JPH0212513B2 - - Google Patents

Description

[Detailed description of the invention]

FIELD OF THE INVENTION This invention relates to methods for making polymeric compositions and, in particular, surface coating compositions. In particular, aqueous dispersions of certain reactive self-curing aqueous dispersion polymers, epoxy-acrylic copolymers, preferably aqueous mixtures containing polyphosphate additives, for use in food and beverage containers and the like. The present invention provides an aqueous can coating composition for internal coating for similar sanitary coating applications. Aqueous coating compositions useful as internal sanitary linings for metal containers are described in US Pat. No. 3,991,216. Such polymers consist of interpolymers of copolymerizable acrylamide monomers, carboxylic acid monomers and other ethylenically unsaturated monomers. However, such polymers are difficult to spray and often form films with poor film deformability, such as poor resistance to ethanol, making them unsuitable for alcoholic beverage containers. Epoxy resins are particularly desirable as surface coating materials for vehicles and as polymeric binders for pigments, fillers and other additives. Epoxy resins are advantageous because of their hardness, flexibility, adhesion, and chemical resistance. Aqueous dispersion coating compositions containing epoxy resins are also highly preferred for use in can coating compositions. For example, coatings for soft drinks and beer cans are limited by taste sensitivity. Such sanitary can coatings must not alter the taste of the canned beverage.
Taste problems can result from leaching of the coating composition into the beverage, absorption of aroma into the coating, sometimes chemical reactions, or a combination of these effects. In the method described in U.S. Pat. No. 4,212,781, an epoxy resin is modified by reacting an addition polymerizable monomer in the presence of at least 3% benzoyl peroxide, based on the weight of the monomer, at a suitable temperature. It describes how to do this. This reaction produces a reaction mixture containing a blend of in-situ resinous materials including an epoxy resin, an epoxy-acrylic graft polymer, and an epoxy-acrylic copolymer mixture containing a non-grafted polymer. In order to achieve stable dispersion of the reaction product obtained in the aqueous medium of the substrate, the monomer polymerized in situ must have an acid functionality (acid functionality).
contain monomers with a certain level of funtionality. In a suitable embodiment of U.S. Pat. No. 4,212,781, a polyglycidyl ether of bisphenol A is reacted with a mixture of addition polymerizable monomers containing acrylic acid, such as methacrylic acid. The epoxy resin has a molecular weight of 41,000 or more and accounts for 50% to 90% of the initial reaction mixture. The reaction occurs in the presence of benzoyl peroxide at a temperature above 80°C, preferably from about 110°C to 130°C, to effect addition polymerization of the monomers to form an addition polymer grafted onto the epoxy resin. The reaction product is dispersed in the substrate aqueous medium to provide an aqueous epoxy-acrylic copolymer mixture. Certain reactive, self-curing, water-dispersed polymers formulated with epoxy-acrylic copolymers and polymerizable phosphates have been found to provide excellent coatings suitable for internal coatings for beverage and food containers. The reactive self-curing water-dispersed polymers include copolymerizable monomers including reactive carboxy, hydroxy, amine or amide monomers and alkylolacrylamide monomers. The monomers can be copolymerized using a conventional one-step method. On the other hand, the monomers react stepwise to concentrate the alkynol acrylamide on the surface of the polymer particles, resulting in improved water-dispersed polymers with surprisingly good viscosity, stability, and rheological properties for spraying. I will provide a. By concentrating the alkynol acrylamide on the polymer surface, the alkynol acrylamide reacts with an addition polymer of a small amount of reactive monomer and an ethylene-type monomer to form a relatively hard polymer particle surface. and stabilize the viscosity of the water-dispersed formulation while providing significant tear resistance during subsequent spraying of the formulation. For optimal thermal curing of the compositions of this invention, the water-dispersed polymer reacts with the reactive monomers in the polymer to self-cure with the alkynol acrylamide.
By combining a reactive self-curing water-dispersed polymer with a water-dispersed epoxy-acrylic copolymer, the formulation provides an excellent internal coating, particularly when applied by spraying onto beverage cans. Additionally, preferred compositions of the invention include phosphated polymers, such as epoxy phosphated polymers. Incorporation of phosphated polymers provides improved coating properties such as solvent resistance and improved void properties. Reactive self-curing water-dispersed polymers are high molecular weight polymers that provide good film-forming properties and have the advantage of high solids content, good sprayability and minimal solvent usage. Other advantages of the invention will become apparent from the detailed description and examples. The present invention involves polymerizing an ethylene type monomer having a carboxy, hydroxy, amine or amide functional group together with an alkylolacrylamide monomer,
It is based on a particular self-curing water-dispersed polymer obtained by subsequently blending the water-dispersed polymer with an epoxy-acrylic acid copolymer and preferably with a phosphated polymer. The compositions of the present invention include a water-dispersed polymer blend of (a) a reactive self-curing water-dispersed polymer and (b) an epoxy-acrylic copolymer. More preferred compositions include (c) a phosphated polymer. Aminoplast crosslinked resins can be added to water-dispersed polymer formulations to provide improved curing properties. In the present invention, the aqueous composition includes certain reactive self-curing water-dispersed polymers formulated with epoxy-acrylic copolymers, phosphated polymers, and aminoplast crosslinked resins. Initially, with respect to reactive self-curing water-dispersed polymers, the reactive self-curing polymer includes (i) an alkylolacrylamide, preferably an alkylated alkylolacrylamide monomer, (ii) a reactive carboxy, hydroxy, A self-reactive alkynol acrylamide polymer of copolymerized ethylenically unsaturated monomers comprising a functional monomer consisting of an amine or amide monomer and (ii) another ethylenically unsaturated monomer. It is used to make water-dispersed polymers. Self-
Curable water-dispersed polymers are synthesized by conventional one-stage copolymerization or stepwise polymerization of monomers in water. This causes the alkylolacrylamide monomer to polymerize in the second polymerization stage. The monomer in the second stage is the first stage/second stage monomer 25/75 or
The weight ratio is 75/25. Alkylated alkylolacrylamide monomers are derivatives of acrylamide, methacrylamide, metallolacrylamide or similar alkyl-modified acrylamide monomers, and are described, for example, in US Pat. Preferably, the acrylamide monomer contains alkyl groups such as methyl, ethyl, propyl, n-
Butyl, isobutyl, and similar alkylated alkylolacrylamide monomers, butylated monomers are suitable. Functional monomers are monomers containing carboxy, hydroxy, amino, amide functional groups. Carboxy-containing monomers are acrylic acid and lower alkyl-substituted acrylic acids; preferred carboxylic acid monomers are acrylic acid and methacrylic acid. Hydroxy-containing monomers are hydroxy-containing ethylenically unsaturated monomers, including hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and methacrylate, 2-hydroxypropyl acrylate and methacrylate, and similar hydroxyalkyl acrylates.
The amide-containing monomer is acrylamide, methacrylamide or similar alkylalkyloacrylamide monomers. Other reactive monomers include N
- methylol acrylamide or methacrylamide monomers. The remaining monomers that are copolymerized with the alkylolacrylamide monomer and the functional monomer to form the reactive self-curing polymer are ethylenically unsaturated monomers such as vinyl monomers. For example, vinyl monomers such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, isopropyl acetate, and similar vinyl esters and vinyl halides such as vinyl chloride. Other ethylenically unsaturated monomers include monomers with ethylenically unsaturated double bonds, such as polymerizable allyl acrylic groups, fumaric acid residues, maleic acid residues, etc. . Furthermore, ethylenically unsaturated monomers include, for example, styrene, methylstyrene, similar alkylstyrenes, chlorostyrene, vinyltoluene, vinylnaphthalene, divinylbenzene, diallyl phthalate, similar diallyl derivatives, butadiene, alkyls of acrylic acid and methacrylic acid. Esters, similar ethylenically unsaturated monomers. Further suitable ethylenically unsaturated monomers are lower alkyl esters of acrylic acid or methacrylic acid having an alkyl group having 1 to 12 carbon atoms and aromatic derivatives of acrylic acid or methacrylic acid. Useful acrylic monomers include, for example, acrylic and methacrylic acids, methyl acrylate and methacrylate, ethyl acrylate and methacrylate, butyl acrylate and methacrylate, propyl acrylate and methacrylate, 2-ethylhexyl acrylate and methacrylate, cyclohexyl arylate and Methacrylate, decyl acrylate and methacrylate, isodecyl acrylate and methacrylate, benzyl acrylate and methacrylate, various reaction products such as butyl, phenyl and cresyl glycidyl ether reacted with acrylic acid and methacrylic acid. Hydroxyalkyl acrylates and methacrylates such as hydroxyethyl and hydroxypropyl acrylates and methacrylates and aminoacrylates and methacrylates. A further improved self-curing water-dispersed polymer comprises a hydroxyalkyl phosphate having at least one unsaturated double bond and an ethylene-type monomer mixture comprising a reactive functional monomer and an alkylolacrylamide monomer. It can be made by polymerizing with ester. Hydroxy alkyl phosphate ester monomers can be made, for example, by reaction of acrylic glycol with phosphorus pentoxide or by reaction of acrylic monoepoxide with perphosphoric acid. The ethylene type monomer mixture according to the invention contains 1% to 10% (by weight) of hydroxyalkyl phosphate ester to form a phosphated self-curing water-dispersed polymer. In yet another variation, water-dispersed self-curing polymers are prepared by combining an ethylene-type monomer mixture of a reactive functional monomer and an alkylolacrylamide monomer in the presence of a high molecular weight epoxy phosphate ester surfactant. The self-curing water-dispersed polymer is polymerized to emulsify or dispersed in water with an epoxy phosphate surfactant. Epoxy phosphate ester is an epoxy compound made by reacting 0.05% to 5% phosphoric acid with a relatively high molecular weight adduct of bisphenol A reacted with a low molecular weight epoxy resin such as Dow DER-333 (Dow). Contains phosphates. During polymerization, it acts as an epoxy-phosphate surfactant, controlling the particle size of the self-curing copolymer and further stabilizing the polymer particles as the particle size increases. The self-curing water-dispersed polymer containing phosphate provides improved self-curing reactivity, with the phosphate acting as a crosslinking promoter. Precipitated by phosphate cross-linking reaction,
The film properties provide improved corrosion resistance. The reactive self-curing alkylolacrylamide water-dispersed polymers are prepared by free radical-induced polymerization, preferably in water, using peroxides, azo catalysts, conventional redox catalysts, ultraviolet irradiation, etc., by the two-step polymerization described above. It is a copolymer made by copolymerizing ethylenically unsaturated monomers in water. Free radical initiators include various peroxides such as persulfate, benzoyl peroxide, tertiary butyl hydroperoxide, cumene hydroperoxide, and similar peroxide catalysts and azo compounds such as azo-isobutyronitrile, dimethylazobis- Contains isobutyrate. In addition, the initiator system contains about 0.1% initiator or catalyst, based on the weight of monomer, containing an alkali metal persulfate, or ammonium persulfate, with or without a reducing agent used to activate the persulfate. Use 1% to 1%. The resulting self-curing water-dispersed polymer contains from 1 to 20% of reactive carboxy, hydroxy, amine or amide monomers, with the remainder being other ethylenically unsaturated monomers.
