have a Hansch value of 1.5 or greater, and an acid number of 0 to 25. The acid number of the polymer is preferably 1 to 20 and more preferably 5 to 15. This polymer component will additionally contain at least 5% by weight (based on the weight of the monomer containing that group) of a carbonyl functional group, capable of reacting with a part of amine nitrogen, preferably at least 8% by weight and more preferably at least 12% by weight, and at least 1% by weight (based on the weight of the monomer containing that group) of a non-acid functional group having hydrogen-bondable portions, preferably at least 3% by weight and more preferably at least 5% by weight.

The hydrogen-bondable parts of the polymer component can include, but are not limited to, the hydroxy, amido, alkyl ether, nitrile, tertiary amino or mercapto. Examples of such functional components include the monomers, such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, acrylonitrile, acrylamide, methacrylamide, N- (hydroxyethyl) (meth) acrylamide, N, N-bis- (hydroxyethyl) ) - (meth) acrylamide, dimethylaminoethyl methacrylate and chain transfer agents or initiators, containing hydrogen-bondable parts, such as h-hydroxyethyl-mercaptan, 2,2'-azobis-isobutyronitrile, 2- (carbamoylazole) isobutyronitrile or 2, 2 • -azobis [2-methyl-N- (2-hydroxyethyl) -propionamide].

The amine reactive carbonyl functional group of the polymer component may include, but is not limited to, the ethylenically unsaturated, functional ketone or aldehyde monomers, such as diacetone-acrylated ida, (meth) acryloxyalkyl-benzophenone, ( met) acrolein, croton-aldehyde, 2-butanone (meth) acrylate, as well as the methylene active compounds, such as the esters and amides of acetoacetic acid. Acetoacetic acid esters are preferred. When one or more monomers that do not carry methylene active groups are used, exclusively in the formation of the polymer or when additional groups of acetoacetate are desired, these acetoacetate groups can be introduced by the use of acetoacetate functional chain transfer agents, such as those disclosed in U.S. Patent No. 4,960,924, or by the subsequent reaction of a copolyzed monomer. The cyanoacetates and cyanoacetamides can be prepared by methods known in the art, such as those disclosed, for example, in U.A.A., Nos. 3,554,987, 3,658,878 and 5,021,511. The patents of E. U. A., Nos. 4,960,924, 3,554,987, 3,658,878 and 5,021,511 are incorporated herein by reference.

In the preparation of the polymer component, any chain transfer agent or mixtures thereof can be used to control the molecular weight. Suitable chain transfer agents include, for example, C 1 to C 2 alkyl mercaptans functional alkyl mercaptans, alkyl or functional alkyl ercaptoalkanoates or halogenated hydrocarbons, and may be employed in the polymer at 0.1 to 10% by weight, based on the weight of the polymer. The ethylenically unsaturated monomers are typically polymerized in the presence of water-soluble or oil-soluble initiators (i.e., persulfates, peroxides, hydroperoxides, percarbonates, peracetates, perbenzoates, azo functional compounds, and other species that generate free radicals).

