MXPA00002416A - Phosphatized amine chain-extended epoxy polymeric compounds - Google Patents

Abstract

This invention provides a novel phosphatized polymeric product which is formed by:(a) forming an amine-extended resinous composition having unreacted epoxy groups by mixing, under free-radical initiated polymerization conditions, a polymerizable, ethylenically unsaturated monomeric component and a polyepoxide component;and (b) phosphatizing at least a portion of the unreacted epoxy groups of the resinous composition. The present invention also provides novel coating compositions containing the aforedescribed polymeric product. While these novel coating compositions have a number of different uses, they are particularly useful for application to metal substrates such as can end stock since they result in a cured film which has excellent performance properties such as flexibility and extensibility, adhesion, resistance to boiling liquid pack tests and boiling water taste test results.

Description

EPOXY POLYM COMPOUNDS PROLONGED PHOSPHATES IN AMENA CHAIN FIELD OF THE INVENTION The present invention relates to epoxy phosphated polymer compositions extended in chain with amine. While these compositions have a number of different uses, they are particularly useful in solvent-borne coatings, such as those designed for application on rolled metal matls and, more specifically, those designed for application on the rolled metal mats of which they make the ends of the cans, which will be referred to hereinafter as "matls for ends of cans".

BACKGROUND OF THE INVENTION It is expected that the coatings, particularly those used in the industries of metal containers for food and beverages, meet a ss of requirements to be commercially viable. One of these requirements includes its ability to adhere well to the base metal on which they are applied. Another requirement is that they possess a certain degree of flexibility, extensibility and adhesion characttics that allow them to withstand the manufacture of the container itself and / or the processing, if any, of the contents of the container. Another requirement for a coating designed for use in the packaging industry with metal containers appears when the coating is applied in such a way as to directly contact the consumer of the contents of the container or with the contents themselves. Under these circumstances, it is necessary that the coating not only be non-toxic, but also have no adverse effects on the taste of the food or beverage stored in the coated container. Yet another requirement for a coating designed for use in the packaging industry with metal containers is the ability of the coating to coalesce and / or form a continuous film. Specifically, if these properties are not present, the contents of the container could be exposed to the metal. This, in turn, can give rise to problems such as: pre-maturation corrosion of the container, contamination of the contents of the container, adverse effects on the taste of the contents of the container and the like. Yet another requirement for coatings designed for use in the packaging industry with metal containers is that they resist "bursting". The term "pop" is used in the coating industry to refer to a particular defect in the coatings that develops during its curing process. Particularly during the coating process of many coatings, gaseous by-products are formed which can then be trapped within the coating. This problem appears more commonly in areas where the coating has a relatively high film thickness. Coatings applicators typically need to take special precautions when working with burst-prone coatings, to ensure that a maximum allowable thickness of the coating is not exceeded over any portion of the article being coated. In some cases, the speed at which the coating is applied (ie, the "line speed") is limited by the tendency to burst of a coating. Even another requirement for coatings designed for use in the packaging industry with metal containers is that they resist "reddening". The term "redness" is used in the coatings industry to refer to another defect in the coatings that develops during its curing process. Specifically, the term "reddening" refers to a film brush that is believed to be produced by water absorption. This defect is particularly evident with container liners that are subjected to high temperature and high vapor pressure conditions during the retorting process of the packaging. A defect that often accompanies redness is the "blistg". The term "blister formation" is used in the coatings industry to refer to a sporadic coating removal as the salts are dissolved., which are present in the interface of the metallic substrate and the coating, by the water that penetrates the film. As indicated above, coatings designed for use inside food and beverage containers should not adversely affect the taste of the contents of the container. Taste problems can occur in a number of ways, such as by leaching the contents of the coating to the beverage, taste adsorption by the coating, a chemical reaction between the contents of the container and the dressing, contact of the contents of the container with the bare metal due to coating defects and / or a combination of these. Since the coatings designed for use in the materials of the ends of the metal containers are applied thereto before cutting the ends and punching them out of the rolled metal material, in addition to all the properties mentioned above they must also be flexible and extensible. For example, the metallic material for can ends is typically coated on both sides. Next, the coated metal material is drilled, the notch is made for opening in the upper position "by burst" and the upper ring is then joined to open the container with a pin that is manufactured separately. The end is then attached to the body of the can by an edge rolling process. Consequently, if it is used on rolled metal materials, from which ends of cans have to be made, the coating applied on them must have associated thereto a minimum degree of hardness and flexibility, in such a way that it can withstand extensive manufacturing procedures. , in addition to being resistant to water and chemical agents, to prevent adverse effects on the taste of the contents of the container. The container industry frequently uses coatings based on epoxy resins to achieve some of these properties. However, epoxy resins as the sole film-forming vehicles do not adequately soak the metal substrate and, therefore, fail to give the desired level of coalescence and film continuity. For these reasons, container coating technology frequently uses epoxy-graft copolymers. An epoxy-graft copolymer is an epoxy resin that has been grafted with monomers such as styrene and methacrylic acid. It has been observed that said epoxy resins, which have been modified with acrylic monomers impart a better coalescence and film continuity to the resulting coating. It has also been observed that simple mixing of an epoxy resin with an acrylic polymer gives a coating composition which lacks the same level of homogeneity and stability as is obtained with an epoxy-graft copolymer. The US Title Certificate 5,252,669 to Maska et al. discloses a water reducible resin suitable for use as a coating for metal substrates, such as metal food and beverage cans. The resin described in that patent is produced by grafting into an organic solvent a thermoplastic polymer (which has no crosslinkable moieties) containing grafting agents in a thermosetting polymer (having crosslinkable moieties) containing acid-functional groups to make the resulting polymer is soluble in water. The thermoplastic polymer is at the same time grafted onto a polyepoxide that has previously been phosphatized. The resulting polymer is used as a resinous binder in a water-borne coating for use as a container liner. The US Title Certificate 5,290,828 to Craun et al. discloses an aqueous low volatile organic content ("VOC") coating containing a polymeric binder, which includes an epoxy and polyester terpolymer grafted with an addition copolymer. According to that patent, the coating described therein is suitable for application by spraying to metal substrates, such as beer cans and beverages. The graft terpolymer includes an unsaturated polyester, an epoxy resin and an addition copolymer grafted to the polyester. The addition copolymer includes from 20 to 100 percent of ethylene carboxy functional monomers. The epoxy polyester grafted with addition copolymer has an Acid Number greater than 30 to facilitate dispersion of the terpolymer in water using a volatile base. The epoxy resin of that patent is not phosphated. The US Title Certificate No. 4,212,781 to Evans et al. describes a process for modifying an epoxy resin by reaction in an organic solvent of the epoxy resin with polymerizable ethylenically unsaturated monomers to produce a reaction mixture that includes an epoxy-acrylic co-polymer mixture containing epoxy resin, epoxy graft polymer -acrylic and non-grafted addition polymer formed in an associative manner. According to that patent, in modified epoxy resins which are suitable for use in water-borne coating compositions applied by spraying onto can coatings, the in-situ polymerized monomer should include acid-functional monomers to obtain sufficiently high acid functionality in the reaction mixture so as to effect a stable dispersion in water, although solvent carriers can also be used. Neither the epoxy groups of the epoxy resin nor those of the final reaction mixture described in that patent are phosphated. The US Title Certificate 5,428,084 to S arup et al. describes an epoxy resin defunctionalized with amine and coating compositions containing said defunctionalized epoxy resin, which are suitable for application on metal surfaces, such as materials for can ends. The epoxy resin defunctionalized with amine is prepared by reacting a polyepoxide with ammonia or an amine having at least two active hydrogens, using a ratio close to 1: 1 equivalents of epoxy to equivalents of ammonia or amine. The reaction of the psyepoxide resin with ammonia or amine involves a ring opening reaction in which the resulting non-gelled product is the amine-terminated product of a polyepoxide resin. The coating compositions described in that patent contain a resinous mixture of amine defunctionalized epoxy with another resin, such as a vinyl addition copolymer containing about 5 to 25 weight percent of an alpha, beta, carboxylic acid. ethylenically unsaturated to achieve dispersibility of the copolymer. The resulting coating compositions are reducible in water and may additionally contain a curing agent. Neither the epoxy groups of the epoxy resin nor those of the final reaction mixture described in that patent are phosphated. According to the specifications of US Patents cited above, the reaction products and the respective water-borne coatings described therein provide water-based dispersions which are suitable for spray application as a sanitary coating or interior spray coating for interiors of beer and beverage cans . In order to facilitate the. Water dispersibility of these reaction products, those skilled in the art know that it is necessary that these coatings contain a minimum amount of acid-functional monomer. When the acid-functional monomers are present in an amount that facilitates dispersibility, their presence in this concentration also tends to promote the hydrophilicity of the resulting coating. The hydrophilicity of these monomers is undesirable, especially when the coating is designed for use inside metal food and beverage containers. Specifically, those skilled in the art know that hydrophilicity can result in greater water absorption of the cured coating. This, in turn, can lead to redness and / or blistering during the processing procedures. Additionally, many of the waterborne coatings of the type described in US Pat. cited above are not suitable for use as roller applied coatings. Therefore, those skilled in the art will not be inclined by the roller application of said re-dressings on the flat metallic material used to manufacture the can ends. As has been demonstrated above, although there are a number of coating compositions that can be applied on the can end material, most conventional coatings have a number of deficiencies associated therewith that require the formulator , applicator and / or processor compensate them. A coating that minimizes and / or eliminates many, if not all, of the aforementioned deficiencies would be well received by the metal packaging industry.

