JPS5949269A - Water-dispersed coating composition and manufacture - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to methods for making polymeric compositions and particularly surface coating compositions. In particular, an aqueous mixture containing a specific reactive self-curing aqueous dispersion polymer, an aqueous dispersion of an epoxy-acrylic copolymer, and preferably an IJ phosphate additive, comprising: a food or beverage container; and similar aqueous can coating compositions for internal coatings for sanitary coating applications.

Aqueous coating compositions useful as internal sanitary linings for metal containers are described in U.S. Pat. No. 3,991,216. Such polymers include copolymerizable acrylamide polymers, These polymers are composed of interpolymers of carboxylic acid monomers and other ethylenically unsaturated monomers. However, such polymers are difficult to spray and exhibit poor film deformability, such as resistance to ethanol. It forms a film with poor quality and is unsuitable for containers for alcoholic beverages.

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 trench epoxy resins are 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 are caused by the leaching of the coating composition into the beverage, the absorption of aroma into the coating, and sometimes by the combined effects of the two, resulting in chemical reactions. [In the method described in Publication No. 4.212.781, an epoxy resin and an addition-polymerizable monomer are combined in a suitable manner in the presence of at least 3% benzoyl peroxide, based on the weight of the body. A method of denaturation by reaction at temperature is described. This reaction yields a reaction mixture containing a blend of in situ generated resinous materials including an epoxy resin, an epoxy-acrylic graft polymer, and an epoxy-acrylic copolymer mixture containing a non-grafted addition polymer. In order to ensure a stable dispersion of the reaction product obtained in the medium, the in-situ polymerization compound has acid functionality.
y). U.S. Patent No. 4.2i2
．． In a suitable embodiment of the '781 publication, the polyglycidyl ether of bisphenol A is a polyglycidyl ether of bisphenol A such as methacrylic acid. During acid-containing additive multiplication, Ji! , reacts with the body mixture.

Epoxy 4vj.I fat has a molecular radius of 41,000 or more, which corresponds to 50% to 90% of the initial J (containing compound).
Preferably occurs at a temperature of 80°C 1-1, approximately 110°C
to 13 (] Perform addition polymerization of basis weight at t:
The epoxy acrylic copolymer mixture is grafted onto the epoxy resin to form a polymer. The reaction product is dispersed in the aqueous substrate medium to provide an aqueous epoxy acrylic copolymer mixture.

It has been discovered that certain reactive self-curing water-dispersed polymers formulated with epoxy-acrylic copolymers and polymerizable phosphates 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 alkynol acrylamide monomers. ) The PL polymer can be copolymerized by 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 [7] to form a relatively hard polymer particle surface. [7] Stabilizes the viscosity of the water-dispersed formulation while providing significant tear resistance properties during subsequent spraying of the formulation.

For optimal thermal curing of the compositions of the present invention, the water-dispersed polymer reacts with the reactive monomer in the polymer and self-cures 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, especially when applied by spraying to drinking cans. Additionally, preferred compositions of the present invention include a phosphated polymer, such as an evogysiphosphated polymer.

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 monomer having carboxy, hydroxy, amine, or monoamide functional groups together with an alkylolacrylamide monomer, and then blending the water-dispersed polymer with an epoxy-acrylic acid copolymer. Preferably, it is based on certain self-curing water-dispersed polymers obtained by incorporating phosphated polymers. The composition of the present invention comprises a water-dispersed polymer blend of (a) a reactive self-curing water-dispersed polymer and (b) an epoxy-acrylic copolymer. A more preferred composition comprises (C) an IJ acid salted polymer. Aminoblast 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 the reactive self-curing water-dispersed polymer, the reactive self-curing polymer Fi (+) alkylolacrylamide, preferably an alkylated alkylolacrylamide monomer, (II) a reactive carboxy, hydroxy,
Functional monomers consisting of amine or amide monomers and (
+1il is a polymer of copolymerized ethylenically unsaturated monomers containing other ethylenically unsaturated monomers to form a self-reactive alkynol acrylamide water-dispersed polymer. Self-curing water-dispersed polymers are synthesized by conventional one-stage copolymerization or stepwise polymerization of monomers in water. As a result, the alkylolacrylamide monomer is polymerized in the second polymerization step. The monomers in the second stage are blended in a weight ratio of 25/75 to 75/25 of the first stage/second stage monomers.