The chelating agents can be used in the emulsion or dispersion polymerization to provide stability. These agents include those that have multifunctional polar groups, and are capable of forming complexes with the metal ions. Typical chelating agents useful in the present invention include, but are not limited to, phosphoric acid, phosphates and polyphosphates; n-phosphonoalkyl-n-carboxylic acids, gem-diphosphonoalkanes and gem-diphosphydroxyalkanes; compounds containing one or more parts of amine-di (methylene phosphonic acid), such as amino-tris- (methylene phosphonic acid), ethylene diamine tetrakis (methylene phosphonic acid) and diethylenetriamine-N, N, N *, N ", N" -penta (methylene phosphonic acid): compounds containing one or more parts of amine-di- (methylene carboxylic acid), such as N- (2-hydroxyethyl) -ethylendia inotriacetic acid ("HEDTA"), ethylenediamine tetraacetic ("EDTA") and nitrile-tris- (methylene carboxylic acid); as well as its alkali metal and ammonium salts. Such agents will be used in the present invention in amounts of 0 to 5%, based on the total weight of the polymer. Surface-active agents are commonly used in emulsion or dispersion polymerization to provide stability, as well as controlling particle size. Conventional surfactants include anionic or nonionic emulsifiers or combinations thereof. Typical anionic emulsifiers include, but are not limited to: the alkali or ammonium alkyl sulfates, the alkyl sulfonates of fatty acids, the esters of sulfosuccinic acid salts, the alkyl diphenyl ether disulphonates, and the free salts or acids of complex organic phosphate esters. Typical nonionic emulsifiers include, but are not limited to: polyethers, for example condensates of ethylene oxide and propylene oxide, including polyethylene glycols and polypropylene glycols-ethers and thioethers of alkyl and alkylaryl, of straight or branched chains, phenoxypoly (ethyleneoxy) -ethanols of alkyl, having alkyl groups with about 7 to 18 carbon atoms, and with about 4 to 100 units of ethyleneoxy, and the polyoxy-alkylene derivatives of hexitol, which include sorbitans, sorbals, mannans and mannures. The surfactants can be employed in the compositions of the present invention at levels of 0.1 to 3% by weight or more, based on the total weight of the final composition. Any nitrogen-containing compound, with at least two carbonyl groups with reactive amine nitrogens, can be employed as the crosslinking agent in the present invention. These compounds can be aliphatic or aromatic, polymeric or non-polymeric, and can be used alone or in combination. Examples of suitable compounds include ethylenediamine, propylenediamine, tetramethylene diamine, pentamethylenediamine, hexamethylenediamine, piperazine, aminoethylpiperazine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, cyclohexyldiamine, isoferonediamine, triaminoethylamine, diaminoethanolamine, phenylenediamine and biphenyldiamine, hydrazine, alkyl dihydrazines, alkyldenyl ether dioxime and water-soluble dihydrazides of dicarboxylic acids (for example, dihydrides of malonic, succinic and adipic acids). Such an interlacing agent is used in an amount sufficient to react with at least 0.25 equivalents of the carbonyl functional group, present in the polymer component, preferably in an amount sufficient to react with at least 0.5 equivalents of the carbonyl functional group, and more preferably at minus 1 equivalent of the carbonyl functional group. That is, the molar ratio of such an interlacing agent to the reactive carbonyl moieties is at least 0.25: 1 to 0.5: 1, and most preferably 1: 1. Other optional components that may be included in this invention include co-solvents, pigments, fillers, dispersants, soaking agents, anti-foaming agents, UV light absorbers, antioxidants, biocides and stabilizers.

The multi-component pack stable, storage stable coating compositions according to the present invention are generally prepared by mixing the polymeric component and the interlacing agent, with stirring, then adding the optional components (as desired) in any order of addition that does not cause incompatibility between the components. Components that do not dissolve in the aqueous carrier (such as pigments and fillers) can be dispersed in the aqueous polymeric component or an aqueous carrier or co-solvent, using a high-cut mixer, such as a sand mill or a COWLES dissolver. The pH of the coating composition can be adjusted by adding an acid or a base, with stirring. Examples of the base include, but are not limited to, ammonia, diethylamine, triethylamine, di-ethyl-ethanolamine, triethanolamine, sodium hydroxide, potassium hydroxide, and sodium acetate. Examples of acids include, but are not limited to, acetic acid, formic acid, hydrochloric acid, nitric acid and toluenesulfonic acid.

The coating compositions of the present invention can be used to provide coatings on suitable substrates, such as wood and reconstituted wood products, concrete, asphalt, fiber cement, stone, marble, clay, plastics (e.g., polystyrene, polyethylene, ABS, polyurethane, polyethylene terephthalate, polybutylene terephthalate, polypropylene, polyphenylene, polycarbonate, polyacrylate, PVC, Norsyl® and polysulfone), paper, cardboard and metal (ferrous as well as non-ferrous).

The coating compositions of the present invention can be applied to the desired substrates, using conventional application techniques, such as conventional or airless spray, roller, brush, curtain, flotation and dip coating methods. Once applied to the substrate, the coating compositions can be cured at ambient or elevated temperatures.

In addition to the coating applications, the compositions of the present invention can be used alone or in combination with other components, for example, with adhesives, sizing agents, composites, impregnants, molders, fillers and non-woven binders.