Suitable water-dispersed polymers can be made by a variety of aqueous polymerization techniques. These polymers include emulsion polymers made by emulsion polymerization of monomers with a water-soluble initiator in the presence of an emulsifier, suspension polymers made by aqueous suspension polymerization using a suspending agent, and microemulsion polymers polymerized in aqueous microemulsion polymers in bulk particles and stabilized with long-chain aliphatic alcohols, or azeotropic emulsion co-emulsions made in water-solvent azeotropes using soap emulsifiers. It is a polymer. Other useful water-dispersed polymers are ionizing agents and U.S. Pat. No. 4,218,356
It can be produced by copolymerizing monomers in water containing a small amount of an organic co-solvent as described in the above publication. Next, regarding the epoxy-acrylic copolymer, the copolymer is an epoxy resin reacted with a monomer including an acrylic monomer or an epoxy resin reacted with a pre-made acrylic copolymer. It is a polymer. Suitable epoxy-acrylic copolymers include epoxy-acrylic graft copolymer mixtures containing an epoxy resin, epoxy-acrylic graft copolymers, ethylenically unsaturated monomers and epoxy resins containing at least 3% benzoyl peroxide (or is a non-grafted addition polymer prepared by polymerization with an epoxy resin in the presence of an equivalent amount of epoxy resin, and is described in particular in U.S. Pat. No. 4,212,781. Generally, in situ polymerization of the monomers is accomplished by reacting the ethylenically unsaturated monomers with an epoxy resin and at least 3% benzoyl peroxide, based on the weight of the monomers. Ethylenically unsaturated monomers include carboxy-functional monomers, including acrylic acid monomers such as acrylic acid, lower alkyl-substituted acrylic acids such as methacrylic acid, and the epoxy-acrylic acid copolymer mixture is dissolved in water. contains carboxy functional groups dispersed in A suitable acrylic acid is methacrylic acid. Other monomers are non-reactive under the intended polymerization conditions. Small amounts of other reactive monomers such as hydroxy monomers such as 2-hydroxyethyl acrylate, amide monomers such as acrylamide, N
- It is also possible to use N-methylol monomers such as -methylol acrylamide. The remaining monomers are non-reactive monomers such as esters of acrylates and methacrylates such as ethyl acrylate, methyl acrylate, isobutyl acrylate, styrene, vinyltoluene, vinyl acetate, vinyl chloride, vinylidene chloride, acrylonitrile, and acrylic acid alkyl esters. , lower alkyl esters, ie esters containing ester groups having 1 to 4 carbon atoms, especially ethyl acrylate. Other useful monomers belonging to this category are
_C1-15 alkyl acrylate esters, methacrylate esters, such as propyl acrylate, isopropyl acrylate, butyl acrylate, isobutyl acrylate, tertiary butyl acrylate, pentyl acrylate, decyl acrylate, lauryl acrylate, isobornyl acrylate, methyl methacrylate, They are butyl methacrylate, isobutyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, and nonyl methacrylate. Other useful monomers are commercially available vinyl monomers, such as styrenic monomers such as styrene, vinyltoluene, divinylbenzene, isobutylene and butadiene. The carboxy-functional polymer produced in situ has a molecular weight of 5,000 to 20,000, preferably 7,000 to 15,000.
It is. The carboxy content (-COOH) is at least 2% (by weight) of the monomer mixture, preferably 5%.
% or more. The epoxy resin part of the epoxy-acrylic acid copolymer is aliphatic or aromatic,
Aromatic epoxy resins are suitable. The most preferred epoxy resins are polyglycidyl ethers of bisphenol A, especially resins with a 1,2-epoxy equivalent of about 1.3 to 2. Its molecular weight is between 350 and 20,000, preferably 4,000 for sanitary coating compositions.
or 10,000. If the polymer formulation polymerized at the plant contains 50% to 90% (by weight) of the total polymer solids epoxy resin, the epoxy resin has a molecular weight
Must be between 4000 and 10000. Mixtures of monoepoxides and diepoxides are preferred.
Another process variation is to introduce aromatic polyethers, phenols, or similar monoreactive epoxy blocking agents that do not contain oxirane functionality by reaction of epoxy groups with benzoic acid.
Yet another variation is to provide an epoxy phosphate as the epoxy resin component of the epoxy-acrylic copolymer, the epoxy phosphate preferably containing no more than about 5% (by weight) of co-reactive phosphate. , the epoxy phosphate is then reacted with an acrylic monomer containing a carboxyl monomer and copolymerized in situ with a peroxide catalyst of at least 3% based on the weight of the monomer to form an epoxy phosphate. An epoxy-acrylic composition is made that includes an allyl chloride graft copolymer.
In a preferred implementation, the epoxy resin is an aromatic polyether containing no oxirane functionality, an aromatic polyether having one oxirane group, and two
It is a mixture of aromatic polyethers having oxirane groups. This mixture of epoxy functionality maximizes miscibility. However, aromatic polyethers that do not contain oxirane functionality can be added later. The mixture can then be heated and agitated to increase the intimacy of the bond between the various components. In situ epoxy-acrylic copolymers can be made by in situ polymerization of ethylene monomers and epoxy resins. The epoxy resin is heated in a reactor where the polymerizable monomer can be added slowly along with the solvent and free radical initiator over a period of at least 2 or 3 hours. Although the reaction can be carried out without a solvent, the use of a solvent is suitable for the in situ polymerization of the monomers in the presence of the epoxy resin. A preferred solvent system includes two miscible solvents, one of which dissolves the epoxy resin;
The other one dissolves the monomer. Particular solvents that are satisfactory for epoxy resins are xylene, benzene, ethylbenzene, toluene, and alkoxyalkanols. As for monomers, alcohols such as methanol, ethanol, propanol, butanol, etc. are suitable. Butanol is particularly suitable. Ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, hexane, mineral spirits, etc. are suitable. In the next step, the dispersion in water, the solvent is a water-soluble substance such as acetone, butanol, ethanol, propanol, ethylene glycol monoethyl ether, and the like. Typically the amount of solvent may be from 5 to 30% (by weight) based on the total weight of other ingredients. In fact, the mixture of epoxy resin and polymerizable monomer is reacted in the presence of a free radical initiator, preferably of the peroxide type, most preferably benzoyl peroxide. Representative and useful free radical initiators are cumene hydroperoxide, benzoyl peroxide, tertiary perbenzoate, tertiary butyl peroxide, lauroyl peroxide,
These include methyl ethyl ketone peroxide and chlorobenzoyl peroxide. Benzoyl peroxide is preferred as a free radical initiator for use in the practice of this invention. The amount of free radical catalyst is expressed in weight percent or equivalents of benzoyl peroxide based on the total weight of polymerizable monomers at the temperature used. The amount of catalyst is at least 3%, preferably 4% (by weight) or equivalent of benzoyl peroxide based on the weight of monomer. The reaction temperature is preferably 80°C to 130°C. The temperature can be adjusted within a relatively wide range depending on the reactivity of the mixture. In this case, the operating temperature is selected from 30°C to 200°C depending on the purpose and operating conditions. After adding the monomers, the reaction temperature is maintained for no more than 3 hours to complete the conversion of the monomers. Epoxy-acrylic graft polymers, in-situ formed carboxy-functional polymers containing at least about 20% polymerized monoethylenically unsaturated carboxylic acid monomers, based on the total weight of monomers, by in-situ polymerization of the monomers. and non-grafted epoxy resins and are described in US Pat. No. 4,212,781. Epoxy-acrylic copolymers are also epoxy-acrylic ester copolymers made from the epoxy resin and copolymerized monomers including carboxy monomers. Epoxy-acrylic copolymers include acidic or carboxy copolymers esterified with epoxy resins. Epoxy-acrylic esters can be made by esterifying solvent-soluble carboxy-functional polymers with epoxy resins. The esterification reaction is preferably carried out in an organic solvent in the presence of a sufficient amount of an amine catalyst to produce a non-gelled epoxy ester copolymer. Esterification reaction is 0.3% to avoid gelation.
can be carried out in the presence of an amount of amine catalyst greater than the amount of catalyst. The epoxy-acrylic ester is also preferably carried out in the presence of an amine esterification catalyst of 2% or more based on the weight of the reactants to be esterified. The preformed acrylic polymer preferably comprises at least about 20% based on the total weight of the copolymer.