Alkylated alkylolacrylamide monomers are derivatives of acrylamide, methacrylamide, mechloracrylamide or similar alkyl-modified acrylamide monomers, such as U.S. RT No. 3.991.216.
;4.097,438:4, 305.859. Preferably, the acrylamide monomer is alkylated with an alkyl group such as methyl, ethyl, propyl, n-butyl, isobutyl, and is a similar alkylated alkylolacrylamide monomer in 1.
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, such as hydroxyalkyl acrylates, e.g.
- Hydroxyethyl acrylate and methacrylate, 2-hydroxyalkyl acrylate and methacrylate, and similar hydroxyalkyl A acrylates. The amide-containing monomer is acrylamide, methacrylamide or a similar alkylalkylolacrylamide 11, -p form. Other reactive monomers include the '1' At form of N-methylolacrylamide or methacrylamide. Alyarol acrylamide M is copolymerized with H3 body and functional monomer and reacts at t1°
The remaining monomers forming the self-(+lIq-forming polymer) are ethylenically unsaturated monomers such as striped vinyl needles. For example, vinyl acetate, vinyl benzoate, vinyl butyrate, vinyl benzoate, ingropyr. Acete←
and similar vinyl esters such as vinyl qM and vinyl halides such as vinyl chloride. Other ethylenically unsaturated monomers include monomers with ethylene double bonds, such as polymerizable allyl acrylic groups, fumaric acid residues, maleic acid residues, etc. have 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 oromonomers. 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 Acrylates and methacrylates, decyl acrylates and methacrylates, isotecyl acrylates and methacrylates, benzyl acrylates and methacrylates, various reaction products such as butyl, phenyl and cresyl glycidyl ether reacted with acrylic acid and methacrylic acid. Hydroxyalkyl acrylates and methacrylates L'=for example hydroxyethyl and hydroxyalkyl acrylates and methacrylates and aminoacrylates and methacrylates.

A further improved self-curing water-dispersed polymer comprises a reactive functional JY polymer and a hydroxyalkyl phosphate ester having at least one unsaturated double bond with an ethylene monomer mixture containing an alkylolacrylamide monomer. It can be made by polymerizing. Hydroxy alkyl phosphate esters Q, ff (form ij: Hydroxy acrylic phosphate ester monolayers can be made, for example, by reaction of acrylic glycol with phosphorus pentoxide or by reaction of acrylic monoepoxide with superphosphoric acid. Invention The ethylene-type monotonic mixture according to
% hydroxyalkyl phosphate ester of Li2S to form a phosphated self-curing water-dispersed polymer.

In yet another variation, a water-dispersed self-curing 1ic composite is prepared by combining an ethylene-type monolithic mixture of a reactive functionalized monolayer with an alkylolacrylamide monolayer in the presence of a polymeric surfactant and an epoxy phosphate ester surfactant. The self-curing water-dispersed polymer is either polymerized under emulsification or dispersed in water with an Epo-V diphosphate surfactant. Epoxy phosphoric acid Nisdel t 005% to 5 thiphosphoric acid and Dow DER
333 (Dow) and a relatively high molecular weight adduct to a bisphenomole.During polymerization, the epoxy phosphorus Acts as an acid salt surfactant and self-
The particle size of the curable copolymer is controlled, and as the particle size increases, the polymer particles become more stable. The self-curing water-dispersed polymer containing phosphate provides improved self-curing reactivity, with the phosphate acting as a crosslinking promoter. Precipitated by a phosphate crosslinking reaction, the film properties give improved corrosion resistance.

The reactive self-curing alkylolacrylamide water-dispersed polymers are preferably prepared in water using peroxides, azo catalysts, conventional redox catalysts, ultraviolet irradiation, etc. Ethylene type F: It is a copolymer made by copolymerizing Awa, Chinese and Japanese types.

Free radical initiators include a variety of peroxides such as persylphate, benzoyl peroxide, tertiary butyl hydroperoxide, cumene hydroxide, and similar peroxyde catalysts, and azo compounds such as azo-isobutyronitrile. , dimethyl azopisuisof] thilate. Additionally, the initiator system includes an alkali metal persulfate, or ammonium persulfate, with or without a reducing agent used to activate the persulfate. Alternatively, about 1 to 1 liter of bamboo catalyst is used, based on the weight of monomer.The resulting self-curing water-dispersed polymer has a concentration of 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 using a water-soluble initiator in the presence of an emulsifier, suspension polymers made by aqueous suspension polymerization using a suspending agent, and Microemulsion polymers are aqueous microemulsion polymerized in bulk particles and stabilized with long-chain aliphatic alcohols, and azeotropic emulsion copolymers made in water-solvent azeotropes using soap emulsifiers. It is a combination. Other useful water-dispersed polymers are ionizing agents and U.S. Pat.
It can be produced by copolymerizing monomers in water containing a small amount of organic co-solvent as described in Japanese Patent No. 6.

Next, regarding the epoxy-acrylic copolymer, the copolymer is an epoxy resin reacted with a monomer containing an acrylic extender or an epoxy resin reacted with a pre-made acrylic copolymer. 8 polymer. Suitable Evogysy' acrylic copolymers include Evogysy acrylic graft copolymer mixtures containing an epoxy resin, Evogysy acrylic graft copolymers containing an ethylenically unsaturated monomer and an epoxy resin containing at least 3% benzoyl peroxide. A non-grafted polymer made by polymerizing with an epoxy resin in the presence of (or an equivalent amount)
It is described in Japanese Patent No. 212,781. Generally, in-situ polymerization of monomers is accomplished by reacting the ethylenically unsaturated monomer with an epoxy resin and at least 3% benzoyl peroxide, based on the weight of the monomer. 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 epoxy-acrylic acid copolymer mixtures are mixed in water. contains carboxy functional groups dispersed in 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-methylol monomers such as N-methylolacrylamide, may also be used. can. The remaining monomers are non-reactive monomers such as esters of acrylates and methacrylates such as ethyl acrylate, methyl acrylate, imbutyl acrylate, styrene, vinyltoluene, vinyl acetate, vinyl chloride, vinylidene chloride, acrylonitrile, and acrylic acid. Alkyl esters, lower alkyl esters, i.e. esters containing ester groups having 1 to 4 carbon atoms, especially ethyl acrylate. Other useful monomers belonging to Tore are C
1-+e Argyl acrylate ester, methacrylate ester, such as propyl acrylate, isopropyl acrylate, butyl acrylate, isobutyl acrylate, tertiary butyl acrylate-1, pentyl acrylate, decyl acrylate, lauryl acrylate, inbornyl acrylate, methyl methacrylate They are acrylate, buty-A, methacrylate, isobutyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, methyl methacrylate, and nonyl methacrylate. Other useful monomers are commercially available vinyl monomers, such as styrenic monomers, such as ethane, vinyltoluene, divinylbenzene, isoprene, and butadiene.