COMPENDIUM OF THE INVENTION An object of the present invention is to achieve a polymeric product and / or coatings containing said polymeric product that are resistant to reddening and / or blistering and that can withstand the processing conditions to which metal containers are subjected in the process. industry of containers for food and drinks. Another object of the invention is to achieve flexible and extensible coatings that adhere well to the metal substrates on which they are applied and which can withstand extensive manufacturing processes. Still another object of the invention is to achieve a water-borne coating that resists bursting and that is suitable for roll coating application at relatively high linear speeds. These and other objects are achieved by the development and formulation of a new phosphatized polymeric product which is formed by means of a process consistent in the following steps: (a) formation of a prolonged resinous composition with amine having non-epoxy groups reacted by mixing, under polymerization conditions initiated by free radicals, a polymerizable monomeric ethylenically unsaturated component and a polyepoxide component, and (b) phosphating at least a portion of the unreacted epoxy groups of the resinous composition. The present invention also provides novel coating compositions containing the polymeric product described above. While these new coating compositions have a number of different uses, they are particularly useful for application to metal substrates, such as can end material, since they result in a cured film having excellent performance properties, such as such as flexibility and extensibility, adhesion, resistance to boiling liquid packet testing and taste test results in boiling water.

DETAILED DESCRIPTION OF THE INVENTION The polymeric product of the present invention is formed by phosphating at least a portion of unreacted epoxy groups in a resinous composition prolonged with amine. As used herein, the term "prolonged amine resinous composition" refers to a composition having at least some amine prolongations associated therewith. These amine prolongations can occur as a result of any means that is apparent to those skilled in the art after reading this description. Some examples of how such amine prolongations can occur are by the use of prolonged amine reagents (eg, amine-extended polyepoxides) and / or by amine prolongation of the resulting resinous composition. Further detailed reativements with amine and / or amine prolongation methods of the resinous compositions are discussed in greater detail below. The level of amine prolongations that need to be present in the resinous composition depends, in part, on the desired end use of the polymer product that is ultimately made with it. Typically, the resinous composition used in practicing this invention is formed into an organic solvent component by mixing with a polyepoxide component, under polymerization conditions initiated by free radicals, and a polymerizable ethylenically unsaturated monomer component. As indicated above, the resinous composition can receive a degree of its extension with amine using a polyepoxide component containing a polyepoxide prolonged with amine. As used herein, the term "extended polyepoxide with amine" refers to the progress of a polyepoxide to increase molecular weight by reaction of a polyepoxide with an amine having at least two active hydrogen atoms. The reaction between the polyepoxide resin and the amine involves a simple ring-opening reaction at the site of an active hydrogen, wherein the resulting product is a higher molecular weight polyepoxide having unreacted epoxy groups. The active hydrogen atoms can be on the same nitrogen atom (for example, primary amines) or on different nitrogen atoms in a compound (for example, diamines or other polyamines), where the active hydrogen atoms can be on the same nitrogen atom or on two or more nitrogen atoms. Examples of primary amines suitable for use in the present invention to prolong the chain of a polyethoxide include, without limitation, at least one of the following compounds: ethylamine, propylamine, isopropylamine and butylamine. A primary amine useful for this purpose is butylamine. On the other hand, suitable diamines and other polyamines include, without limitation, at least one of the following compounds: hydrazine, ethylenediamine, propylene diamine, butylene diamine, hexylenediamine, diethylenetriamine, tetraethylenepentamine, N-methylethylenediamine, N-methylbutylenediamine, N, N- dimethylethylenediamine, N, N-dipropylethylenediamine and N, N-dimethylhexylenediamine. Hydroxylalkylamines are also suitable for use in the present invention. Examples of suitable hydroxylalkyl amines include, without limitation, at least one of the following compounds: monoethanolamine, diethanolamine, N-methylethanolamine and dimethylethanolamine. In a preferred embodiment of the invention, the polyepoxide component consists of a polyephoxide which is chain extended with amine with monoethanolamine. Without inclining to the theory, we believe that monoethanolamine is preferred because its two active hydrogen atoms are both on the same nitrogen atom and, through the ring-opening reaction of an epoxy group of two independent polyepoxide molecules , one at the site of each of the active hydrogens, the polyepoxide can be linearly extended in the chain with amine. Another reason observed for the monoethanolamine preference is the fact that each ethanolamine molecule thus reacted provides a pendant hydroxyl group for cross-linking with a suitable curing agent. The polyepoxide component can consist of: polyepoxides prolonged with amine, polyepoxides not prolonged with amine or a mixture of these. If the polyepoxide component is exclusively constituted by non-prolonged polyepoxides with amine, the resinous composition is prolonged with amine before being phosphatized. On the other hand, if the polyepoxide component is exclusively constituted by non-prolonged polyepoxides with amine, it is typically not necessary to extend the resin composition still with amine. However, if the polyepoxide component is constituted by a mixture of extended polyepoxides with amine and not prolonged with amine, the resinous composition may still need to be prolonged with amine, depending on the desired properties of the polymeric product made therewith. The polyepoxide useful in the polyepoxide component of this invention is typically a compound or mixture of compounds having more than 1.0 epoxy groups per molecule. A preferred class of polyepoxides includes, without limitation, the polyglycidyl ethers of polyphenols. This preferred class of polyepoxides are typically produced by etherification of a polyphenol with epichlorohydrin in the presence of an alkali. The phenolic compound in said process may include, without limitation, at least one of the following compounds: 2, 2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) ethane, 1, 1-bis ( 4-hydroxyphenyl) isobutane, 2,2-bis (4-hydroxybutylter-cyanophenyl) propane, bis (2-hydroxynaphthyl) ethane, 1,5-dihydroxynaphthalene and 1,1-bis (4-hydroxy-3-allylphenyl) ethane. Another quite useful class of polyepoxides are produced in a similar way from polyphenolic resins. Polyglycidyl ether of Bisphenol A is preferred. Also suitable for use in the polyepoxide component are the polyglycidyl ethers of polyhydric alcohols derived from polyhydric alcohols such as ethylene glycol., diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1, -butylene glycol, 1,5-pentanediol, 1,2,6-hexanetriol, glycerol and 2,2-bis (4-hydroxycyclohexyl) propane. Cycloaliphatic polyepoxide resins can also be used. Said resins are prepared by epoxidation of cyclic olefins with organic percents (for example, peracetic acid). The polymerizable ethylenically unsaturated monomer component can be selected from a wide variety of materials, depending on the desired properties. The selection of the appropriate contents of this monomeric component will be apparent to those skilled in the art after reading this description.