The following examples are presented to illustrate several additional aspects of the present invention, but they, in no way, attempt to limit the scope of the invention. Example 1 A stirred reactor, containing 1012 grams ("g") of deionized water, 2.3 g of sulphonated nonyl phenolethoxylate surfactant and 29.7 g of itaconic acid, was heated to 822C under a nitrogen atmosphere. A load of 155 g of the monomer emulsion, shown below, was added to the reactor with 25 g of deionized rinse water, followed by 5 g of ammonium persulfate dissolved in 30 g of deionized water. After 13 minutes, the remainder of the monomer emulsion and a solution of 3 g of ammonium persulfate in 100 g of deionized water was pumped into the reactor over a period of 2.5 hours, while maintaining the reactor temperature in 82se. Thirty minutes after completing the charges, the batch was cooled to 65 ° C and aqueous solutions of 0.15% ferrous sulfate heptahydrate, 10% t-butyl hydroperoxide and 7% ascorbic acid were added to the reactor. The batch was further cooled to 452C and neutralized with aqueous ammonia to a pH of 9 to 9.5. The final dispersion of the polymer had a solids content of 46.5%.

Example 2 A stirred reactor, containing 1047 g of deionized water, 2.3 g of sulphonated nonyl phenolethoxylate surfactant and 6.9 g of sodium carbonate, was heated under a nitrogen atmosphere. A load of 155 g of the monomer emulsion, shown below, was added to the reactor with 25 g of deionized rinse water, followed by 5 g of ammonium persulfate dissolved in 30 g of deionized water. After 18 minutes, the remainder of the monomer emulsion and a solution of 3 g of ammonium persulfate in 100 g of deionized water was pumped into the reactor over a period of 2.5 hours, while maintaining the reactor temperature at 802C. Thirty minutes after completing the charges, the batch was cooled to 65 ° C and aqueous solutions of 0.15% ferrous sulfate heptahydrate, 0.0% t-butyl hydroperoxide and 7% ascorbic acid were added to the reactor. The batch was further cooled to 45se and neutralized with ammonia to a pH of 9 to 9.5. The final dispersion of the polymer had a solids content of 46.5%.

Examples 3 to 25 The following Examples 3 to 25 were prepared using methods similar to those of Examples 1 and 2, except that alternative monomer compositions were used, as indicated in the following table. The monomer composition is shown as% by weight of the total content of monomers, used to prepare the polymer examples. The abbreviations used in Examples 3 to 25 are listed below EA Ethyl Acrylate EHA Ethylhexyl Acrylate BA Butyl Acrylate STY Styrene MMA Methacrylate Methyl AAEM Acetoacetoxyethyl methacrylate HEMA Hydroxyethyl methacrylate ALMA Allyl methacrylate PGMM Propylene glycol monometacry IA Itaconic acid MAA Methacrylic Acid MAM Methacrylamide AEP Aminoethyl-Piperazine HMDA Hexamethylene-Diamine Dytek A * 2-methylpentamethylene-Diamine * available from E. U. DuPont de Nemours, Wilmington, Delaware Examples 3 to 25 were tested on the storage stability of a package by mixing 50 g of the composition of the example with 1 molar equivalent of the amines listed in the table. The mixing ratios are based on the weight of the molar equivalent of aceto-acetoxyethyl methacrylate of the composition of the example and the equivalent weight of the reactive amine nitrogen of the selected amine. Once mixed, the samples were placed in a sealed container, which was then placed in an oven for 10 days at 60SC. Samples that did not gel during these stability tests were considered stable in the storage of a package ("Approve").

The Hansch values were used as a relative measure of the hydrophobicity of the polymer composition. These Hansch values of the monomer were obtained using the method described by A. J. Leo in Chem. Rev..93 (4): 1281-1306 (1993). The Hansch values of the polymer in the following tables were calculated by adding the percentages by weight of the monomers with their Hansch values of the respective monomers.