The carboxy-functional polymer produced in situ has a molecular weight of 5.0
00 t, 20,000, preferably 7,000, 15.0 (10) Carboxy-containing M: (
COO old is at least 2% of the monophagous mixture (Jp month)
, preferably t < tel, less than 5.

The epoxy resin portion of the epoxy-acrylic acid copolymer is aliphatic or aromatic, and aromatic epoxy resins are suitable. The most preferred epoxy resin is a polyglycidyl ether of bisphenol A, especially about 1.3 to 2.
It is a resin equivalent to ゜2-epoxy 1. Its molecular weight is 35
0 to 20,000, and 4,000 to 1.0.0 (10) for preferred sanitary coating compositions. When containing 90% (M, total) of epoxy resin,
Epoxy resins should have a molecular weight of 4,000 to 10,000, especially when making sanitary coating compositions. Mixtures of monoepoxides and dieboxides are preferred. Another process variation is the introduction of aromatic polyether, phenol or similar monoreactive epoxy blocking agents that do not contain oxirane functionality by reaction of the epoxy groups with benzoic acid. Still 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 phosphorus. The epoxy phosphate, containing the acid salt, then reacts with the acrylic monomer containing the carboxyl monomer, producing at least three peroxide catalysts based on the weight of the monomer. 7″1:tsu-C
The cat is copolymerized to form a J-boxyaryl composition containing epoxy phosphoric acid, (mono-aryl graft copolymer). In a preferred practice, 1. epoxy resin d. A mixture of an aromatic polyneedle, an aromatic polyether with one oxirane group, and an aromatic polyether with two oxirane groups.This mixture with govoxy functionality maximizes miscibility. However, an aromatic polyether that does not contain oxirane functionality can be added later.The mixture can then be heated and finger pressed to increase the intimacy of the bond between each heel sole.

In situ epoxy-acrylic copolymers can be made by polymerizing ethylene intermediates and epoxy resins in one batch. The epoxy resin can be heated in a reactor and the polymerizable monomer added gradually over a period of at least 2 or 3 hours along with the solvent and free radical initiator. Although the reaction can be carried out in a solvent I7, the use of a solvent is suitable for the in situ polymerization of the monomers in the presence of the epoxy t8.1 fat.

A preferred solvent system includes two miscible solvents, one of which dissolves the epoxy resin and the other which dissolves the heptad. Particular solvents that are satisfactory for epoxy resins are cylene, benzene, ethylbenzene, toluene, and alkoxyalkanols. About monomer, 7#:f
For example, alcohol, alcohol, ethanol, propatool, butanol, etc. are suitable. Butanol is particularly suitable. Ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, etc., 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, propatool, ethylene glycol monoethyl ether, and the like. Typically, the M of the solvent may be from 5 to 30 inches (M#) based on the weight of the other components i+. In fact, it is preferred that the mixture of the epoxy resin and the abrasive agent be reacted in the presence of a free radical initiator, eg penzoylpa-oxide.

Representative and useful free radical initiators are cumene hydroperoxide, benzo pulperoxide, tertiary perbenzoate, tertiary butylpero-V-site, lauroyl peroquinide, methyl ethyl ketone peroxide, chlorobenzoyl peroxide. Oxide etc. Benzoyl peroxide is preferred as a free radical initiator for use in the practice of this invention. The amount of free radical catalyst is determined by the weight of penzoyl permoxide per total weight of polymerizable debris at the temperature of use.
It is expressed as rA-chi or portrait. The catalyst needle contains at least three doses of benzoyl peroxide based on the weight of the monomer,
For women, it is 4chi (M:ii7) or the equivalent. On the other hand, the mA degree is preferably 80°C to 130°C (2). The temperature can be adjusted within a relatively wide range based on the reactivity of the mixture. In this case, the operating temperature is 30°C to 200°C depending on the purpose and operating conditions. After the monomers are added, the reaction temperature is maintained for up to 3 hours to complete the conversion of the monomers.In situ polymerization of the monomers results in at least about 20 % of polymerized monoethylenically unsaturated carboxylic acid monomers, producing in situ carboxy-functional polymers, epoxy-acrylic graft polymers and non-grafted epoxy resins, ↓ U.S. Pat. No. 4.21.781 It is described in.