When the polymeric product is to be used in can end materials, the ethylenically unsaturated polymerizable monomer component typically consists of an aromatic vinyl compound. Examples thereof include, without limitation, at least one of the following aromatic compounds: styrene, alpha-methylstyrene, butyl (tertiary) styrene, vinyltoluene and vinylxylene. Said monomers are preferred for their good resistance to water and pasteurization. When used, these monomers are typically present in an amount ranging from about 10 to about 70 weight percent of the monomer mixture, more typically in an amount ranging from about 20 to about 50 percent by weight. weight and, even more preferably, in an amount ranging from about 25 to about 40 weight percent. In addition to the foregoing, the ethylenically unsaturated polymerizable monomer component may also include, without limitation, alkyl esters of methacrylic acid containing from 1 to 3 carbon atoms in the alkyl group. Specific examples of such esters are methyl methacrylate and ethyl methacrylate. These monomers are typically used in an amount of up to about 40 weight percent of the monomer component, more typically in an amount ranging from about 5 to about 30 weight percent and, even more preferably, in a amount ranging from about 10 to about 20 weight percent, where the percentages by weight are based on the total weight of the monomer component. Other monomers which may be included in the monomeric component are the alkyl esters of acrylic acid having from 2 to 17 carbon atoms in the alkyl group and alkyl esters of methacrylic acid of 4 to 17 carbon atoms in the alkyl group. Examples of monomers of this type include, without limitation, at least one of the following compounds: ethyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, butyl methacrylate, methacrylate 2 -ethylhexyl, lauryl methacrylate and stearyl methacrylate. These monomers are typically used in an amount of up to about 40 weight percent of the monomer component, more typically in an amount ranging from about 5 to about 30 weight percent and, even more typically, in an amount which it varies between about 10 and about 20 weight percent, where the percentages by weight are based on the total weight of the monomer component. Still other monomers that can be used in the monomeric component include, without limitation, vinyl monomers, such as ethylene, propylene and the like, vinyl halides, vinylidene halides, vinyl versatate, vinyl acetate, dialkyl maleate. , allyl chloride, allyl alcohol, 1,3-butadiene, 2-chlorobutene, methyl vinyl ether, acrylamide, methacrylamide, acrylonitrile, methacrylonitrile and mixtures thereof. These other monomers, when used, are typically present in an amount of up to about 10 weight percent of the monomer component, more typically in an amount ranging from about 1 to about 7 weight percent, and even more. typically, in an amount ranging from about 2 to about 5 weight percent. Preferred monomers which can be used in the copolymerization initiated by free radicals are N- (alkoxymethyl) acrylamide or N- (alkoxymethyl) ethacrylamide with 1 to 4 carbon atoms in the alkoxy group. These monomers are preferred because they provide an in-ternal crosslinking through self-condensation. The preferred member of this group is N- (butoxymethyl) methacrylamide. Examples of other members include, without limitation, N- (butoxymethyl) -acrylamide, N- (ethoxymethyl) acrylamide and their mixtures. These (meth) acrylamide monomers, when included, are present in amounts typically in the range of about 5 to about 35 weight percent of the monomeric component, more typically in an amount ranging from about 10 to about 10. about 30 weight percent, and even more typically, in an amount ranging from about 15 to about 25 weight percent. Other preferred monomers which can be used in the copolymerization initiated by free radicals are the hydroxyalkyl esters of acrylic acid and the hydroxyalkyl esters of methacrylic acid. These monomers are preferred to provide hydroxyl groups for cross-linking with an aminoplast, phenolic or isocyanate curing agent. A preferred member of this group is the hydroxyalkyl ester of methacrylic acid, such as hydroxyethyl methacrylate. Examples of other members include, without limitation, hydroxyethyl acrylate, hydroxypropyl acrylate, and hydroxypropyl methacrylate. These monomers, when included, are present in amounts typically in the range of about 5 to about 35 weight percent of the monomer component, more typically in an amount ranging from about 10 to about 30 weight percent and, even more preferably, in an amount ranging from about 15 to about 25 weight percent. However, polymerizable ethylenically unsaturated acid functional monomers can also be used in the copolymerization initiated by free radicals, since said monomers tend to be hydrophilic.; are typically present in an amount ranging from about 1 to about 7 weight percent, typically in an amount ranging from about 2 to about 5 weight percent, said weight percentages being based on the weight of Total resin solids of the polymer product. Acid-functional monomers at levels greater than about 7 percent by weight can cause instability in a solvent-borne coating composition. Additionally, the hydrophilicity of these monomers is undesirable, since it may result in greater water absorption of the cured coating, which would cause redness and / or blistering upon exposure to high temperature / high humidity conditions or during the indicted. Examples of acid-functional monomers that may be used include, without limitation, alpha-beta-ethylenically unsaturated carboxylic acids containing from 3 to 8 carbon atoms, such as acrylic acid and methacrylic acid. In a preferred embodiment of the present invention, the ethylenically unsaturated monomer consists of a mixture of N- (butoxymethyl) methacrylamide, butyl acrylate, styrene and acrylic acid. Even more preferred is a mixture consisting of hydroxyethyl methacrylate, styrene, butyl methacrylate, methacrylic acid and mixtures thereof. The copolymerization process used in the preparation of the resinous composition is carried out in the presence of an organic solvent component, which consists of at least one organic solvent compound. The organic solvent component typically consists of at least one solvent that dissolves the polyepoxide (s) present in the polyepoxide component and / or the monomer (s) present in the monomer component. Any organic solvent that can dissolve the polyepoxide (s) and / or monomer (s) used in the practice of this invention can be used. Examples of such organic solvents include, without limitation, at least one of the following: xylene, methyl ethyl ketone, methyl butyl ketone, ethanol, propa-nol, isopropanol, butanol, butoxy ethanol, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether and mixtures thereof. The organic solvent component may also consist of a mixture of at least two miscible solvents, where one dissolves the polyepoxide (s) present in the polyepoxide component and the other dissolves the monomer (s) present) in the monomer component. In a preferred embodiment, the organic solvent component consists of a mixture of methyl ethyl ketone and xylene. In an even more preferred embodiment, the organic solvent component is in a mixture of at least two of the following diethylene glycol monobutyl ether, ethylene glycol monobutyl ether and N-methylpyrrolidone. Typically, the polymeric product of the present invention is produced by refluxing the po-lipoxide component and an organic solvent (s) that is (are) capable of dissolving the polyepoxide (s) present ( s) in the polyepoxide component. Next, a initiator component is added to the polymerizable ethylenically unsaturated monomer component under free radical initiated copolymerization conditions. This forms a resinous composition containing unreacted epoxy groups. If none of the polyepoxides present in the polyepoxide component is chain extended with amine prior to copolymerization initiated by free radicals in situ, the resinous composition is chain extended with an amine. On the other hand, if any of the polyepoxides present in the polyepoxide component is extended in chain with amine before co-polymerization initiated by free radicals in itself, the resinous composition may need to be further chain-extended with an amine, depending on the properties desired of the resulting product. In carrying out the present invention, the ratio of the weight percent of the polymerizable ethylenically unsaturated monomer component to the weight percentage of the polyepoxide component typically ranges between about 5:95 and about 20:80, where the percentages by weight are based on the total weight of the monomer component and of the polyepoxide component. Preferably, the ratio of the weight percent of the monomer component to the weight percentage of the polyepoxide component ranges from about 10:90 to about 25:75. After having obtained a prolonged resinous composition with amine having unreacted epoxy groups, at least a portion of the non-reactive epoxy groups of the resinous composition are phosphated to form a polymeric product. The phosphating can be carried out by any means that is evident to those skilled in the art after reading this description. An example of a way of phosphating the non-reactive epoxy groups of the resinous composition is by reaction of phosphoric acid with unreacted epoxy groups, typically in a solvent or mixture of organic solvents. This reaction is an esterification between the hydrogen ions of the phosphoric acid and the epoxy groups. It should be noted that, for purposes of phosphating here, phosphoric acid is considered to be monofunctional with respect to epoxy. The phosphoric acid can be a 100 percent phosphoric acid, superphosphoric acid or its aqueous solutions, such as a 85 percent phosphoric acid solution. Other forms of phosphoric acid and triphosphoric acid may be used. In addition, polymeric or partial anhydrides of phosphoric acids can be used. Typically, aqueous phosphoric acid solutions are used which are about 70 to 90 percent, preferably about 85 percent, of phosphoric acid. The amount of phosphoric acid typically used in the practice of the present invention is from about 0.1 to 2.0 percent, preferably from about 0.2 to 1.0 percent, where the percentages are based on the total weight of the resin solids. For the purposes of the present invention, it is desirable that no excess of phosphoric acid be present, since the ex-ceased acid tends to impart hydrophilicity to the cured coating and may form salts during the high pressure steam retort process required for some foods and drinks. In those cases in which such a high degree of flexibility for final use is not critical, the resinous composition does not need to contain any chain extension with amine. This can be achieved by using a polybudo component that does not contain any polyepoxide extended in chain with amine. When the polymeric product of the present invention is used as part of a coating composition, it is typically mixed with a curing agent. The types and amounts of curing agents employed depend, in part, on the desired properties of the resulting product. Notwithstanding the above, typical examples of curative agents that may be employed include, without limitation, at least one of the following compounds: aminoplasts, phenolic curing agents and blocked or unblocked isocyanates. In many cases, the preferred curing agent consists of an aminoplast. Although the vinyl addition resins derived from N- (alkoxymethyl) methacrylamide and N- (alkoxymethyl) acrylamide are capable of crosslinking without an external crosslinking agent, said curing agents may, however, be added. The aminoplast curing agents are the condensation products of an aldehyde (for example, formaldehyde, acetaldehyde, crotonaldehyde and benzaldehyde) with a substance containing amino or amido groups (for example, urea, melamine and benzoguanamine). Products obtained from the reaction of alcohols and formaldehyde with melamine are preferred, urea or benzoguanamine. Alcohols useful in the preparation of the etherified products are monohydric alcohols, such as methanol, ethanol, propanol, butanol, hexanol, benzyl alcohol, cyclohexanol and ethoxyethanol. An etherified melamine-formaldehyde resin is an example of a preferred aminoplast curing agent. On the other hand, phenolic curing agents include the condensation product of an aldehyde with a phenol. In many cases, formaldehyde and acetaldehyde are the preferred aldehydes used when preparing phenolic curing agents. Various phenols can be used. Examples of these include, without limitation, at least one of the following: phenol, cresol, p-phenylphenol, p-tert-butylphenol, p-tert-amylphenol and cyclopentylphenol. In many cases, the preferred phenolic curing agent is the condensation of a phenol with formaldehyde, such as METHYLON 75108, a phenolic curing agent marketed by Occidental Chemical Corp. A series of blocked polyisocyanates are satisfactory crosslinking agents for use with the polymeric product of the invention. present invention. Suitable polyisocyanate crosslinking agents will be obvious to those skilled in the art after reading this description. In general, the organic polyisocyanates are blocked with a volatile alcohol, epsilon-caprolactam or ketoxime. These blocked polyisocyanates are typically deblocked at elevated temperatures (e.g., at temperatures above about 100 ° C). Typically, in the coating composition of the present invention, the polymer product is present in an amount of up to about 100 weight percent. Preferably, the polymer product is present in an amount ranging from about 60 to about 99 weight percent, more preferably, in an amount ranging from about 80 to about 97 weight percent e, even more preferably , in an amount ranging from about 90 to about 95 weight percent, where the percentages by weight are based on the weight of the total resin solids in the coating composition.