(by weight) of copolymerized ethylenically unsaturated monomers. The epoxy resin part is at least approx.
40% epoxy-acrylic ester polymer, containing oxirane functionality in a stoichiometric deficit of about 1:2 to 1:20 to carboxy functionality in a pre-carboxyl-preformed polymer.
The excess carboxy functionality in the epoxy-acrylic ester reacts with the substrate to provide a means for dispersing the polymer in water, allowing the reaction product to self-emulsify in water. The details are published in European Patent Publication No. 0006334 (1980, 1
(Released on September 9th). Another method of making epoxy-acrylic copolymers involves reacting an epoxy resin with a preformed carboxy polymer of polymerized ethylenically unsaturated monomers in the presence of an amine and a significant amount of water. The goal is to create complex quaternary ammonium-amine salt bonds in epoxy-acrylic copolymers. The details are in the US Patent No.
It is described in Publication No. 4247439. A further modification of the epoxy-acrylic copolymer is to prepare a pre-formed carboxy polymer of polymerized ethylene monomers containing carboxy monomers in the presence of a melamine resin, then add the pre-formed carboxy polymer The purpose of the combination is to react with an epoxy resin in the presence of a large amount of amine, and is described in US Pat. No. 4,289,811. Additionally, the epoxy-acrylic copolymer is comprised of an epoxy phosphate ester and an acrylic copolymer to form the epoxy-acrylic portion of the mixture containing the self-curing water-dispersed polymer. Epoxy phosphate esters can be made by reacting polymeric epoxy resins with 0.05% to 5% phosphoric acid. The acrylic copolymer is preferably a resinous copolymer made by polymerizing an acrylic monomer and an ionizable functional monomer, such as acrylic acid or methacrylic acid, in water containing an ionizing agent that ionizes the functional groups of the functional monomer. It is a polyelectrolyte polymer. With regard to the phosphorylated polymers which can optionally and preferably be added to the polymer formulations of the present invention, mono- and dialkyl esters of phosphoric acid of the phosphorylated polymers, phosphorylated epoxidized oils,
Phosphated epoxidized polybutadiene copolymer,
phosphated acrylic copolymers, phosphated polyesters, phosphated copolymers containing copolymerized phosphated monomers, epoxy phosphates, and phosphated epoxy-acrylic copolymers. Phosphate esters of alkyl alcohols include phosphoric acid and carbon atoms of 2 to 20, preferably 4 to 8 carbon atoms.
A mixture of phosphoric acid mono- and dialkyl esters made by reacting with aliphatic alcohols is described in US Pat. No. 2,005,619. Other water-dispersed phosphated copolymers can be made by polymerizing the monomers in water containing an ionizing agent and a small amount of an organic cosolvent, such as those described in US Pat. No. 4,218,356. The polymer is phosphated. Water-dispersed phosphated copolymers contain an aqueous dispersion of resinous polyelectrolytes produced by addition polymerization of ethylenically unsaturated monomers in water, and have functional groups such as carboxyl groups that can be ionized in water. Contains at least 1 part of monomer. The water here contains an ionizing agent for neutralizing at least a portion of the functional groups in the resulting copolymer, as described in US Pat. No. 4,218,356. Phosphated resinous polyelectrolytes are made into an aqueous medium containing a co-solvent, an ionizing agent is added prior to or alternating with the monomers, and the monomers are polymerized by free radical polymerization and dispersed in water. Make a resinous polymer electrolyte. The remaining oxirane groups are then phosphated to form a water-dispersed phosphated polymer. Phosphated epoxidized oils include phosphate esters of epoxidized oils or epoxy polybutadiene copolymers and are made by reacting an epoxidized polymer with up to 5% phosphoric acid. Phosphated acrylic copolymers can be made by reacting acrylic copolymers containing oxirane or hydroxy functionality with phosphoric acid. Acrylic copolymers contain ethylenically unsaturated monomers, especially glycidyl acrylate or methacrylate or hydroxy-functional monomers and other ethylenically unsaturated monomers such as methyl methacrylate, butyl methacrylate, hexyl methacrylate, octyl methacrylate. , isodecyl methacrylate, stearyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, decyl acrylate, and dodecyl acrylate, substituted alkyl esters such as hydroxyethyl and hydroxypropyl acrylate and methacrylate , styrene, alpha-methylstyrene, alpha-chlorostyrene and vinyltoluene. Phosphated acrylic copolymers can be made by reacting oxirane or hydroxy functionalized acrylic copolymers with phosphoric acid. The acrylic copolymer here comprises copolymerized ethylene monomers such as glycidyl acrylate or methacrylate or hydroxy-functional monomers. Phosphated polyesters are polyesters with terminal hydroxyl groups that have been reacted with phosphoric acid, whereas the original polyesters are dicarboxylic saturated or unsaturated acid polyesters esterified with simple glycols. Glycol is ethylene glycol,
propylene glycol, diethylene glycol,
Dipropylene glycol, 1,3 or 1,4 butanediol, hexanediol, and small amounts of polyols such as pentaerythritol, triethylene glycol, trimethylolpropane, or glycerol. The unsaturated dicarboxylic acid component is an alpha-beta unsaturated dicarboxylic acid or anhydride such as maleic acid, fumaric acid, itaconic acid, and the like. Saturated dicarboxylic acids or anhydrides are phthalic anhydride,
or phthalic acid, terephthalic acid, isophthalic acid, adipic acid, sebacic acid, succinic acid or similar saturated acids or anhydrides thereof. Small amounts of monocarboxylic acids or fatty acids can also be added. Also lower alkyl acids, lauric acid, palmitic acid,
Myristic acid and stearic acid may also be included. Hydroxy-terminated polyesters are made by reacting excess equivalents of glycols and polyols with under-equivalents of carboxylic acid. Here, excess hydroxyl groups are converted into phosphates with phosphoric acid. Similarly, polyesters containing terminal glycidyl groups react with phosphoric acid to form phosphated polyesters. Phosphated copolymers can be made by copolymerizing ethylene monomers with phosphated hydroxyethyl acrylate or similar phosphated monomers. Phosphating copolymers obtained by copolymerizing an ethylenically unsaturated monomer with a phosphorylated ethylenically unsaturated monomer can be obtained by combining the ethylenically unsaturated monomer with the phosphorylating monomer using an aqueous polymerization process, such as suspension. , emulsification, aqueous ionizable resin polymer dispersants, microemulsion azeotropic methods, and polymerization methods similar to those described above. Phosphated epoxy-acrylic copolymers can be made by polymerizing ethylene-type monomers, including ethylene carboxy monomers, in situ in the presence of an epoxy phosphate resin to form phosphated epoxy graft copolymers. can. Other phosphated epoxy-acrylic copolymers are prepared by reacting an epoxy resin with a pre-formed acrylic carboxylic acid copolymer in the presence of a large amount of an amine to form an epoxy-acrylic ester copolymer or An epoxy-acrylic quaternary ammonium copolymer can be made in the presence of water. Here, phosphoric acid is reacted after or before the formation of the epoxy acrylic copolymer. Other phosphated epoxy polymers include epoxy polymers that react with phosphoric acid to form phosphated epoxy ester polymers. The phosphated epoxy polymer contains at least about 0.1 equivalents of phosphate per equivalent of epoxy;
Preferably it contains 0.1 to 1 equivalent of phosphate.
In this case, one mole of monoepoxy polymer can contain up to about one mole of phosphate. On the other hand, one mole of diepoxy polymer can contain up to two moles of phosphate. The phosphated epoxy polymer is about 0.05% to 5%, preferably 0.1% to 3%.
% of reacted phosphoric acid. A significant excess of phosphate reactant is undesirable. Phosphated epoxy resins are prepared by heating an epoxy polymer solvent dispersed in a suitable solvent such as methyl ethyl ketone or 2-butoxyethanol and then reacting with phosphoric acid or preferably polyphosphoric acid at a reflux temperature of 120°C to 145°C.
The reaction is carried out for 8 to 8 hours to complete the reaction between the reacting epoxy group and the phosphoric acid. The manufacturing method of epoxy phosphate resin is disclosed in US Pat. No. 4,289,812 and US Pat.
It is described in Publication No. 4316922. In a further variation of the invention, epoxy phosphates can be made by reacting unphosphated epoxy resins with epoxy resins containing a high amount of phosphate. The resulting epoxy resin mixture contains about 0.05% to 5% (by weight) of co-reacted phosphoric acid. For example, 9 parts by weight of an unphosphated epoxy resin and 1 part by weight of a phosphated epoxy resin are reacted at about 120°C for at least 2 hours to give a
% reacted phosphoric acid containing epoxy phosphate. In fact, unphosphated epoxy resins can be reacted with phosphated (10%) epoxy resins at sufficiently high temperatures and for sufficiently long periods of time to convert the mixture primarily to monophosphates. To hydrolyze the phosphated mixture, approximately 2% water, based on solids, can be added to accelerate the hydrolysis. Preferably, the mixture can be changed to mainly a monophosphated epoxy resin.