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. The esterification reaction can be carried out in the presence of an amine catalyst in an amount greater than 0.3 t catalyst to avoid gelation. The epoxy-acrylic ester is also preferably carried out in the presence of two or more amine esterification catalysts based on the weight of the reactants to be esterified. Preformed acrylic polymers are preferred [7] or copolymers containing at least about 20 g (by weight) based on the total weight of the copolymer (also copolymers containing monoethylene-type subsaturated carboxy monomers [7]). The epoxy resin portion contains at least about 40% epoxy-acrylic ester! In the polymer formed by pre-carboxyl groups, the chemical The excess carboxy functionality in the epoxy-acrylic ester reacts with the substrate and provides a means of dispersing the polymer in water, with the oxirane functionality in a ratio of about 1:2 to 1:20. The product is made self-emulsifiable in water, details of which can be found in European Patent Publication No. 0.006.334 (1).
980° (released on January 9th). epoxy
Another method of making acrylic copolymers is to react 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 to form the epoxy resin. - Creating complex quaternary ammonium-amine salt bonds in acrylic copolymers. Details thereof are described in US Pat. No. 4,247,439. 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 method of reacting the combination with an epoxy resin in the presence of a large amount of amine is described in U.S. Pat. No. 4,289,811.

Furthermore, the epoxy acrylic copolymer is epoxylin Htj
The epoxy-acrylic part of the mixture is made of X ester and acrylic copolymer and includes a self-curing water-dispersed polymer. Epoxy phosphate esters can be made by reacting polymeric epoxy resins with 0.05% to 5% phosphoric acid. Acrylic copolymers are preferably prepared 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 resin-like polymer electrolyte polymer made from

With regard to the phosphorylated polymers which may optionally and preferably be added to the polymer formulations of the present invention, the mono- and dialkyl esters of phosphoric acid of the phosphorylated polymers;
Phosphated epoxidized oils, phosphated epoxidized polybutadiene copolymers, phosphated acrylic copolymers, phosphated polyesters, phosphated copolymers containing copolymerized phosphated monomers, epoxy phos Ph-1-, and phosphated epoxy-acrylic copolymers.

Phosphate esters of alkyl alcohols are mixtures of phosphoric acid mono- and dialkyl esters prepared by the reaction of phosphoric acid with an aliphatic alcohol having 2 to 20 carbon atoms, preferably 4 to 8 carbon atoms, and are described in U.S. Pat. It is described in Publication No. 005.619. Other water-dispersed phosphated copolymers may be used with ionizing agents and small amounts of organic cosolvents, such as those described in US Pat.
It can be made by polymerizing the monomer in water containing a co-solvent as described in 218.356. It contains an aqueous dispersion of a resinous polymer electrolyte produced by addition polymerization (7) of a saturated monomer, and contains at least one part of a monomer having a functional group that can be ionized in water, such as a carboxyl group.

The water contains an ionizing agent for neutralizing at least a portion of the functional groups in the resulting copolymer, as described in US Pat.
It is described in Publication No. 218.356. The phosphated resinous polyelectrolyte is prepared by forming an aqueous medium containing a co-solvent and adding an ionizing agent prior to or alternating with the monomers.
The monomers are polymerized by free radical polymerization to form a water-dispersed resinous polyelectrolyte. The remaining oxirane groups are then phosphated to form a water-dispersed phosphated polymer. Phosphated epoxidized oil contains phosphate ester of epoxidized oil or evoquinbolybutadiene copolymer and contains 5% of epoxidized polymer.
It is made by reaction with phosphoric acid up to . Phosphated acrylic copolymers can be made by reacting oxirane-containing acrylic copolymers containing hydroxy functional groups with phosphoric acid. Acrylic copolymers contain four ethylenically unsaturated monomers, especially glycidyl acrylate, 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 argyl esters such as hydroxyethyl and hydroxypropyl acrylate and methacrylate, styrene, α-methylstyrene, α-
They can also be made by reacting with hydroxyalkyl esters such as chlorostyrene and vinyltoluene. Phosphated acrylic copolymers can be made by reacting oxirane or hydroxy functionalized acrylic copolymers with phosphoric acid. The acrylic copolymers here contain copolymerized ethylene monomers, such as glycidyl acrylate or methacrylate, or hydroxy-functional monomers.

Phosphated polyester is a polynisder having a hydroxyl group at the end after reacting with phosphoric acid, and the original polynisder is esterified with a simple glycol and is a 9-dicarboxylic acid saturated or unPU a H polyester. Glycols include ethylene glycol, propylene glycol, diethylene glycol, diglopylene glycol, 1.
3 or 1.4 butanediol, hexanediol, and small amounts of polyol examples, t hagentaerythritol, triethylene glycol, trimethylolpropane,
It is also Hagrise T'-le. The unsaturated dicarboxylic acid component is an alpha-beta unsaturated dicarboxylic acid or anhydride such as ehama, leic acid, fumaric acid, itaconic acid, and the like. The saturated dicarboxylic acid or anhydride is phthalic anhydride, or the anhydride of phthalic, terephthalic, isophthalic, adipic, cepatic, succinic or similar saturated acids. Small amounts of monocarboxylic acids or fatty acids can also be added. It can also include lower alkyl acids and lauric, palmitic, myristic and stearic acids.

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-based bulkers with phosphated hydroxyethyl acrylate or similar phosphated monomers. Ethylenically unsaturated mono-
M.