If used, the curing agent is typically present in an amount ranging from about 2 to about 40 weight percent, where the percentages by weight are based on the weight of the total resin solids in the coating composition. Preferably, the curing agent is present in an amount ranging from about 3 to about 15 weight percent and, more preferably, in an amount ranging from about 5 to about 10 weight percent. The coating compositions of this invention may contain other optional components, such as pigments, fillers, antioxidants, flow control agents, surfactants and the like. When used, these eventual components are typically present in amounts of up to about 30 weight percent of the coating composition, more typically in amounts of up to about 20 weight percent, and, even more preferably, in amounts up to about 20 weight percent. about 10 weight percent. Additionally, adjuvant resins, such as polyether polyols, polyester polyols, alkalis and acrylic polymers, can be mixed with the coating composition prepared according to this invention. In a preferred embodiment of the invention, the coating composition contains polytetramethylene glycol (for example, POLYMEG 1000, marketed by QO Chemicals, Inc.). Adjuvant resins, when used, are typically present in amounts of up to about 30 weight percent of the coating composition, more typically in amounts of up to about 20 weight percent and, even more typically, in amounts of up to about 10 weight percent. The coatings of the present invention have been found to have particular advantages when used in high speed roller coating lines for coating aluminum chaperone intended for containers, but the coatings could be applied to any substrate, particularly metal substrates, by any conventional procedure. Typically, the coatings are cured at elevated temperatures in the order of about 572 ° F to about 662 ° F (300 ° C to 350 ° C) up to a peak metal temperature of about 450 ° ± 30 ° F (232 ° ± 17 ° C) ). The coating thicknesses, determined by the weight of the dry film, typically range from about 1 to about 10 milligrams per square inch, more typically from about 3 to about 9 milligrams per square inch and, even more preferably, from about 5 to about 8 milligrams per square inch.