The epoxy phosphate containing 0.05% to 5% reacted phosphoric acid can then be dispersed in the amine and water mixture by mechanical mixing. The resulting water-dispersed epoxy phosphate can be added to an epoxy-acrylic copolymer composition to form a self-curing water-dispersed polymer. A highly desirable sprayable coating composition can be prepared by mixing a reactive self-curing polymer, an epoxy-acrylic copolymer, and a phosphated polymer as a matrix polymer. Generally, the composition will include about 5% to 99% self-curing polymer;
Contains 1 to 70% epoxy-acrylic copolymer and 0 to 50% phosphate polymer. The preferred coating composition of the present invention is 40% by weight
to 90% reactive self-curing polymer, about 1%
to 30% epoxy-acrylic copolymer and 0
It contains from 3% to 30%, preferably from 3% to 20%, most preferably from 3% to 15% phosphate polymer.
The binder matrix polymer composition is then mixed with a water-dispersed crosslinking component to serve as an aminoplast resin suitable for heat curing and crosslinking with the carboxy functional groups of the epoxy-acrylic copolymer mixture. The coating composition adhesive is based on the weight of the polymer.
% to 15%, preferably 1% to 10%, of an aminoplast crosslinked resin and 85% to 100% of the matrix polymer composition. With respect to aminoplast crosslinked resins, the aminoplast is a melamine or melamine derivative such as methylolmelamine or similar alkylated melamine-
It is formaldehyde resin. Additionally, aminoplasts include benzoguanamine, acetoguanamine and urea-formaldehyde. Commercially available water-soluble or water-dispersible aminoplasts for this purpose are Cymel 301, Cymel 303, Cymel 370.
and Kumel 373 (made by American Cyanamid, Stanford, Connecticut) (American
cyanamid, Stamford, Conn.). The aminoplast is melamine-based, e.g. hexamethoxy-methylmelamine (Kumel 301).
(And Beetle 80 (manufactured by American Cyanamid) is a methylated or butylated urea.
Other suitable aminoplast resins are aldehyde and formal guanamine; amerine; 2-chloro-
4,6-diamine-1,3,5-triazine; 2
-Phenyl-P-oxy-4,6-diamino-
It is a reaction product with 1,3,5-triazine and 2,4,6-triethyl-triamino-1,3,5-triazine. Mono-, di- or triarylmelamines such as 2,4,6-triphenyl-
Triamino-1,3,5-triazine is suitable. Water-dispersed coating compositions can be made by mixing together various water-dispersed polymers. Self-curing polymers are made in aqueous solvents. Aminoplast polymers can be dispersed in water by mechanical mixing. Epoxy-acrylic copolymers and phosphate polymers are made in a solvent and then fugitive bases such as primary, secondary
Dispersions in water can be made using primary and tertiary alkyl, alkanol, aromatic amines, or mixed alkanolalkyl amines such as mono-ethanolamine, dimethylethanolamine, diethanolamine, triethylamine, dimethylaniline, ammonia hydroxide, and the like. US Patent No.
It is described in Publication No. 4212781. On the other hand, one of the polymers of the formulation can be prepared in the presence of one of the other polymers in the polymer formulation of the invention. Water-dispersed self-containing alkylalkylol acrylamide monomers
The curable polymer can be polymerized in the presence of an epoxy-acrylic copolymer or a phosphated polymer or mixtures thereof. Similarly, epoxy-acrylic copolymers or phosphated polymers are made by polymerizing the monomers in situ in the presence of other preformed polymers or in the presence of self-curing polymers. It can be made by polymerization on the spot. The amount of water contained in the coating composition containing the epoxy-acrylic copolymer, the reactive self-curing polymer, the phosphated polymer and the aminoplast resin is adjusted to the desired viscosity in relation to the method of use. For spraying, preferred coating compositions have a polymer solids content of 10% to 30% (by weight).
and water containing small amounts of other volatile components such as solvents.
Contains 70 to 90% (by weight). For applications other than spraying, the aqueous polymer dispersion can contain about 10% to 40% water. Organic solvents can be used for spraying or other uses. Other solvents are normal-butanol, 2-butoxy-ethanol-1, xylene,
Contains toluene. Also preferably normal-butanol is used in combination with 2-butoxy-ethanol-1. The coating compositions of the present invention can be colored and/or opacified with known pigments and opacifiers. For many applications, including food applications, a suitable pigment is titanium dioxide. The aqueous coating compositions obtained can be satisfactorily applied by conventional methods known in the coatings industry. In this case, spraying, rolling, dipping and flow coating methods can be used for transparent as well as colored films. Moreover, spraying is appropriate. The coating is heated to about 95°C or more after being applied to the metal material.
It can be thermally cured at a temperature of 235° C. or higher, which is sufficiently high to complete the cure or volatilize the volatile components. Upon thermal curing, the reactive self-curing polymer becomes reactive and self-curing. Here the alkyl group of the alkoxyacrylamide is split from the alkylol acrylamide chain, and the acrylamide chain of the polymer is reacted with a functional monomer of carboxy, hydroxy, or amide group or with an epoxy-acrylic copolymer mixture and an epoxy phosphoric acid. Can react with carboxy or hydroxy functional groups in salts and aminoplast resins. Metal sheet materials for beverage containers, especially containers for carbonated beverages such as beer, are coated with 0.5 to 15 polymer coats per square inch of exposed metal surface.
Must be used in milligrams. For application, the water dispersion coating may be 0.1 to 1 mil thick. Next, the present invention will be explained with reference to Examples. All parts are parts by weight, all percentages are percent by weight, and all temperatures are at 0°C. Example 1 Method of Preparing a Self-Curing Copolymer A two-step heat-curing acrylic emulsion copolymer containing styrene/ethyl acrylate/methacrylic acid/N-isobutoxymethylol acrylamide was prepared using 100 parts deionized water and 0.80 parts sodium. Dihexyl sulfosuccinate was charged to the reactor and heated to 76-77° C. with stirring under nitrogen flow. At the controlled reaction temperature, nitrogen bubbling is discontinued and 0.10 part of ammonium bicarbonate salt is added. A mixture of 3.0 parts styrene and 2.0 parts ethyl acrylate was then added to the reactor and emulsified for 10 minutes. Now 0.25 parts of ammonium persulfate is added and monomer stage no.
1 was reacted for 20 minutes before starting. Monomer stage No. 1 contained 33.0 parts styrene, 26.5 parts ethyl acrylate, and 3.50 parts methacrylic acid. The monomer stage was added to the reactor at a constant rate. Addition was completed after 3.0 hours. Monomer stage No. 2 is 14.0 parts styrene, 11.5 parts ethyl acrylate, 1.5 parts methacrylic acid, and 0.5 parts methacrylic acid.
of N-isobutoxymethylol acrylamide. It was then added continuously to the reactor over a period of 1.25 hours. After monomer mixture No. 2 was completed, the batch was maintained at reaction temperature for 2 hours. It was then cooled and filtered. The size of the monomer stages is not limited to this example. Satisfied spray characteristics are determined by the 1st stage/2nd stage ratio.
A weight ratio of 25/27 to 75/25 was maintained. Examples 2-10 Other self-curing copolymers were prepared with alkylolacrylamides in the second monomer stage in a manner similar to Example 1.

TABLE 3 Hydroxyethyl Acrylate Examples 11-13 In contrast to Examples 1-10, the emulsion polymers were prepared to contain equal amounts of alkylolacrylamide in both monomer stages.

[Table] Mid-level

[Table] Example 14 (A) Production of epoxy-acrylic copolymer An epoxy-acrylic graft copolymer was produced according to the following recipe. 1047.8 grams (2.31 pounds) of epoxy resin (DER-333) was heated to about 82°C in a stirred reactor. Bisphenol A 530.7 grams (1.17 pounds) was added with stirring. The reactor was then heated to about 191°C for 2 hours. It was heated for an additional 2 hours. The viscosity and oxirane content were checked periodically. The target oxirane number was approximately 0.6% and the viscosity was between Z and Z ₁ at 25°C (Gardner-Holt). When these values are reached, 2-butoxy-ethanol-1612.4
grams (1.35 lbs.) and then 920.8 grams (2.03 lbs.) of N-butanol. At this point, the molecular weight of the epoxy resin was approximately 5500 based on oxirane content. 290.3 g (0.64 lb) methacrylic acid, styrene in separate container
18.1 g (0.4 lb), ethyl acrylate
199.6 grams (0.44 lb) and 45.4 grams (0.1 lb) of benzoyl peroxide were charged and mixed. The monomer mixture was added at a constant rate to the reactor containing the epoxy resin over a period of 2 hours. The reaction temperature was maintained at 118°C. Viscosity was checked periodically. The batch was cooled to 85°C.
The acid value was 85 based on solid content. The resin batch was then fed to a stirred reduction vessel containing a mixture of 4966.9 grams (10.95 pounds) of deionized water (resistance of at least 50,000 ohm-centimeters) and 258.6 grams (0.57 pounds) of dimethylethanolamine. The temperature of the resulting mixture was 50°C. Maintain this temperature for approximately 1 hour, then add cooled deionized water to the formulation.
2268 grams (5 pounds) was added and cooled to below 32°C. (B) Effect of changes in composition In the above examples, the amount of benzoyl peroxide used during the reaction was about 6.8% (by weight) based on the weight of the monomer mixture. The effect of changes in the composition in the ratio of epoxy resin and several monomers in the monomer mixture is shown in Table 3.