Phosphated copolymers are obtained by copolymerizing the ethylene type monomer with a phosphated ethylenically unsaturated monomer by aqueous polymerization methods such as suspension, emulsification, and aqueous ionization resin. It can be produced by polymerization using a polymeric dispersant, a microemulsion azeotropic method, or a method similar to the above-mentioned method.

Phosphated epoxy-acrylic copolymers are prepared by polymerizing ethylene-type polymers containing ethylene carboxy monomers in situ in the presence of epoxy phosphate resins to produce phosphated epoxy-acrylic copolymers. I can do it. Other phosphated epoxy-acrylic copolymers are produced by reacting an epoxy resin with a pre-formed acrylic carboxylic acid copolymer in the presence of a large amount of amine to form an epoxy-acrylic ester copolymer! Epoxy in the presence of F or amine and water
It is possible to make an acrylic quaternary ammonium copolymer. Here, phosphoric acid is added after the epoxy acrylic copolymer is formed.
Or react before that.

Other phosphated epoxy polymers include epoxy polymers that react with phosphoric acid (7) to form phosphated epoxy ester polymers.
Contains at least about 0.1 equivalent ml of phosphate, preferably 0.1 to 1 equivalent ml, of phosphate per ml. in this case,
1 mo/L of monoepoxy polymer can contain up to about 1 moA of nordic acid salt. On the other hand, 1 mole of diepoxy polymer can contain up to 12 moles of phosphorus salt. Phosphated epoxy polymers contain about 0.05 to 25% of reacted phosphoric acid (-7%), preferably 0.1 to 3% of reacted phosphoric acid; a significant excess of phosphate reactant is preferred. Not.

Phosphated epoxy resins are prepared by heating a solution of an epoxy polymer dispersed in a suitable solvent such as methyl ethyl ketone and 2-butoxycetanol (1), then pouring over phosphoric acid (preferably [7]).
Alternatively, the epoxy group is reacted with polyphosphoric acid at a reflux temperature of 120° C. to 145° C. for 2 to 178 hours to complete the reaction between the reacting epoxy group and the phosphoric acid. The method for producing epoxy phosphate resins is disclosed in U.S. Patent Nos. 4.289.812 and 4.31.
It is described in Publication No. 6.922. In a further variant 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 unphosphated epoxy resin and 1 part by weight of phosphated (
7. React with an epoxy resin at about 120°C for at least 2 hours (1, 1) Add an epoxy phosphate containing phosphoric acid to the 7. Phosphate (10) (, J-boxy tree R”
+ A and react at a sufficiently high temperature and for a sufficiently long time [7. AA I'll be able to sing. Phosphation [7]11. In order to hydrolyze the a substance, approximately 2 Lfo of water is added (7) on a solid basis to accelerate the hydrolysis. From 0.05'A to 5% of the reacted phosphoric acid fl-b epoxy phosphate can then be dispersed by mechanical mixing in the mixture of amine and water. In addition to the water-dispersed epoxy resin composition, a self-curing water-dispersed polymer can be prepared.

7. A sprayable coating composition can be prepared by mixing a reactive self-curing polymer, an epoxy-acrylic copolymer, and a phosphated polymer as matrix polymers. can. Generally the composition is about 5% to 9%
90mm self-curing polymer, 1 to 70mm epoxy
Contains acrylic copolymer and O to 50% IJ phosphate polymer.

Preferred coating compositions of the present invention include, by weight, 40% to 90% reactive self-curing polymer, about 1% to 30% reactive poxy-acrylic copolymer, and 0% to 30% reactive self-curing polymer;
0%, preferably 3 to 20%, most preferably 3 to 15% phosphate polymer. The binder matrix polymer composition is then combined with a water-dispersed crosslinking component to serve 12 with an aminogellast resin suitable for thermal curing and crosslinking with the carboxy functional groups of the epoxy-acrylic copolymer mixture. The coating composition adhesive contains 0% to 15%, preferably [7 or 1 to 10% by weight of the polymer].
The composition is a mixture of 85% (or 100%) of the aminoplast crosslinked resin and 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-formaldehyde resins.

Additionally, aminoplasts include benzoguanamine, aptatoguanamine, and urea-formaldehyde. Commercially available water-soluble or water-dispersible aminoplasts for this purpose are Cymel 301 (cymel), Cymel 303, Cymel 370 and Cymel 373 (manufactured by American Cyanamid, Stamford Conn., USA).
an cyanamld, stamford,
Conn, , ) are included. The aminoplasts are melamine-based, for example hexamethoxymethylmelamine (Kumel 301χ and Beetle 80 (B
eetle) (manufactured by 7'/7Namide, USA) and is a methylated or butylated urea. Other suitable aminoplast resins are aldehydes and polmarguanamines; ameline:2-chloro-4,6-diamine-1,3,5-)riazine; 2-phenyl-P-oxy-4,6-diami2-1, 3. It is a reaction product of s-triazine and 2°4.6-) ethyl triaminol, 3°5-triazine. mono.

di- or triarylmelamine e.g. 2゜4.6-)
Riphenylutriamino-1,3°5-triazine is suitable.

The water-dispersed crosslinking component can be prepared by mixing together various water-dispersed polymers. Self-curing polymers are made in aqueous solvents. Aminoplast polymers are 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 and tertiary alkyls, alkanols, aromatic amines, alkanol-alkyl mixed inhibitors, etc. These compounds can be dispersed in water using compounds such as mono-ethanolamine, dimethylethanolamine, jetanolamine, triethylamine, dimethylaniline, ammonia hydroxide, and the like. It is described in US Pat. No. 4,212,781.