EXAMPLES The present invention is illustrated in more detail in the following examples, which are intended to be illustrative only and are not intended to limit its scope. Unless otherwise indicated, all percentages by weight are based on the total weight of the resin solids.

PREPARATION OF POLYMERIC PRODUCTS COMPARATIVE EXAMPLE 1 This comparative example illustrates the preparation of a polymer product, where an epoxy resin was phosphatized with phosphoric acid. The polymer product was prepared from the mixture of the following ingredients: 1 Bisepoxy with an epoxy equivalent weight in the range of 1,850 to 2,300, marketed by Shell Oil and Chemical Co. 2 Marketed as BUTYL CARBITOL, of Union Carbide Corp. 3 Aqueous solution 85% active. Charge 1 was added at room temperature and EPON 1007 was allowed to dissolve in the solvent mixture. The reaction temperature was increased to 100 ° C, at which time Charge 2 was added and the batch was kept at that temperature for about 30 minutes. Charge 3 was then added with a maintenance period of 2 hours then.

The polymer product thus formed was then diluted with Charge 6 to a theoretical solids content of about 53.55%.

EXAMPLE 2 This example illustrates the preparation of a phosphatic polymer product of the present invention, wherein, in the presence of an epsxy resin, the ethylenically unsaturated monomers are copolymerized under polymerization conditions initiated by free radicals. The unreacted epoxy groups are subsequently phosphated with phosphoric acid. The polymer product was prepared from the mixture of the following ingredients: Aqueous solution, 85% active.

To a suitable reaction vessel, equipped with a stirrer, a reflux condenser, a thermometer, a heating jacket and a nitrogen inlet, Charge 1 was added and the epoxy resin was allowed to dissolve in the solvents at room temperature. The temperature was then increased to reflux (140 ° C to 150 ° C), at which time the premix of Char 2 monomers and Charge 3 initiator solution were added at a constant rate over a period of time. 3 hours, while maintaining a reflux. The temperature was maintained at a temperature of 140 ° C to 150 ° C for one more hour, after which the two additions of Charge 4 initiator solution were carried out separately, with a maintenance period of 90 minutes after each addition. Next, the reaction temperature was reduced to 120 ° C and Charge 5 was added, with a subsequent maintenance period of 30 minutes. The deionized water of Charge 6 was then added and the reaction temperature was maintained at 120 ° C for a further 2 hours. The polymer product thus formed was then diluted with diethylene glycol monobutyl ether at a theoretical solids content of 50%.

EXAMPLE 3 This example describes the preparation of a polymeric product of the present invention, wherein the epoxy is extended in the chain before polymerization in itself initiated by free radicals of ethylenically unsaturated monomers and subsequent phosphating of the unreacted epoxy groups. The polymer product was prepared from the mixture of the following ingredients: Aqueous solution, 85% active.

To a suitable reaction vessel, equipped with a stirrer, a reflux condenser, a thermometer, a heating mantle and a nitrogen inlet, the epoxy resin of Charge 1 was added, which was then dissolved in the diethylene glycol monobutyl ether room temperature. The temperature was increased to 120 ° C, at which time the monoethanolamine was added to prolong the epoxy chain. The reaction temperature was maintained at that temperature until the epoxy equivalent weight of the reaction mixture reached 5,832. The temperature was then raised to reflux (140 ° C to 150 ° C), at which time the premix of monomers of charge 2 and the initiator solution of Charge 3 were added simultaneously at a constant rate throughout the a period of 3 hours, while it was maintained at reflux. The temperature was maintained at 140 ° C to 150 ° C for one more hour, after which the two additions of Charge 4 initiator solution were made separately, with a maintenance period of 90 minutes after each addition. Next, the re-action temperature was reduced to 120 ° C and Charge 5 was added, with a subsequent maintenance period of 30 minutes. The deionized water of Charge 6 was then added and the reaction temperature was maintained at 120 ° C for a further 2 hours. The polymer product thus formed was then diluted with diethylene glycol monobutyl ether at a theoretical solids content of 50%.