【table】

[Table] Example 15 Method A Epoxy phosphate was made according to the following recipe. Butyl cellosolve with epoxy resin (DER-
333) 1005 grams and 340.5 grams of bisphenol A were charged into a round bottom flask, size 5, equipped with a stirrer, condenser and thermometer and heated to 140°C.
When the temperature reaches 140℃, change the heating to external heat188
I raised it to ℃. When the external heat temperature reached its peak, the batch was maintained at 175°C and heated for an additional 5 hours.
Viscosity and oxirane content were measured periodically. The desired oxirane number was about 2.28%, with a non-volatile property of 40% and a viscosity between I and J. When this value was reached 227 grams of butyl cellosolve was added.
The batch was cooled to 120°C. When the batch temperature reached 120° C., a mixture of 63.64 grams of 85% phosphoric acid and 20 grams of butyl cellosolve was added dropwise. The temperature of the batch was raised to 145°C using external heat. 120℃
and maintained at this temperature for 30 minutes. 27 grams of water was added to the reaction mixture. The batch was heated at 120°C for an additional 4 hours. Then 241 grams of butanol,
78 grams of butyl cellosolve, 122.5 grams of dimethylethanolamine and 2500 grams of deionized water were each added. The final mixture was heated for 2 hours to obtain a stable emulsion. Method B Epoxy phosphate is epoxy resin (DER-
333) by adding 816 grams of bisphenol A, 384 grams of bisphenol A, and 163 grams of butyl cellosolve to a 5-size round bottom flask equipped with a stirrer, cooler, and thermometer and heating to 140°C. When the temperature reaches 140℃, stop heating and increase the external heating temperature to 155℃
I gave it up to When the external heating temperature reaches its maximum,
The temperature was maintained at 175°C for an additional 2 hours. Viscosity and oxirane content (%) were measured periodically. The oxirane value was approximately 0.87%. The viscosity was X-Y at 40% NV in butyl cellosolve. When these values were obtained, 163 grams of butyl cellosolve was added and the batch was cooled to 125°C. A mixture of 14.2 grams of polyphosphoric acid (FMC) and 50 grams of butyl cellosolve was added over a period of 45 minutes. An excess of 30 grams of butyl cellosolve was added. The batch was maintained at 120°C for 1 hour. Then 23 grams of deionized water was added to the reaction mixture. The batch was maintained at 120°C for an additional 2 hours. Heating was then discontinued and 203 grams of butanol was added over a period of 8 minutes. 1550 grams of deionized water and 17.4 grams of dimethylethanolamine were heated to 60° C. in a container. The above resin was gradually dropped into the aqueous amine mixture to obtain a stable emulsion. The resulting emulsion was adjusted to 25% NV by adding 1000 grams of deionized water. Next, stirring was continued for 2 hours to obtain a homogeneous mixture. Various epoxy phosphates were prepared according to Method A or Method B with the following molecular weight changes.

Table: Example 16 Polymer Formulation Approximately 860 grams of the emulsion copolymer obtained from Example 1 was added to a Content 5 reaction flask along with deionized water to produce approximately 23% NVM. The resulting mixture was gently stirred for approximately 15 minutes to prevent foaming. Thereafter, a premix of 15.5 grams of DMEA and 82.8 grams of water was added and stirred continuously for about 30 minutes. Approximately 72.8 grams of butoxyethanol was added and stirred for 30 minutes. Thereafter, 220.8 grams of the epoxy phosphate obtained from Example 15 and 815 grams of the epoxy acrylic copolymer obtained from Example 14 were slowly added over a period of about 1 hour. Normal-butanol 259.3
grams and mixed with vigorous stirring for about 15 minutes. Approximately 31.3 grams of the aminoplast resin Kumel 303 was then added and mixed for approximately 15 minutes. Deionized water approx.
68.1 grams were added and mixed for approximately 1 hour. The resulting polymer mixture is excellent as a composition for spray coating the interior of cans. Several formulations are shown in Table 5 to show the effects of varying the compositions of epoxy phosphate, water-dispersed copolymer, and epoxy acrylic copolymer. The epoxy phosphate was Example 15. The epoxy acrylic was Example 14(a). The water-dispersed copolymers were those from Examples 1 to 10.

【table】

[Table] Example 17 Polymer formulation for coating Similar to Example 16, a coating composition was prepared as follows. Add 1031 grams of emulsion from Example 13 to deionized water.
Content 5 was added to the reaction flask along with 922 grams. The mixture was stirred gradually to prevent foaming. A premix of 18.7 grams of DMEA and 40.0 grams of water was added and pre-stirred for about 30 minutes.
Next, 73.6 grams of butoxyethanol was added and stirred for 30 minutes. Then normal-butanol
263.7 grams were added and mixed by vigorous stirring for approximately 15 minutes. Next, 354.0 grams of the epoxy acrylic copolymer from Example 14 and 183.0 grams of the epoxy phosphate salt from Example 15 were slowly added over a period of about 1 hour. 31.3 grams of the aminoplast resin Kumel 303 is added to the resulting polymer mixture to provide an excellent spray composition suitable for spray coating the interior of beverage cans. The spray coated cans are heat cured to provide an excellent cured can coating. Example 18 Coating Polymer Formulation Similar to Example 16, a coating composition was made as follows. Approximately 1000 grams of the emulsion copolymer obtained from Example 1 was slowly added to the Content 5 reaction flask with stirring. A premix of 18.1 grams of DMEA and 37 grams of water was gradually added to the latex with constant stirring. Approximately 226 grams of butanol was added over one hour. Then Example 14
Approximately 711 grams of the epoxy acrylic copolymer obtained from the above were added over a period of 15 minutes. Approximately 72.5 grams of butoxyethanol was then added, followed by 900 grams of deionized water. The mixture was gradually stirred for an additional hour. The resulting polymer mixture provides an excellent coating composition suitable for spray coating the interior of cans when mixed with an aminoplast crosslinker. The coating applied to the can by spraying cured to give an excellent can coating. Example 19 Polymer formulation for coating A coating composition was prepared in the same manner as in Example 16 as follows. Approximately 1000 grams of the water-dispersed copolymer from Example 13 was added to the Content 5 flask with gentle stirring along with 770 grams of deionized water.
A premixed mixture of 18.4 grams of DEMA and 100 grams of water was added over a period of about 30 minutes with constant stirring. Next, a premix of 72 grams of butoxyethanol, 226 grams of normal butanol, and 130 grams of water was added and mixed over 30 minutes.
Epoxy acrylic copolymer from Example 15 approx.
716.8 grams were added over about 30 minutes followed by 32.8 grams of aminoplast resin Kumel 303 and 80 grams of water. The resulting polymer mixture was further stirred for 2 hours to ensure complete mixing. The resulting coating composition was sprayed onto the interior of the can and heat cured to provide an excellent internal can coating. Example 20 Coating Polymer Formulation Similar to Example 16, a coating composition was made as follows. Contents 5: A mixture of 500 grams of the emulsion copolymer from Example 1 and 500 grams of deionized water.
into a reaction flask. A premixed solution of 10 grams of DMEA and 100 grams of deionized water was added to the emulsion over a period of 30 minutes. Then 243.0 grams of epoxy phosphate from Example 15 and Example
1326.1 grams of epoxy acrylic copolymer from No. 14 was added over a period of one hour with vigorous stirring.
Approximately 87 grams of normal butanol and 30.5 grams of Cumel 303 were added and 340 grams of deionized water was added. The final polymer mixture was stirred for an additional hour.
The coatings obtained by this method are excellently suitable for spray application. The cured film had excellent integrity properties. Example 21 Preparation of Epoxy-Acrylic Ester Copolymer (a) Epoxy resin, liquid spray resin DER-333 (Dow Chemical Company, Midland, Mich.) (Dow
Chemical Company, Midland, Michigan)
4144 g of bisphenol-A, 2135 g of bisphenol-A and 409 g of 2-butoxy-ethanol-1 were charged. A water-cooled condenser was installed in one neck of the flask. An air-driven mechanical stirrer was installed in the second neck.
Nitrogen gas was supplied through the third neck.
A thermometer was placed on the fourth neck. The mixture was stirred in the flask under 15 inches of vacuum. The temperature was increased to 140°C and heating and vacuum were discontinued. Approximately 40 grams of volatiles were collected. This is water,
Consists of xylene (from DER333) and 2-butoxy-ethanol-1. The reaction temperature was raised to about 175°C by external heating. This temperature was maintained for 5 hours. After 1 hour, the viscosity of the epoxy resin is Y
Gardner-Holt (2-
Butoxyethanol-1 40% solution). It was Y ⁺ after 3 hours and Z after 5 hours. After 5 hours, 2-butoxy-2-ethanol-1
Added 1012 grams. The epoxy solution was allowed to cool to room temperature. (b) Acrylic Terpolymer, 5503 grams of butanol was charged to a 12-content four-necked round-bottomed flask.
The four necks were equipped with a water-cooled condenser, an air-driven mechanical stirrer, a thermometer-nitrogen inlet, and a monomer dropping funnel. The solvent was heated to 113°C. A monomer mixture of 1764 grams of methacrylic acid, 924 grams of styrene, 26 grams of ethyl acrylate, and 182 grams of benzoyl peroxide was slowly added to the solvent under reflux. The addition was carried out for 2 hours and the reaction mixture was maintained at 114° C. for an additional hour before being cooled to room temperature. The non-volatile content of the reaction mixture is 347
It was hot. Epoxy-acrylic ester copolymer Contents: Epoxy resin (a) in a round-bottomed four-necked flask.