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-curing polymers containing alkylalkyloacrylamide monomers are polymerized in the presence of epoxy-acrylic copolymers or phosphated polymers or mixtures thereof.

Similarly, epoxy-acrylic copolymer-straddled phosphated polymers are self-curing polymers in which the monomers are polymerized in situ in the presence of other preformed polymers (made with 7 or straddled). It can be made by polymerizing on the spot in the presence of polymers.
V Sea Acrylic Co-Jn Combination, Reactive Self-Hardening Stainless Steel '1
°The amount of water contained in coating compositions containing polymers, phosphated polymers and aminoplast resins is related to the method of use [7
Coating compositions of 1, 12 and 12, adjusted to the desired viscosity (7) have a polymer solids content of less than 10%, 30
% (by weight) and 70 to 90% (by weight, t) of water, including small amounts of other volatile components such as solvents. For applications other than spraying, the aqueous polymer dispersion can contain about 10 to 1740% water. Organic solvents can still be used for other applications. Other solvents are normal-butanol, 2-
Contains butoxy-ethanol-1, xylene, and toluene. Also preferred is normal-butanol used in combination with 2-butoxy-ethanol-1. The coating compositions of the present invention can be colored and/or coated with known pigments and opaque substances.
It can still be made opaque. In many applications, including food,
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 on transparent as well as colored films. Moreover, spraying is appropriate. After application to the metal material, the coating can be thermally cured E7 at a sufficiently high temperature, from about 95° C. to 235° C. or higher, to complete the cure or volatilize the volatile components. Upon thermal curing, reactive self-curing polymers are reactive (and also self-curing). Here, the alkyl group of the alkoxyacrylamide is the alkylolacrylamide chain, which is a carboxy, hydroxy, or amide group. The carboxyl group in the epoxy-acrylic copolymer mixture and the epoxy phosphate and monoamino/plast resin can be reacted with a functional precipitate or with a hydroxyl functional group.

Beverage containers, particularly containers for carbonated beverages such as beer, utilize metal sheet coatings that cover the exposed metal surface by a polymeric coating.1. Must use I7 at 5 mg. For application, the water dispersion coating may be 0.1 to 1 mil thick.

Next, the present invention will be explained by referring to examples. All parts are parts by weight, all fractions are weight percent, and all temperatures are O°Cτ-f. Example 1 Preparation of self-curing copolymer Styrene/ethyl acrylate/'methacrylic acid/N
- A two-step heat-cured acrylic emulsion copolymer containing imbutoxymethylol acrylamide was prepared with 100 parts of deionized water and O
, 80 parts of sodium dihexyl sulfosuccinate was charged into a reactor, and heated to 77°C while stirring in a nitrogen stream.
heated to. At the controlled reaction temperature, the nitrogen blowing is discontinued and 0.10 part of ammonium bicarbonate salt is added. Next, 3.0 parts of styrene and 20 parts of ethyl acrylate
of the mixture was added to the reactor and emulsified for 10 minutes.

0.25 parts of ammonium persulfate was then added and the reaction was carried out for 20 minutes before the single body stage Na 1 was started.

Monomer stage Nα1 contained 33.0 parts styrene, 26.5 parts ethyl acrylate, and 3.50 parts methacrylic acid. The single mouse stage was added to the reactor at a constant rate. Addition ended after 30 hours 1, monomer stage 1α
2 is 14.0 parts of styrene, 11.5 parts of edyl acrylate, 1.5 parts of methacrylic acid, and 0.5 parts of N.
- Consisting of isobutoxymethylol acrylamide. It was then added continuously to the reactor over a period of 1.25 hours. After completion of monomer mixture No. 2, the batch was maintained at reaction temperature for 2 hours. It is then cooled and filtered.

The size of the monomer stages is not limited to this example. Satisfactory spray characteristics are achieved by maintaining a first stage/second stage ratio between 25/27 and 75/25.1. Ta.

Similar to Example 1, another self-curing copolymer, L2, was molded with alkylolacryl-amide in the second monomer stage. .

Good Example 11-13 In contrast to Examples 1-10, the emulsion polymer was rounded to contain an equal amount of -r-rukyrolacrylamide 4') in both monomer stages.

Table 2 Experiment N (LJl Experiment Nll) 2 Experiment N [L13
Anoshiki 11-ruacrylamide NMA Nth 3MA
NiBMA alkylol acrylamide level 3.0 5.0
10.0 Power A boxy, Kodatai level 5.0 5.0
5.0 Polymer Tg 30 40 50 Example 14 An epoxy acrylic guccinocopolymer was made according to the following recipe.

Epoxy resin (DER-333) 1 (147.8 grams C2.31 bond) was heated to about 82°C in a stirred reactor. Bisphenol A330.7 grano (i
, 17 Bond) was added with stirring. The reactor was then heated to about 191° C. for 2 hours. It was heated for an additional 2 hours. Check the viscosity and oxirane content periodically. The target oxirane number is approximately 0.6%, and the viscosity is 25°C and 2%.
．． (Gardner-Bolt)
er-Hoot). When these values were reached, 1612.4 grams (1.35 pounds) of 2-butoxy-ethanol was added, followed by 920.8 grams (920.8 grams) of N-butanol.
2,,03 bond) was added.