EXAMPLE 4 This example describes the preparation of a polymeric product of the present invention, wherein the epoxy is extended in the chain prior to the in situ polymerization initiated by free radicals of the ethylenically unsaturated monomers. The unreacted epoxy groups were not phosphatized below. The polymer product was prepared from the mixture of the following ingredients: fifteen twenty To a suitable reaction vessel, equipped with a reflux condenser and a means for maintaining a blanket of nitrogen, Charge 1 was added at room temperature with gentle stirring. The mixture was heated to 110 ° C, at which time Charge 2 was added. The reaction mixture was maintained at this temperature until the epoxy equivalent became constant. Charge 3 was then added and the mixture was heated to reflux at about 150 ° C. The flow of nitrogen was interrupted and then Loads 4 and 5 were added over a period of about 3 hours. Charge 6 was then added, followed by a maintenance of about 1.5 hours. Charge 7 was then added, followed by a maintenance of about 1.5 hours. The temperature was allowed to drop below 80 ° C, at which point Charge 8 was added. The polymeric product thus formed had a theoretical solids content of about 45%.

EXAMPLE 5 This example describes the preparation of a polymeric product of the present invention, wherein a mixture of epoxy resins with monoethanolamine and ammonia is chain prolonged before the addition of ethylenically unsaturated monomers under polymerization conditions initiated by free radicals. The unreacted epoxy groups were not phosphated. The polymer product was prepared from the mixture of the following ingredients: 1 Bisepoxy at 65% resin solids, with an equi-valent weight of about 2,200, the synthesis of which is described in Pat. USA No. 5,528,084.

Aqueous solution at 28%. To a suitable reaction vessel equipped with a reflux condenser and a means for maintaining a blanket of nitrogen, the ingredients of Charge 1 were added with gentle stirring at room temperature. The mixture was heated to 100 ° C and maintained at this temperature until the epoxy equivalents became constant, at which time the temperature was increased to 120 ° C. Loads 2 and 3 were then added over 3 and 4 hours, respectively, at a constant rate. The reaction temperature was subsequently maintained for 2 hours at 120 ° C. The reaction temperature was then reduced to 60 ° C, followed by addition of Charges 4 and 5, and maintained at this temperature until all the epoxy groups reacted, as measured by the epoxy equivalent weight (PEE). (It is considered here that an EEPS greater than 20,000 indicates that all epoxy groups have reacted). The reaction temperature was increased and maintained at 120 ° C for 2 hours. The product thus formed was then diluted with methyl ethyl ketone to a theoretical solid content of about 35%.

COMPARATIVE EXAMPLE 6 By way of comparison, this example illustrates the three-stage preparation of a resinous product formed by cold-blending an extended chain epoxy resin with a separate synthesized acrylic polymer. In step (A), a mixture of epoxy resins of the epoxy resins which were used in Example 5 immediately preceding with monoethanolamine and ammonium hydroxide was chain prolonged. In step (B), a polymer was separately formed under free radical polymerization conditions from the same mixture of ethylenically unsaturated monomers as that used in immediately preceding Example 5. In step (C), the extended chain epoxy resin of (A) was mixed cold with the polymer of (B). The resinous product was formed in three stages from a mixture of the following ingredients: 1 Bisepoxy at 65% resin solids with an epoxy equivalent weight of approximately 2,200, the synthesis of which is described in Pat. USA No. 5,528,084. 2 Aqueous solution at 28%. Step (A): To a suitable reaction vessel equipped with a reflux condenser and a means for maintaining a blanket of nitrogen, the ingredients of the Al Charge were added with gentle stirring at room temperature. The reaction was heated to 55 ° C, at which time the A2 Load was added over 15 minutes. The A3 Load was then added over 15 minutes. The mixture was maintained at 55 ° C, until the epoxy equivalent became constant. At this time, 66 grams of the solvent was diled. The product solids were adjusted to approximately 35% with methyl ethyl ketone. Step (B): To a separate suitable reaction vessel, equipped with a reflux condenser and a means for maintaining a blanket of nitrogen, Charge Bl was added and heated to reflux. The ingredients of Loads B2 and B3 were added at a constant rate to the reaction vessel over a period of 4 and 7.5 hours, respectively. After completing the additions of Loads B2 and B3, the reaction mixture was maintained at 100 ° C for 2 hours. The polymer thus formed was then diluted with Charge B4 to a theoretical solids content of about 42%. Step (C): The extended chain epoxy mixture from Step A and the polymer from Step B were mixed with gentle agitation under ambient conditions to form a cold-mixed resinous product.

EXAMPLE 7 This example describes the preparation of a chain-lengthened epoxy phosphated polymeric product with amine of the present invention. A mixture of resins with monoethanolamine was chain-lengthened with amine and a mixture of ethylenically unsaturated monomers, including N- (butoxymethyl) acrylamide (NBMA), was polymerized in itself under polymerization conditions initiated by free radicals. The unreacted epoxy groups were subsequently phosphatized. The polymer product was prepared from a mixture of the following ingredients: 1 Bisepoxy at 65% resin solids, with an epoxy equivalent weight of approximately 2,200, whose synthesis is You are written in Pat. USA No. 5,528,084 2 Bisepoxy with an epoxy equivalent weight of approximately 523, marketed by Shell Oil and Chemical Co. 3 55% active in a butanol / xylene mixture (82.2% / 17.8%). 4 Aqueous solution, 85% active. To a suitable reaction vessel, equipped with a reflux condenser and a means for maintaining a blanket of nitrogen, the ingredients of Charge 1 were added with gentle stirring at room temperature. The mixture was heated to 100 ° C and maintained at that temperature until the epoxy equivalents became constant. The reaction temperature was then increased to 120 ° C, at which time Charge 2 and Charge 3 were added at a constant rate over 3 and 4 hours, respectively. The reaction temperature was subsequently maintained at 120 ° C for 2 hours, followed by addition of Charge 4. The reaction temperature was then reduced to approximately 100 ° C, followed by addition of Charge 5. The reaction temperature and kept at 120 ° C for 2 hours. The polymer product thus formed was then diluted with Charge 6 to a theoretical solids content of approximately 40%.

PREPARATION OF COATING COMPOSITIONS EXAMPLE A This example describes the preparation of a coating composition of the present invention containing the phosphatized epoxy resin, EPON 1007, of Example 1. The coating composition was prepared by mixing with gentle agitation the following ingredients: 1 Product of phenol condensation with 3-chloropropene and formaldehyde, marketed by Occidental Chemical Corp.

After having thoroughly mixed the above ingredients, the coating composition was then reduced to a viscosity of application of "Ford Cup" at 22 seconds of # 4, having 32.6% by weight of theoretical content in solids, with the following solvent mixture: 32.6% methyl ethyl ketone, 30% diethylene glycol monobutyl ether, 28% n-butanol and 10% N-methylpyrrolidone. The resulting coating composition was applied to an aluminum-treated aluminum substrate (0.0088 inch gauge) using a coiled wire draw bar. The coated substrate was cured at a peak temperature of the metal surface of 465 ° E (241 ° C).