1306 grams and 694 grams of acrylic resin (b) were charged. The reaction mixture was stirred while bubbling nitrogen. This temperature was maintained for 4 hours. Thereafter, 23.6 grams of dimethylethanolamine and 144 grams of 2-butoxy-ethanol-1 were added over 4 minutes. The reaction mixture was maintained at 102-105°C for 1/2 hour. The viscosity of the resin is U1/4 (1 part resin,
(from 1 part pyrrole). A 2 gallon stainless steel container was charged with 2043 grams of deionized water and 86.1 grams of dimethylethanolamine.
Place the container on a hot plate and keep the water temperature at 50℃.
It was hot. Then content the resin from a five-sided flask.
1500 grams were dropped into the stirring water. An emulsion was easily formed. The non-volatile content of the emulsion is 23.5
% viscosity in feed #4 cup was 38 seconds, acid number 34.1 and alkaline number 76.4. Adhesive Composition An adhesive composition was made by mixing the following components. 1200 grams of emulsion copolymer of Example 1, 893 grams of deionized water, 21.7 grams of dimethylethanolamine, 86.8 grams of deionized water, 106.7 grams of 2-butoxy-ethanol-1, 225.5 grams of epoxy phosphate, epoxy from above. −Acrylic ester 284.3
grams, normal butanol 363.6 grams, Cumel 303 32.7 grams, deionized water 400.5 grams. The above formulation was evaluated as an internal can coating.
NVM was 18.8%. Viscosity was 15 seconds in a #4 food cup. Acid value 35.5; alkaline value 29;
Neutralization value 81.7%; organic solvent/solid content ratio 0.9; 2-butoxy-ethanol-1/n-butanol ratio
30/70; and cumel was 5% on solids. The coating was air dried and baked to form a clean continuous coating. The coating had a 24% wedge defect and became slightly red after pasteurization for 10 minutes at 75.5°C (170°C). The red adhesion was excellent. The void ratio was less than 1, the MEK Masatsu was 24 overall, and the general film properties were excellent. Example 22 Preparation of epoxy-acrylic grafted quaternary ammonium copolymer The high molecular weight epoxy resin was Epon 828 [Cell Chemical Company, Heathon, Texas (Shell
The liquid epoxy resin bisphenol type (Chemical Co., Houston, Texas) was prepared by reacting 438 grams of a liquid epoxy resin (bisphenol type) and 248 grams of bisphenol A in 125 grams of 2-butoxy-ethanol-1 and 23 grams of xylene. A solution of 0.32 grams of sodium acetate trihydrate dissolved in 3.6 grams of water was added. The reaction mixture was charged into a 12-millimeter four-necked round-bottomed flask. The first neck is equipped with an air-driven mechanical stirrer, the second neck is equipped with a water cooler, the third neck is equipped with a thermometer and nitrogen inlet, and the fourth neck is equipped with a thermometer and nitrogen inlet. was equipped with an addition funnel. Heating was performed using a heating mantle. temperature
When 140°C was reached, heating was discontinued and the temperature of the reaction mixture was brought to 175°C by external heating. temperature is 175
It was maintained at ℃ for 5 hours. Thereafter, the viscosity of the epoxy resin (40% solution of 2-butoxy-ethanol-1) was A1-Z2 (Gardner-Holdt viscosity).
Heating was discontinued and 484 grams of normal butanol was carefully added. The temperature after butanol addition is approx.
It was 115℃. 114 grams of methacrylic acid, 60 grams of styrene, 1.6 grams of ethyl acrylate, benzoyl peroxide (78% active in water) and 145 grams of 2-butoxy-ethanol were added to the epoxy resin over a period of 2 hours. The temperature was maintained at 115°C. After adding the monomer mixture, add 25 g of n-butanol using a funnel and heat at 115 °C.
It was maintained for 1 hour. 888 grams of styrene, 350 grams of ethyl acrylate, 186 grams of methacrylic acid,
Benzoyl peroxide (78% active in water) 36.4
289 grams of 2-butoxy-ethanol-1 and 148 grams of n-butanol were slowly added to the epoxy-acrylic graft copolymer at 115°C. The addition took 3 hours. The reaction mixture was maintained at 115°C for an additional 30 minutes before 719 grams of n-butanol was added. Mixture from 115℃
Cooled to 85°C and slowly added 828.450 grams of epoxy resin Epon, then maintained at 90°C for 1/2 hour.
Then 80 grams of dimethylethanolamine and 50 grams of water were added and the reaction mixture was maintained at 80° C. for 1 hour. Then add 29 grams of dimethyl ethanol and add 20
A dispersion of %NVM was obtained. The resulting copolymer is believed to be an epoxy-acrylic graft copolymer containing quaternary ammonium functionality. The film's boiling properties and voids were significantly improved. Example 23 N-Isoptoxymethylacrylamide (NiBMA) self-curing copolymer by suspension polymerization (a) Deionized water in a round bottom four-necked flask containing 5
I prepared 2211 grams. The flask is equipped with a nitrogen gas inlet, a thermometer, a water-cooled condenser, and an air-driven mechanical stirrer. After heating the water to 60℃,
Vinol 523 (Vinol) (Polyvinyl alcohol from Air Proact and Chemical, Uaine, Baa) (Air Proact and Chemical,
Wayne, Pa.) was added and took approximately 20 minutes to dissolve. The monomer mixture was prepared by adding 544 grams of styrene, 435 grams of ethyl acrylate, 54.5 grams of methacrylic acid, 64 grams of NiBMA monomer (85% in isobutanol) and 13 grams of lauroyl peroxide to an aqueous solution at approximately 70°C and polymerizing. This was carried out at 70°C for about 5 hours. At the end of this time, the polymerization mixture was cooled to room temperature, the non-volatile part of the suspension was 29.2%, and the viscosity was that of a #4 cup of food.
It was hot in 25 seconds. A mixture of suspension polymer (a), epoxy-acrylic graft copolymer (Example 14a) and epoxy phosphate (Example 15) was made as follows. Contents: Polymer (a) suspended in a four-necked round-bottomed flask.
1000 grams, and 754.5 grams of deionized water. The flask was equipped with a nitrogen gas inlet, a thermometer, a water-cooled condenser, and an air-driven mechanical stirrer. The mixture was heated to 38°C and 18 grams of dimethylamine ethanol and 83.6 grams of deionized water were added. The temperature rose to 48°C. Mixing continued for 15 hours. Then 2-ethoxy-butanol-155.9
grams and then 2.8 grams of deionized water. The mixture was stirred at 43°C for 40 minutes. epoxy
200.3 grams of phosphate (Example 15) was added over 30 minutes, followed by 68.2 grams of deionized water over 15 minutes. Next, 378.1 grams of epoxy-acrylic graft copolymer was added over a period of 30 minutes.
Next, 77.1 grams of deionized water was added over a period of 5 minutes. Next, 168.4 grams of normal butanol was added over a period of 10 minutes. An additional 29.1 grams of Schimmel 303 was added. In addition, 55.2 grams of normal butanol 15
and then 205.4 grams of deionized water. The non-volatile content of the formulation was 15.1% and the viscosity was 13 seconds in a #4 cup of food. The film was drawn onto a glass plate and then heated to 194°C (380°C).
〓) for 5 minutes on a pot plate to give a smooth coating. Example 24 Formulations Containing Epoxy-Grafted Acrylic-Containing Phosphate Monomers 434.5 grams of 2-butoxyethanol were charged to a 5-volume flask equipped with a stirrer, thermometer, condenser, and nitrogen gas inlet and heated to 150°C. did. When the temperature rose to 150°C, 1000 grams of solid epoxy resin (Epon 1009) was gradually added and dissolved in the solvent. When all the epoxy resin was dissolved, the temperature was lowered to 115°C and 507.7 grams of normal butanol was slowly added, maintaining the temperature at 115°C. 159.1 grams of methacrylic acid, styrene
83.2 grams, ethyl acrylate 2.3 grams, glycidyl methacrylate phosphate 25.6 grams, benzoyl peroxide 21.7 grams and 2
The epoxy solution was added over a period of 1-1/2 hours. After all the monomer mixture was added, 34.9 grams of normal butanol was added using an addition funnel.
The reaction mixture was maintained at 115°C for 3 hours to complete the polymerization. Then wash the resin with 2550 grams of deionized water and
Charged to a stirred reduction vessel containing a mixture with 103 grams of DMEA. The temperature of the resulting formulation was 50°C. Maintain this temperature for approximately 1 hour, then bring the formulation to 32°C by adding 100 grams of chilled deionized water.
Cooled down to below. The phosphated epoxy-acrylic graft copolymer was mixed with the emulsion copolymer from Example 1 to make an excellent spray can interior coating. Example 25 Formulation Comprising Epoxy Acrylic Melamine Graft Copolymer 125 grams of the emulsion copolymer from Example 1 was added to a Content 5 flask along with 112.5 grams of deionized water. This mixture was gently stirred for approximately 15 minutes. 1.3 grams of dimethylaminoethanolamine and 12.5 grams of deionized water were added with constant stirring. Then add 9.5 grams of 2-butoxyethanol, then add 25.2 grams of the epoxy phosphate from Example 15.