N / T = Not Tested Results of the AEP Stability Test Fail Approve Approve Approve Approve Fail Approve HMDA Fail Approve Approve N / T N T N / T N / T Dytek A N / T N / T Approval Approval Approval Fail Approval Diacusiention Examples 3 and 4 demonstrate that hydrophilic polymers (those with low Hansch values) are not stable in storage when mixed with polyfunctional polyamines. Example 5 demonstrates marginal stability as is evident by being free of remaining gel when mixed with polyfunctional polyamine (HMDA), but not another (AEP). Examples 7-18, 20-23 and 25 demonstrate that hydrophobic polymers (those having a Hansch value above 1.5) are stable in storage, with the proviso that the polymers contain non-acidic functional groups with parts that can be hydrogen bonding (HEMA, PGMM and MAM are examples of monomers which, when incorporated into a polymer, provide such parts.) Examples 6, 19 and 24 demonstrate that, even if the polymer is hydrophobic (as is evident from a Hansch value greater than 1.5), without the presence of the non-acid functional groups, which have parts that can bind to the hydrogen in the polymer, storage stability is not achieved.

The following Examples 26-28 illustrate the utility of the compositions of the present invention as binders for coating applications. The test methods used to demonstrate the utility of the compositions of the present invention as binders for coating applications are described below. Hot Block Test - Test specimens of hardboard (7.6 x 10.2 x 1.3 cm) were coated with a dry sizing paint of approximately 38 microns thick, and cured at a peak surface temperature of the board of 177se and they were allowed to cool to a surface temperature of 60 sec. The test specimens were then placed perpendicularly, face to face, and pressed for 6 minutes at 15.5 kg / cm2, using a Carver Press. Favorable insulation boards were used on either side of the test specimen. The plates did not heat up. The coating was considered acceptable if only a slight force or no force was required to separate the specimens without damaging the film.

Adhesion Test - Hardboard test specimens (7.6 x 10.2 x 1.3 cm) were coated with a dry sizing paint of 38 microns and cured at a peak surface temperature of 177sc. After allowing the os to condition at room temperature for at least one day, a tape (# 250) was applied to the surface and detached by pulling rapidly at an angle of 902. adhesion was recorded with% loss. Alternatively, the test can be performed on an X-scribed surface, or one which has been soaked with deionized water for 1 hour before the test.

Double rubs with the MEK - The test specimens of hardboard (7.6 x 10.2 x 1.3 cm) were coated with a dry sizing paint of 38 microns and cured under the specified conditions. A thin grade 20B fabric was wrapped around the index finger, covered with a rubber glove, of the tester. The finger coated with the thin cloth was then immersed in the methyl ethyl ketone (MEK), removed and then placed on the surface of the cured film at a 45 degree angle. The surface of the film was then rubbed with moderate pressure, using strokes back and forth. The number of runs required to break the film and expose the substrate was considered the end point.

Example 26 A pigment base was prepared using a CO LES dissolving apparatus of the components listed in the following table.

To 59.3 g of this pigment base were added 50 g (46.2% by weight total solids) of the emulsion polymer prepared in Example 13, 2.4 g of ethylene glycol monobutyl ether and 0.4 g of aminoethylethanolamine. The resulting paint was applied to a reconstituted board substrate, using a lay bar (to give a dry film of 38 microns thick) and cured for 30 seconds in a 177se oven, followed by infrared heating, until the temperature of the surface of the board came to 177se. After cooling to room temperature, the coating was tested and found to withstand more than 200 double rubs of methyl ethyl ketone ("MEK") and had 0% adhesion loss.

Example 27 To 60.24 g of pigment base, described in Example 26, 50 g (46.8% by weight total solids) of the emulsion polymer prepared in Example 20, 2.4 g of ethylene glycol monobutyl ether and 0.53 g of aminoethylpiperazine. The paint, thus prepared, was applied as in Example 26, to give a film that supports more than 200 double rubs of the MEK and has good resistance to hot block formation (as is evident because it does not adhere to the panel when the coated surfaces of the substrate are placed face to face and pressed at 15.5 kg / cm2 and 66 seconds, for 6 minutes). Example 28 A white pigment base was prepared using the CO LES dissolving apparatus, with the components listed in the following table.