EXAMPLE B This example illustrates the preparation of a coating composition of the present invention containing the polymer product of Example 2, where, in the presence of EPON 1007 epoxy resin, a premix of ethylenically unsaturated monomers, including hydroxyethyl methacrylate, is copolymerized under conditions of polymerization initiated by free radicals. The resulting polymer product is then phosphatized. The coating composition was prepared by mixing with gentle agitation the following ingredients: After thoroughly mixing the above ingredients, the coating composition was then reduced to an application viscosity of "Ford Cup" at 22 seconds of # 4, having 32.1% by weight of theoretical content in solids, with the solvent mixture described. previously in Example A. The resulting coating composition was applied and cured as before in Example A.

ASSAY PROCEDURES Coating compositions were studied cured in a variety of performance properties. Dry adhesion was studied according to ASTM D3359 (Method B). The pencil hardness was studied according to ASTM D3363-92a using BEROL EAGLE TURQUOISE T-2375 pencils from Empire Berol USA. The solvent resistance was studied by rubbing with MEC according to ASTM D5402 using methyl ethyl ketone. The orange soda stain test can identify the ability of the coating to resist extraction of colorants from the food or beverage contained in the metal container. Cured test panels were immersed for five minutes in boiling orange soda. The panels were then well rinsed and compared with known commercial standards to determine the degree of staining (0 = better). Boiling DIET COKE® and boiling acetic acid tests can identify the ability of a coating to withstand exposure to acidic foods and beverages. The resistance to redness and adhesion were studied after immersing cured test panels for 15 minutes in DIET COKE®. The resistance to redness was determined by comparing the test panels immediately after the test with a control or commercial standard (0 = better). The adhesion was studied according to ASTM D3359 (Method B). The results are given as the percentage of adhesion of the coating to the substrate. The resistance to redness and adhesion were also studied after immersing the cured test panels for 30 minutes in a solution of acetic acid (3% by weight of glacial acetic acid in deionized water) boiling. The resistance to redness and adhesion were studied as described immediately above for boiling DIET COKE®. The flexibility ("flex") of the cured film was studied according to the following procedure. Test panels were cut into pieces of 2 inches x 4 1/2 inches, being the direction of the fiber of the substrate perpendicular to the length of 41/2 inches. Each test piece was folded around an inch H-mandrel along its length of 41 2 inches with the coated side facing out. Each bent test piece was then subjected to an impact test using an impactor weighing approximately 2.1 kilograms, dropped from a height of approximately 12 inches, such that one end was hermetically closed by the impact, forming a cradle. All test wedges were then soaked in a solution consisting of 350.4 grams of DIET SPRITE® and 20.8 grams of orthophosphoric acid (85%) at 120 ° F (49 ° C) for 16 hours. The results of the bending are given in "failure in millimeters", that is, the measurement in millimeters (mm) of the continuous cracking or appearance of spots measured from the closed end of the wedge. The comparison of the coating compositions of Examples A and B illustrates the advantages in terms of film continuity and appearance provided by the copolymerization of the ethylenically unsaturated monomers in the presence of the epoxy resin. Although the performance data in this high temperature cure were quite similar for both coating compositions, the appearance of the coating composition of Example A, which contained only the phosphatized resin, was poor, ie the film had craters and the flow was poor. In the following TABLE 1 the results for the tests described above are given.

EXAMPLE C This example describes the preparation of a coating composition of the present invention containing the phosphatic polymer product of Example 2, where, in the presence of the epoxy resin and under polymerization conditions initiated by free radicals, the ethylenically unsaturated monomers were polymerized in if you The unreacted epoxy groups were subsequently phosphatized. The coating composition was prepared by mixing with gentle agitation the following ingredients: 1 Benzoguanamide curing agent, marketed by Cytec Industries, Inc. The coating composition was reduced to 32.0% by weight solids with the solvent mixture described above in Example A. The resulting coating composition was applied to a glass substrate. chrome-treated aluminum (0.0088-inch gauge) using a coiled wire drawbar. The coated substrate was cured for approximately 25 seconds at 549 ° F (287 ° C), that is, at a peak metal surface temperature of 430 ° F (221 ° C).

EXAMPLE D This example describes the preparation of a coating composition of the present invention containing the phosphatized polymer product of Example 3, where, under polymerization conditions initiated by free radicals, the ethylenically unsaturated monomers were polymerized in the presence of the epoxy resin previously prolonged in chain with amine. The unreacted epoxy groups were then phosphatized. The coating composition was prepared by mixing with gentle agitation the following ingredients: 1 Benzoguanamine curing agent, marketed by Cytec Industries, Inc. The coating composition was reduced to 22.0% by weight solids with the solvent mixture described above in Example A. The resulting coating composition was applied to a coating substrate. chrome-treated aluminum (0.0088-inch gauge) using a coiled wire draw bar. The coated substrate was cured for approximately 13 seconds at 529 ° F (276 ° C) in an air convection oven, that is, at a peak metal surface temperature of 430 ° F (221 ° C). The cured test panels were studied according to the test methods described above for Examples A and B.

EXAMPLE E This example describes the preparation of a coating composition of the present invention containing the phosphatic polymer product of Example 4, where, under polymerization conditions initiated by free radicals, the ethylenically unsaturated monomers were polymerized in the presence of the epoxy resin previously extended in chain with amine. The unreacted epoxy groups were not subsequently phosphatized. The coating composition was prepared by mixing with gentle agitation the following ingredients: The coating composition was reduced to 21.0% by weight solids with the solvent mixture described above in Example A. The resulting coating composition was applied to a Chromium-treated aluminum substrate (0.0088-inch gauge) using a coiled wire draw bar. The coated substrate was cured for approximately 13 seconds at 529 ° F (276 ° C) in an air convection oven, that is, at a peak metal surface temperature of 430 ° F (221 ° C). The cured test panels were studied according to the test methods described above for Examples A and B. The comparison of the coating compositions of Examples C, D and E illustrates the advantages in terms of flexibility of the use of the polymer product containing Prolonged epoxy in chain with amine, as well as the advantages of phosphating unreacted epoxy groups. The results are shown in the following TABLE 2. TABLE 2 It is evident from the foregoing that various modifications can be made, which are obvious to those skilled in the art, in the embodiments of this invention without departing from its spirit and scope. Having thus described the invention, the following is claimed.

Claims (30)

Claims

1. A polymeric product formed by a process consisting of the following steps: (a) forming a prolonged resinous composition with amine having unreacted epoxy groups by mixing, under polymerization conditions initiated by free radicals, reagents consisting of: (i) a monomeric component ethylenically unsaturated polymerizable and (ii) a polyepoxide component, and (b) phosphatizing at least a portion of the unreacted epoxy groups of the resinous composition.

2. The polymer product of claim 1, wherein the polyepoxide component consists of a polyepoxide prolonged with amine.

3. The polymer product of claim 2, wherein the amine-extended polyepoxide is prepared by reacting a polyepoxide with an amine component.

4. The polymer product of claim 3, wherein the amine component consists of at least one compound selected from the group consisting of primary monoamines, polyamines with at least two primary amine groups and polyamines with at least two secondary amine groups.