Gram and U.S. Pat. No. 4,289,811 Example 1
56.4 grams of epoxy acrylic melamine graft polymer made by the method of . Then add 28.5 grams of normal-butanol, 3.7 grams of aminoplast resin and 3.7 grams of cumel 303,
Mixed well. Next, 0.5 grams of DMEA and 3.7 grams of deionized water were added and mixed for 1 hour. The resulting polymer mixture provided an excellent spray coating on the interior of the can. Example 26 Phosphorylated Hydroxy-Terminated Polybutadiene Blend Hydroxy-terminated polybutadiene (Hiker 1300 x 29 B.F. Gutdrich) was added to a suitable reactor.
(Hycar1300×29, BFGoodrich) 184 copies and 2-
79 parts of butoxyethanol were added. Heating and stirring were performed by blowing nitrogen gas. 1.84 at 50℃
A mixture of 1 part superphosphoric acid and 44 parts 2-butoxyethanol was slowly added over a period of 11 minutes. The reaction temperature was maintained at 125°C for 25 minutes. then water
3.7 parts were added and the reaction mixture was maintained at a temperature of 125°C for 2 hours. The temperature was then lowered to 75°C and 3.7 parts of dimethylaminoethanolamine was added followed by water.
Added 303.2 copies. Next, 110 parts of 2-butoxyethanol were added, followed by 25 parts of butanol.
The solids were adjusted to the desired amount by adding 26 parts of DMEA followed by 200 parts of water. Formulation Composition: 100 grams of the water-dispersed copolymer from Example 13 was added to the reaction flask of Example 5 along with 754 grams of water. The mixture was slowly stirred for 15 minutes. A premixed mixture of 18 grams of DMEA and 200 grams of water was added with constant stirring. Next, 341.7 grams of polyptadiene phosphate from the previous example was added and 17 grams of water was added. Then 379.1 grams of epoxy acrylic copolymer from Example 14 was added and 19 grams of water was added. Next, normal-butanol 228.7
gram, followed by a mixture of 8.73 grams of butanol and 29.1 grams of Cumel 303. To adjust the resulting mixture to the desired solids content,
Added 63.4 grams of water. The resulting mixture produced a good film of spray coating. Example 27 Phosphorylated Polyester Containing Formulation Tall oil fatty acids (Sylfat V-18) were added to a conventional polymerization reactor equipped with a stirrer, a cooler, a water separator, a thermometer and a nitrogen inlet. was prepared and heated to 80℃. When the temperature reached 80℃, resinous polyol (Monsanto RJ-
101) (Monsanto) was added and heated to 125°C. 45.7 centimeters (18 inches) to draw water captured by RJ-101
A vacuum was required. The reaction mixture was heated to 240°C and xylene was added as needed to aid in water removal. The temperature was maintained at 240°C for 2-1/2 hours and the acid number of the solid was 3.9. Heating was discontinued and the reaction mixture was cooled to 120°C. When the temperature reached 120°C, 1567 grams of acetone was added very gradually. After addition, the temperature of the batch was 51°C. The obtained polyester was subjected to phosphorization treatment as follows.
A conventional vessel equipped with a stirrer, condenser and thermometer was charged with 386.1 grams of the resin from above. twenty five
15 grams of phosphorus pentoxide solids were added with stirring. The reaction mixture was heated to 125°C and diluted to 77.9% solids by adding 79 grams of 2-butoxyethanol. The phosphorylated polyester is then added to the water dispersion copolymer (Example 13) and the epoxy-acrylic copolymer (Example 14) and sprayed onto the interior of the can to provide a superior coating. Example 28 Preparation of Phosphated Epoxy-Acrylic Graft Polymer An epoxy phosphated acrylic copolymer was prepared as follows. 95% Epon 828 in xylene,
1141 grams, 614 grams of bisphenol A, and 310 grams of 2-butoxyethanol were charged to a Content 5 flask equipped with a stirrer, thermometer, nitrogen inlet, condenser, and dropping funnel. Mixture at 90℃
The mixture was heated while blowing nitrogen. When the temperature reached 90℃, 0.52 grams of sodium acetate, and 3 grams of water
grams of mixture were added and heating continued to 140°C.
Heating was discontinued when the temperature reached 140°C. The temperature was increased to 160°C by external heating. The temperature was raised to 175°C by heating. The reaction mixture was maintained at 175°C for 5 hours and cooled to 125°C with the addition of 360 grams of 2-butoxyethanol. When the temperature reached 125°C, a mixture of 7.32 grams of polyphosphoric acid and 20 grams of 2-butoxyethanol was slowly added and the temperature was maintained for 30 minutes. Next, 347 grams of water was slowly added to the reaction mixture and maintained at 125°C for 2 hours.
After 2 hours, 888 grams of butanol was added to the reaction mixture. The temperature dropped to 113°C. A mixture of 283 grams of methacrylic acid, 148 grams of styrene, 4 grams of ethyl acrylate, 38.5 grams of benzoyl peroxide and 32.4 grams of 2-butoxyethanol was added over a period of 2 hours, then the reaction mixture was
It was maintained at 114°C for an additional 2 hours. The resulting resin was then dropped into a mixture of 3867 grams of deionized water and 162 grams of dimethylethanolamine. The phosphated epoxy-acrylic graft copolymer was mixed with latex (Example 13). The resulting emulsion was a stable milky emulsion when cured with 5% Kumel 303 and provided an excellent protective coating for steel cans used for soft drinks. Example 29 Thermosetting Copolymer Containing Alkyl Hydroxy Phosphate Surfactant Alkyl hydroxy phosphate was made by reacting superphosphoric acid and alkyl epoxide by the method described in U.S. Pat. No. 3,487,130. . By using 1,2-epoxyhexadecane,
240 parts of 1,2-epoxyhexadecane were added dropwise to a solution of 105 parts of superphosphoric acid dissolved in 200 parts of tetrahydrofuran while stirring. The reaction mixture was maintained at 10-15°C during the addition of epoxyhexadecane. After that, the temperature gradually rose to room temperature. 300 parts of diethyl ether were then added to the batch, and the solution was washed with 2 parts of 200 milliliters of saturated sodium chloride solution.
The organic layer was dried with sodium sulfate and the solvent was evaporated.
Approximately 300 parts of hexadecane hydroxyphosphate were obtained. Under this manufacturing condition, the mono- and diesters contain large amounts of reaction products. Separation of hydroxyphosphate mono- and diesters does not need to be used with water-dispersed copolymers or epoxy/acrylic mixtures. To prepare the thermosetting emulsion copolymer containing the alkyl hydroxyphosphate as a surfactant, 115 parts of deionized water and 0.10 parts of hexadecane hydroxyphosphate were placed in a reactor and heated to 50 to 52°C. 50
The pH of the solution was adjusted to 8.5-9.0 at 0.degree. C. by addition of dimethylethanolamine and then heated at 76.degree.-78.degree. C. with stirring and bubbling nitrogen gas. When the reaction temperature was maintained at equilibrium, the nitrogen gas blowing was stopped and 1.2 parts of styrene and 0.80 parts of ethyl acrylate were added.
The mixture was added to the reactor and emulsified for 10 minutes.
Thereafter, 0.30 parts of ammonium persulfate was added to the reactor and allowed to react for at least 20 minutes before starting the monomer feed. The monomers supplied were 55.0 parts of styrene, 26.0 parts of ethyl acrylate, 5.0 parts of methacrylic acid, and N-
Consists of 12.0 parts of isobutoxymethylacrylamide. The monomers are added to the reactor at a constant rate over a period of 4.5 to 5.0 hours, during which time the batch is heated between 76°C and 78°C.
The temperature was maintained at ℃. The batch was then maintained at reaction temperature for an additional 2 hours before being cooled and filtered. Example 30 Thermosetting Copolymer Containing Phosphate Functionality Monomers containing phosphate functionality were made as described in U.S. Pat. No. 3,686,371 by reaction of phosphorus pentoxide with hydroxyethyl acrylate. . In this method, 140 parts of phosphorus pentoxide was gradually added to a solution of 350 parts of hydroxyethyl acrylate and 0.05 parts of MEHQ inhibitor with vigorous stirring. The reaction temperature was maintained at 25-35°C by external cooling. After the addition of phosphorus pentoxide is complete, the reaction is carried out at 30°C.
The reaction was completed by stirring for 2.5 hours and then heating at 45° C. for 2 hours. Mono and diesters are present in the reaction mixture but do not require separation before polymerization. Phosphate monomers can be emulsion or solution copolymerized using standard semi-continuous methods. Solution polymerization uses butoxy-ethanol and n-butanol 1:
It is best carried out in a mixture of the two. Emulsion polymerizations can be carried out in aqueous liquids without further uptake of organic solvents. The thermoset emulsion copolymer containing phosphate monomer was charged to a reactor with 110 parts of deionized water and 0.10 parts of sodium dihexyl sulfosuccinate.