At this point, the molecular weight of the epoxy resin was approximately 5,500 based on oxirane content. 2 methacrylic acid in a separate container
90.3 g (0.64 lb), styrene 18.1
grams (0.4 lbs.) of ethyl acrylate 199.
6 grams (0.44 bond) 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 patch was cooled to 85°C. The acid value was 85 based on solid content.

The resin patch is then dehydrated (resistance of at least 5
0,000 ohm-centimeter) 4966.9 grams (10,95 bond) and dimethylethanolamine 2
58.6 g (o, s 7 bond) of the mixture was fed to a stirred reduction vessel containing a mixture of 58.6 g (o, s 7 bond). The temperature of the resulting mixture was 50°C. Maintain this temperature for approximately 1 hour, then add 2268 grams (5 bonds) of cooled deionized water to the formulation.
was added and cooled to below 32°C.

In the example described above, the amount of benzoyl peroxide used during the reaction was about 6.8 inches (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.

3rd Table U 7013 8 985 Z-Z, 3013342385 Z-Zl 7013 7.70.3852-Zl
8013 6.80.285Z 5032.517.
00.5210Y 6025.7513.850.4
168Z! l 8013 6.80.285 [Note] 2MAA Methacrylic Acid 38T Styrene 4EA Ethyl Acrylate Example 15 Method A The epoxy phosphate was made according to the following recipe.

Butyl cellosolve with epoxy resin (DER-333) 1
005 grams and Bisphenol A 3405 Grano were charged into a 51-volume round bottom flask equipped with a stirrer, condenser and thermometer and heated to 140°C. temperature is 140
When the temperature reached 188°C, the heating was changed to external heat and raised to 188°C.

When the external heating 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 is approximately 2.28
% and is 40% non-volatile and has a viscosity of 100% and 40%. When this value is reached, Butyl Cellsolve 227
Added grams. The batch was cooled to 120°C. When the batch temperature reaches 120℃ [7, 85 tyrinic acid 63
．． A mixture of 64 grams and 20 grams of butyl cellosolve was added dropwise.

The temperature of the batch was raised to 145° C. by external heating.

The batch was cooled to 120°C and maintained at this temperature for 30 minutes. 27 grams of water was added to the reaction mixture. batch is 120
Heated for an additional 4 hours at . Then butano) LA24
1 gram, butyl cellosolve 784 grams, dimethylethanolamine 1225 grams and deionized water 2.5 grams
00 grams were added to each. The final mixture was heated for 2 hours to obtain a stable emulsion.

Method B Epoxy phosphate ν epoxy resin (DER-333)
81.6 Gudim, 384 grams of bisphenol A and 163 grams of butyl cellosolve were added to a 5 ton round bottom flask equipped with a stirrer, cooler and thermometer and heated to 140°C.
It was made by heating. When the temperature reached 140°C, heating was stopped 7 and the external heating temperature was increased to 155°C. When the external heating temperature reached the maximum, the temperature was increased to 175°C for another 2 hours.
It was maintained at that temperature.

The viscosity and oxirane content (%) were measured periodically. The oxirane number was about 0.87.

Viscosity is 40% N Y in Butyl Cernolp
Met. When these values were obtained, Butyl Cellsolve 163 Grano was added and the batch was cooled to 125°C.

A jJip compound of polyphosphoric acid (FMC) i4.2 gum and butyl cellosolve 5o grano was added over a period of 45 minutes (and an excess of 30 grams of butyl cellosolve was added. was maintained at 120 T for 1 hour. 23 grams of deionized water was then added to the reaction mixture. The batch was maintained at 120 °C for an additional 2 hours [,,,, fr-0, then heating was discontinued and the butanol 2 (13 grams were added over 8 minutes. 1550 grams of deionized water and 17.4 grams of dimethylethanolamine were added in a container at
Heat to 1°C. The resin was gradually added dropwise into the aqueous amine mixture to form a stable emulsion.

1000 grams of deionized water was added to the resulting il f emulsion to adjust the NVK to 25% (-1). Stirring was then continued for 2 hours to obtain a homogeneous mixture.

Each epoxy phosphate was prepared according to Method A or Method B with the following molecular weight changes.

Table 4 94100.34 0.3530.3 Good 6150
0.52 0.3934.4 Good 4000 0.8
0 0.9234.9 Good 3080 1.04 0
．． 9232.8 Good 2500 1.26 2.30
23.0 Good 14002.28 4.2022.4
Successful Example 16 Approximately 860 grams of the emulsion copolymer obtained from Example 1 was added to a 5 ton reaction flask along with deionized water to make approximately 23 tons of NVM. The resulting mixture was stirred frequently for about 15 minutes to prevent foaming. Then DMEA15.5
Add a pre-mixed mixture of gram and water 82.8 to approx.
Stirring was continued for 0 minutes. Putokishechnol approx. 72.
8 grams were added and stirred for 30 minutes. Then Example 15
220.8 grams of epoxy phosphate obtained from Example 14 and 81 grams of epoxy acrylic copolymer obtained from Example 14.
5 grams were added gradually over approximately 1 hour. Normal
259.3 grams of butanol was added and mixed with vigorous stirring for about 15 minutes. Next, aminoplast resin Kumel 3
Approximately 31.3 grams of 03 was added and mixed for approximately 15 minutes.