5. The polymer product of claim 3, wherein the amine component consists of a diamine.

6. The polymer product of claim 3, wherein the amine component consists of at least one compound selected from the group consisting of butylamine, monoethanolamine and ethylenediamine.

7. The polymer product of claim 3, wherein the amine component consists of monoethanolamine.

8. The polymer product of claim 1, wherein the polyepoxide component consists of at least one polyepoxide compound having at least 1.0 epoxy groups per molecule.

9. The polymer product of claim 8, wherein the polyepoxide component consists of at least one compound selected from the group consisting of: polyglycidyl ethers of a polyphenol, polyglycidyl ethers of polyhydric alcohols and cycloaliphatic polyepoxides.

10. The polymer product of claim 9, wherein the polyepoxide component consists of at least one polyglycidyl ether of a polyphenol.

11. The polymer product of claim 10, wherein at least one polyglycidyl ether of a polyphenol is selected from the group consisting of: 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) ethane, , 1-bis (4-hydroxyphenyl) isobutane, 2,2-bis (4-hydroxybutyl-tertiary-phenyl) propane, bis (2-hydroxynaphthyl) methane, 1,5-dihydroxynaphthalene and 1,1-bis (4-hydroxy-3) -alylphenyl) ethane.

12. The polymer product of claim 9, wherein the polyepoxide component consists of at least one poly-glycidyl ether of a polyhydric alcohol.

13. The polymer product of claim 12, wherein at least one polyglycidyl ether of a polyhydric alcohol is derived from a polyhydric alcohol selected from the group consisting of: ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,4-butylene glycol, 1, 5-pentanediol, 1,2,6-hexanotriol, glycerol and 2,2-bis (4-hydroxycyclohexyl) propane.

14. The polymer product of claim 1, wherein the ethylenically unsaturated monomer component consists of at least one compound selected from the group consisting of: (a) vinyl aromatics, (b) alkyl esters of methacrylic acid having from 1 to 3 atoms of carbon in its alkyl group, (c) alkyl esters of acrylic acid having from 2 to 17 carbon atoms in its alkyl group, (d) alkyl esters of methacrylic acid having from 4 to 17 carbon atoms in the alkyl group , (e) vinyl monomers, (f) hydroxyalkyl esters of (meth) acrylic acid and (g) polymerizable ethylenically unsaturated acid functional monomers.

15. The polymer product of claim 14, wherein the ethylenically unsaturated monomer component consists of at least one aromatic vinyl compound selected from the group consisting of: styrene, alpha-methylstyrene, butyl-tertiary-styrene, vinyltoluene and vi-nilxylene.

16. The polymer product of claim 14, wherein the monomeric ethylenically unsaturated component consists of at least one alkyl ester of methacrylic acid containing from 1 to 3 carbon atoms in its alkyl group, selected from the group consisting of methyl methacrylate and methacrylate of ethyl.

17. The polymer product of claim 14, wherein the monomeric ethylenically unsaturated component consists of at least one alkyl ester of acrylic acid having from 2 to 17 carbon atoms in its alkyl group, selected from the group consisting of: ethyl acrylate, acrylate of propyl, butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate and stearyl methacrylate.

18. The polymer product of claim 14, wherein the ethylenically unsaturated monomer component consists of at least one vinyl monomer selected from the group consisting of; : ethylene, propylene, vinyl halides, vinylidene halides, vinyl versatate, vinyl acetate, dialkyl maleate, allyl chloride, allyl alcohol, 1,3-butadiene, 2-chlorobutene, methyl vinyl ether, acrylamide, methacrylamide, acrylonitrile and methacrylonitrile.

19. The polymer product of claim 14, wherein the monomeric ethylenically unsaturated component consists of at least one hydroxyalkyl ester of (meth) acrylic acid selected from the group consisting of: hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate and hydroxypropyl methacrylate.

20. The polymer product of claim 14, wherein the monomeric ethylenically unsaturated component consists of at least one polymerizable ethylenically unsaturated acid-functional monomer selected from the group consisting of: alpha, beta-ethylenic, unsaturated carboxylic acids containing from 3 to 8 carbon atoms; carbon.

21. The polymer product of claim 1, wherein the ethylenically unsaturated monomer component consists of at least one compound selected from the group consisting of: alpha, beta-ethylenically unsaturated carboxylic acids, alkyl esters of methacrylic acid, alkyl esters of acrylic acid, hydroxyalkyl esters of methacrylic acid, hydroxyalkyl esters of acrylic acid, N- (alkyloxymethyl) -acrylamide and N- (alkyloxymethyl) methacrylamide.

22. The polymer product of claim 21, wherein the ethylenically unsaturated monomer component consists of at least two of the compounds selected from the group consisting of: N- (butoxymethyl) methacrylamide, butyl (meth) acrylate, (meth) acrylic acid and methacrylate of hydroxyethyl.

23. The polymer product of claim 1, wherein at least a portion of the unreacted epoxy groups of the resinous composition are phosphated by reacting them with a phosphoric composition consisting of a phosphoric acid.

24. The polymer product of claim 23, wherein the phosphating composition consists of at least one compound selected from the group consisting of: orthophosphoric acid, superphosphoric acid, triphosphoric acid, polymeric phosphoric acids and partial anhydrides of phosphoric acids.

25. The polymer product of claim 1, wherein the reactants mixed together in step (a) further include an organic solvent component.

26. The polymer product of claim 25, wherein the organic solvent component consists of at least one organic solvent selected from the group consisting of: xylene, methyl ethyl ketone, methyl butyl ketone, ethanol, propanol, isopropanol, butanol, butoxy ethanol, ethylene glycol monobutyl ether and diethylene glycol monobutyl ether .

27. A coating composition consisting of: (a) a polymeric product formed by a process consisting of the following steps: (i) forming an extended resinous composition with amine having epoxy groups not reacted by mixing, under polymerization conditions initiated by radial free, reagents consisting of: a. a monomeric polymerizable ethylenically unsaturated component and b. a polyepoxide component, and (ii) phosphating at least a portion of the unreacted epoxy groups of the resinous composition, and (b) a curing agent.

28. The coating composition of claim 27, wherein the curing agent consists of at least one compound selected from the group consisting of: aminoplast curing agents, phenolic curing agents and isocyanate curing agents, blocked or unblocked.

29. The coating composition of claim 27, wherein the polymer product is present in an amount ranging from about 60 to about 99 weight percent and wherein the curing agent is present in an amount ranging from about 2 to about 2 weight percent. and about 40 weight percent, said percentages by weight based on the weight of the total resin solids in the coating composition.

30. The coating composition of claim 27, which further contains at least one of the following: pigments, fillers, antioxidants, flow control agents, surfactants, polyether polyols, polyester polyols, alkalis and acrylic polymers.