The solution was heated at 76°C to 78°C under a stream of nitrogen gas. At equilibrium reaction temperature, nitrogen gas was removed and 0.10 part ammonium bicarbonate was added. Then styrene 1.2
1 part and 0.80 part of ethyl acrylate were added to the reactor and emulsified for 10 minutes. In this case, 0.30 part of ammonium persulfate was added and the monomers were allowed to react for 20 minutes before starting to feed. The monomer mixture contained 35.5 parts styrene, 50.0 parts ethyl acrylate, 4.0 parts methacrylic acid, 10.0 parts N-isobutoxymethylacrylamide, and 0.50 parts 2-phosphate ethyl methacrylate. Monomer was added to the reactor at a constant rate over a period of 4.5 to 5.0 hours. Meanwhile, the reaction temperature is 76 to 78
It was maintained at ℃. The batch was then maintained at reaction temperature for an additional 2 hours, during which time an additional 400 parts of deionized water was added to reduce the viscosity. Example 31 Thermosetting Copolymer Containing Alkyl Phosphates Alkyl phosphates were made by reacting superphosphoric acid with aliphatic alcohols. The method used is an example
The method is identical to that used for phosphate hydroxyalkyl acrylates as described in 29. The thermoset emulsion copolymer containing alkyl phosphate was prepared by charging a reactor with 115.0 parts of deionized water and 0.10 parts of octyl phosphate and heating to 50-52°C. At 50°C to 52°C, the pH of the aqueous phase
The pH was adjusted to 7 to 7.5 with dimethylethanolamine. Next, while blowing in nitrogen gas and stirring
Heated to 76°C to 78°C. At equilibrium reaction temperature, the nitrogen gas blowing was stopped and a mixture of 1.2 parts styrene and 0.8 parts ethyl acrylate was added to the reactor. The monomer portion was emulsified for 10 minutes, then 0.30 parts of ammonium persulfate was added to the reactor and the monomer feed initiator reacted for 20 minutes. Monomers containing 45.0 parts of styrene, 38.5 parts of ethyl acrylate, 5.0 parts of methacrylic acid, and 10.0 parts of N-isobutoxymethylacrylamide were used.
Monomer was added to the reactor over a period of 3.5 to 4.0 hours and the batch temperature was 76°C to 78°C. An additional 900 parts of deionized water was added to the batch while the monomer was being fed to reduce the viscosity. The batch is 3 at the reaction temperature.
After maintaining for an hour, it was cooled and filtered. The above emulsions made as described in Examples 29-31 were mixed with epoxy-acrylic copolymers according to the method of the present invention to produce excellent can interior coatings. Example 32 Preparation of a water-soluble dispersant Deionized water was added to a flask of contents 5 equipped with a thermometer, a condenser, a stirrer, and a nitrogen gas inlet tube.
1000 grams and dimethylaminoethanol
114.6 grams of the mixture was charged. Mixture at 85℃
heated to. The monomer mixture is 548 grams of styrene;
487.1 grams of ethyl acrylate, methacrylic acid
121.7 grams, benzoin 24.3 grams, butyl cellosolve 379.5 grams, normal butanol 379.5 grams
60.9 grams of N(isobutoxymethyl)acrylamide and 34.8 grams of tert-butyl hydroperoxide were added over a period of 4 hours. After the monomer mixture addition was complete, the reaction mixture was maintained at 85° C. for 1 hour. Next, 900 grams of deionized water was added, followed by a mixture of 100 grams of deionized water and 34.8 grams of tertiary butyl hydroperoxide. The reaction mixture was maintained at 85° C. for an additional 2 hours to complete polymerization. Formulated Composition To a Content 5 flask equipped with a condenser and stirrer was added 1514 grams of the water soluble dispersion from the above water soluble dispersion along with 463 grams of deionized water. The mixture is
Mixed for 15 minutes. Next, 200.3 grams of epoxy phosphate from Example 15 was added and washed with 200 grams of deionized water. The resulting mixture was mixed for one hour, then 379.1 grams of the epoxy-acrylic copolymer from Example 14 was added and rinsed with 200 grams of deionized water. The mixture was stirred for 1 hour. A mixture of 13 grams of normal butanol and 29.1 grams of Shimel 303 was then added followed by 100 grams of deionized water. The resulting mixture was mixed for 2 hours and then filtered. The resulting polymer mixture cured and provided a good can interior coating. EXAMPLE 33 Blend with Ammonium Phosphate 1000 grams of the latex from Example 1 was added to a Content 5 flask with a condenser and stirrer in deionized water.
Added along with 1000 grams. A mixture of 18.1 grams of dimethylethanolamine and 50 grams of deionized water was slowly added. Next, 76.6 grams of butyl cellosolve and 222.8 grams of normal-butanol were added to the mixture. Then 715 grams of the epoxy acrylic copolymer from Example 14 was added and stirring continued for 2 hours. Then 1.33 grams of ammonium phosphate was added and stirring continued for an additional hour. The resulting mixture was mixed with 5% Kumel 303. The coating is cured;
It was a clean film with good film properties.

Claims (1)

[Claims] 1. (i) an ethylenically unsaturated alkylolacrylamide monomer; and (ii) an ethylenically unsaturated functional monomer containing at least one functional group of carboxy, hydroxy, amine, and amide groups. and (iii) another ethylenically unsaturated monomer. It is obtained by two-stage emulsion polymerization carried out in the second stage, whereby alkylolacrylamide is concentrated on the surface of the polymer and crosslinked with a small amount of the above functional monomer to form a relatively hard polymer. An aqueous dispersion coating composition capable of forming particle surfaces. 2. Based on the weight of the polymer solids, it contains 5% to 99% of the self-curing copolymer, and further contains 1% to 70% of the epoxy-acrylic copolymer and 0% to 50% of the phosphated polymer. An aqueous dispersion coating composition according to claim 1. 3. Claim 2, wherein the phosphated polymer is 3% to 20% by weight of polymer solids.
Compositions as described in Section. 4. A composition according to any preceding claim, wherein the composition further comprises 1% to 10% aminoplast resin, based on the weight of polymer solids. 5. The composition of any one of the preceding claims, wherein the alkylolacrylamide component of the self-curing copolymer is an alkylated alkylolacrylamide. 6. The epoxy-acrylic copolymer is a graft copolymer and is present in a mixture with a non-grafted polymer, an epoxy resin and a non-grafted acrylic mixed polymer. Composition of. 7. The composition of any one of the preceding claims, wherein the epoxy-acrylic copolymer is a phosphated epoxy-acrylic polymer. 8. The composition according to any one of the preceding claims, wherein the epoxy-acrylic copolymer is an epoxy-acrylic ester copolymer. 9. Any one of the above claims, wherein the self-curing copolymer is produced by copolymerizing its constituent monomers in the presence of a phosphate or phosphoric acid.
The composition described in Section. 10. A composition according to any preceding claim, comprising a phosphorylated polymer, the phosphorylated polymer comprising an epoxy phosphate. 11 A phosphorylated polymer, the phosphorylated polymer being (a) a resin-like compound produced by reacting an ethylenically unsaturated monomer containing a carboxy or hydroxy monomer in water containing an ionizing agent; Polyelectrolyte phosphated polymers, (b) phosphated epoxidized oils, (c) phosphated epoxidized butadiene copolymers, (d) polymers containing copolymerized phosphate monomers, ( e) A composition according to any one of the preceding claims, which is selected from phosphated polyesters. 12 (i) an ethylenically unsaturated alkylolacrylamide monomer, (ii) an ethylenically unsaturated functional monomer containing a reactive functional group, and (iii) another ethylenically unsaturated monomer as a copolymer component. A water-dispersible coating composition according to claim 1, further comprising a water-dispersible self-curing polymer containing phosphate as a copolymer component. 13. The composition according to claim 12, wherein the phosphate is an alkyl phosphate ester monomer copolymerized with other monomers. 14 Claim 2, wherein the epoxy-acrylic copolymer is a quaternary ammonium polymer.
The composition according to any one of items 1 to 6. 15 The epoxy-acrylic copolymer is prepared by reacting an epoxy resin with a melamine graft copolymer of melamine and an acrylic copolymer in the presence of a sufficient amount of amine to form a non-gelling epoxy-acrylic ester copolymer. 7. A composition according to any one of claims 2 to 6 made by. 16 A method in which (i) an alkylolacrylamide, (ii) a functional monomer selected from carboxy, hydroxy, amine and amide monomers, and (iii) other ethylene type monomers are emulsion polymerized in two steps. In the second step, the alkylolacrylamide is polymerized such that a small amount of the alkylol acrylamide reacts with a small amount of the functional monomer to form a relatively hard polymer particle surface. A method for producing a water-dispersed polymer. 17. The method of claim 16, wherein the acrylamide monomer is an alkylated alkylolacrylamide monomer. 18. The method of claim 17, wherein the monomer of the alkylated alkylolacrylamide is a butylated alkylolacrylamide. 19 The ethylenically unsaturated monomers (i), (ii) and (iii)
comprises 1 to 20% by weight of an alkylolacrylamide monomer, 1 to 20% by weight of a functional monomer, and the balance other ethylene type monomers. The method described in. 20. Any one of claims 16 to 19, wherein the monomer of the self-curing water-dispersed polymer is polymerized in the presence of an ionizing agent to produce a resinous polymer electrolyte water-dispersed self-curing polymer. The method described in Section 1. 21 After producing the self-curing water-dispersed polymer, the self-curing water-dispersed polymer is further mixed with an epoxy-acrylic copolymer and, if necessary, a phosphated polymer. 1% to 99% of the above epoxy-acrylic copolymer
70% to 70% and 0% to 50% phosphated polymer
21. A method according to any one of claims 16 to 20, characterized in that an aqueous dispersion composition containing % is obtained. 22. The method according to claim 21, wherein the monomer is phosphorylated in the presence of a phosphate surfactant. 23 (i) an ethylenically unsaturated alkylolacrylamide monomer; (ii) an ethylenically unsaturated functional monomer containing at least one functional group of carboxy, hydroxy, amine, and amide groups; and (iii) others. an aqueous dispersion coating composition having a self-curing copolymer comprising as a component an ethylenically unsaturated monomer of Methods of using dispersible coating compositions.