To 38.5 g of the white pigment base were added 83.5 g (46.5% by weight of total solids) of the emulsion polymer prepared in Example 22, 3.3 g of 10% propylene glycol monobutyl ether and 1.5 g of 2% strength. -methyl-l, 5-pentanediamine. The paint was applied to a reconstructed wood substrate, and allowed to dry for 14 days at room temperature. The cured coating demonstrated a good coating performance, as is evident from the 0% loss of adhesion after a belt pull test. Example 29 This example demonstrates the utility of a polyfunctional polyamine polymer as an interlacing agent for the polymers of the present invention. A gray paint at 45% (volume concentration of the pigment) was prepared by mixing together (with stirring) 25.0 g of a polymer emulsion with 46.4% by weight, prepared in Example 14, 2.59 g of a 29% solution in weight of the poly (hydroxyethylaminoethyl) methacrylate, 35.7 g of pigment base, prepared in Example 26 and 1.4 g of ethylene glycol monobutyl ether. The painting, thus prepared, contained 0.5 molar equivalents of reactive amine nitrogen per 1.0 molar equivalent of the polymer containing acetoacetoxy functional groups. The paint was applied to a hard board substrate, using a wire laying bar, to give a dry film of 38 microns, after curing for 30 seconds at 177 seconds, followed by curing in an infrared oven until the temperature of the surface of the board was 177se. After cooling to room temperature, the cured film withstood more than 200 MEK double rubs and had a Cobb value of 2g / 100 cm2. This Cobb test (TAPPI Standard Test Method, T 441 os-77) is a measure of the water absorbed through a paint film on a wood-based substrate.) The cured film was also tested on the block resistance in hot, pressing two specimens coated with paint, face to face, at a pressure of 15.5 kg / cm2 and a temperature of 66 e, for six minutes. The paint in this example showed no stickiness or damage to the film, after testing on the hot block strength, as described.

Example 30 This example demonstrates the utility of the present invention as an interlacing binder at room temperature in a 20% white coating (pigment concentration by volume.

An emulsion polymer, having a composition of 46.8% by weight of 2-ethylhexyl acrylate, 38.2% by weight of methyl methacrylate, 10% by weight of acetoacetoxyethyl methacrylate, 3% by weight of hydroxyethyl methacrylate, 1.5% by weight of itaconic acid and 0.5% by weight of allyl methacrylate, was prepared according to the method of Example 1. To 67.2 g of this emulsion emulsion (46% solids) were added (with stirring, using a COWLES dissolver) 1.6 g of dispersant, 12.4 g of titanium dioxide (TIO2), 1.4 g of silica, 1.5 g of talc, 7.4 g of clay, 0.04 g of bentonite (thickener), 10.2 g of water and 0.14 g of defoamer. At the end of the mixing in the COWLES apparatus, 1.0 g of l, 5-diamino-2-methylpentane and 1.6 g of ethylene glycol monobutyl ether were added with moderate agitation. The paint, thus prepared, was applied to an aluminum panel using a wire laying bar, to give, after drying, a film of 38 microns thick. After 1 week of curing at room temperature, the panel withstood more than 200 double rubs with the MEK. Example 31 This example demonstrates the storage stability, of a package, of an emulsion polymer that does not contain acid.

An emulsion polymer, having 44.6% by weight of solids content and a composition of 35% by weight of butyl acrylate, 45% by weight of styrene, 15% by weight of acetoacetoxyethyl methacrylate and 5% by weight of methacrylate of hydroxyethyl, was prepared according to the method of Example 1. To 50.0 g of the emulsion polymer was added, with stirring, 089.2 g of diaminocyclohexane. The mixture, thus produced, was found to be storage stable, from a package, as is evident by the remaining, gel-free fluid, after heat aging in a 60sc oven, for 10 days. EXAMPLE 32 This example illustrates the effect that the acid functionality of the polymer has on increasing the penetration of water through a cured paint film, composed of the polymer containing the acid functionality.

An emulsion polymer, having 46.4% solids content and a composition of 31% by weight of 2-ethylhexyl acrylate, 46.9% by weight of styrene, 15% by weight of acetoacetoxyethyl methacrylate, 4.6% by weight of methacrylate of hydroxyethyl, 2.0% by weight of methacrylic acid and 0.5% by weight of allyl methacrylate, was prepared according to the method of Example 1. A second emulsion polymer, which has no acid functionality, with a composition of 31% by weight of 2-ethylhexyl acrylate, 48.9% by weight of styrene, 15% by weight of acetoacetoxyethyl methacrylate, 4.6% by weight of hydroxyethyl methacrylate and 0.5% by weight of allyl methacrylate was prepared simultaneously. Paints (52% pigment concentration by volume) were obtained from each emulsion, mixing 50.0 g of each emulsion polymer with 1.15 g of 1,2-diaminocyclohexane and 114 g of a paint-based grind, with 69.2% by weight of solids, consisting of titanium dioxide, clay, iron oxide, defoamer, propylene-glycol-onobutil-ether, and water. Each painting was applied using a wire-laying bar to hardboard test specimens of 7.6 x 10.2 x 1.3 cm, and cured for 30 seconds in an oven with a temperature of 177se, followed by surface heating in an infrared oven. , until a surface temperature of 177se was attained. The water permeability was measured using the Cobb method, which involves securing a tube 2.5 cm high by 6 cm in diameter to the painted surface of the test specimen, filling the tube with water and measuring the weight gain of the specimen of test, after 24 hours, as a function of the grams of water absorbed per 100 cm2 ("g / 100 cm2"). The prepared paint of the emulsion polymer, which contains acid, gave a Cobb value of 9g / 100 cm2, while the prepared paint of the above-described emulsion polymer, which has no acid, gave a Cobb value of 3 g / 100 cm2.

Examples 33-35 The following Examples 33 to 35 illustrate the effect on water permeability when a polyoxyalkylene polyamine amine is used to crosslink a functional acetoacetate polymer. Paints (20% pigment concentration by volume) were prepared according to the following table and were crosslinked with either polyoxyalkylene polyamine (Mn = 600) or an aliphatic diamine (1,2-diaminocyclohexane).

The paints of Examples 33 to 35 were applied using a wire laying bar, to hardboard test specimens of 7.6 x 10.2 x 1.3 cm, to give equivalent dry film thicknesses. The test coated specimens were cured at room temperature for 1 week, then tested for water permeability using the Cobb method. Example 33 gave a Cobb value of 14 g / 100 was2. Example 34 gave a Cobb value of 17 g / 100 cm 2 and Example 35, a value of 12 g / 100 cm 2. which illustrates that the increase in the concentration of the polyoxylene polyamine interlayer results in increases in water permeability.

Claims (10)

1. An aqueous, self-interlacing polymer dispersion, which comprises: (a) a polymeric component, including an aqueous dispersion of latex polymer particles, neutralized to a pH of not less than 6, the polymer particles have a Hansch value of 1.5 or greater, an acid number of 0 to 25 , at least 5 weight percent of a carbonyl functional group, capable of reacting with a part of nitrogen, and at least 1% by weight of parts of a non-acid functional group having hydrogen-bondable portions; Y (b) an interlacing agent, comprising a nitrogen-containing compound, having at least two functional nitrogen groups, capable of reacting with a functional part of carbonyl, in which the molar ratio of such cross-linking agent to reactive carbonyl parts , is at least 0.25: 1.

2. The polymer dispersion according to claim 1, wherein the acid number of the polymer particles is from 1 to 20.

3. The polymer dispersion according to claim 1 or claim 2, wherein the polymer particles have at least 8% by weight of a carbonyl functional group, capable of reacting with a portion of amine nitrogen.

4. The polymer dispersion according to any of claims 1 to 3, wherein the polymer particles have at least 3% by weight of a non-acid functional group, which has parts that can bind to hydrogen.

5. The polymer dispersion according to any of claims 1 to 4, wherein the molar ratio of the crosslinking agent to the reactive carbonyl portions is at least 0.5: 1.

6. An aqueous, storage stable, interlaxable coating composition comprising the polymer dispersion of any one of claims 1 to 5.

7. A method for supplying an interlaced protective coating on a substrate, which comprises the steps of: applying a coating of the composition, according to any of claims 1 to 6, to the substrate; and allowing the composition to cure at room temperature or at a higher temperature.

8. The method according to claim 7, wherein the substrate is selected from the group consisting of: wood and reconstituted wood products, concrete, asphalt, fibers, cement, stone, marble, clay, plastics, paper, cardboard and metal.

9. The use of the polymer dispersion according to any of claims 1 to 6, as a binder for one-component, storage stable coating compositions capable of undergoing interlacing at room temperature or a higher temperature.

10. The use of the polymer dispersion according to any of claims 1 to 6, as an adhesive.