Approximately 68.1 grams of deionized water was added, mixed for approximately 1 hour, and filtered.

The resulting polymer mixture is superior to the composition for spray coating the interior of cans (7). Therefore, several types of blended compositions are shown in Table 5. The epoxy phosphate was Example 15. The 7-epoxy acrylic was Example 14 (A). The water-dispersed copolymer was Example 14 (A). They were from Examples 1 to 10.

Example 17 Similar to Example 16, a coating composition was made as follows.

I 03 i□grams of emulsion from Example 13 were added to a 51 content reaction flask along with 922 grams of deionized water. The mixture was stirred gradually to prevent foaming. D
A premix of 18.7 grams of MEA and 40.0 grams of water was added and stirred for about 30 minutes. Next, add 73.6 grams of butogin ethanol and stir for 30 minutes. Ta. Thereafter, 263.7 grams of normal-butanol was added and mixed by vigorous stirring for about 15 minutes.

Next, epoxy acrylic copolymer 354 from Example 14
．． 0 grams and epoxy phosphate 183 from Example 15
．． 0 grano was gradually added over a period of about 1 hour. Aminoplast resin, Kumel 303 was added to the resulting polymer mixture.
31.3 grams 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 a 5 ton reaction flask with stirring.

A premix of 18.1 grams of DME A and 37 grams of water was slowly added to the latex with constant stirring. Approximately 226 grams of butanol was added over a period of 1 hour. Approximately 711 grams of the epoxy acrylic copolymer from Example 14 was then added over a period of 15 minutes.

Approximately 72.5 grams of butoxethanol 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 A coating composition was prepared in the same manner as in Example 16 as follows. about 1000 grano of water-dispersed copolymer from Example 13,
was added to a 5 ton flask along with 770 grams of deionized water while stirring gently. DMEA],
8.4 grams and 100 grams of water were premixed (7) and the mixture was added over about 30 minutes with constant stirring.

Next, 72 grams of butoxycetanol, 226 grams of normal butanol and 130 grams of water were mixed in advance
7 ingredients were added and mixed over 30 minutes. Example 15
716.8 grams of epoxy acrylic copolymer from 1. Then 30,332.8 grams of the aminoplast resin Cumel and 80 grams of water were added. The resulting polymer mixture was further stirred for 2 hours to ensure thorough 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 A covering composition was prepared in the same manner as in Example 16 as follows. A mixture of 500 grams of the emulsion copolymer from Example 1 and 500 grams of deionized water was charged to a 51 ml reaction flask. DMEAIO duram and deionized water],
A premixed solution of 0.00 grams was added to the emulsion over a period of 30 minutes. Next, 243.0 grams of epoxy phosphate from Example 15 and 1326.1 grams of epoxy acrylic copolymer from Example 14 were added over a period of 1 hour.
Added while stirring vigorously. Approximately 87 grams of normal butanol and 305 grams J2 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 Method (a) Epoxy resin, liquid spray resin DER-333 (Dow Chemical Company, Midland, Michigan) (L)ow C
chemical company, Midland.

Mjchigan) 41449, bisphenol-A
2135 grams and 2-putogyzoethanol-14
1. 09g was prepared. A water-cooled condenser was installed at the neck of the flask. An air-driven mechanical stirrer was installed in the second neck. Supplying nitrogen gas 1. The third neck was run at 1lfi, t,"0. Temperature n1 was established in the fourth neck. The mixture was stirred in the flask under a vacuum of 38.1 inches (54 inches).

Raise the temperature to 140 °C and stop heating and vacuum 1.
Approximately 40 grams of lr0 volatiles were collected. It consists of water, xylene (1) from ER333) and 2-poxyethanol-1. The reaction temperature is approximately 1 with external heating.
The temperature was raised to 75°C.

This salt layer was maintained for 5 hours. After 1 hour, the viscosity of the epoxy resin was Y Gardner-Holt (2-butoxyshetanol-140 solution). 3 hours later Y15 hours later 2. After 5 hours, 1012 grams of 2-butoxy-2-ethanol-1 was added. The epoxy solution was allowed to cool to room temperature (7 hours).

(b) Acrylic terpolymer, 5503 g of butanol was charged into a 12 t four-neck round bottom 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. 1764 grams of methacrylic acid,
A stoichiometric mixture of 924 grams of styrene, 26 grams of ethyl acetate, and 182 grams of Pennsylvanian 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 (7
After that, it was cooled to room temperature. The non-volatile content of the reaction mixture is 347
Met.

Epoxy resin (a) in a round-bottom four-necked flask with inner W5z,
1.306 grams and 694 grams of acrylic resin (b) were charged. The reaction mixture was stirred for 7 hours while bubbling with nitrogen. 1 was maintained at this temperature for 4 hours, then 23.6 grams of dimethylethanolamine and 2-butoxy-
-1144 grams of ethanol was added over 4 minutes.

The reaction mixture was maintained at 1,10'5°C for 4 hours [
It's 7. The viscosity of the resin is U1/4 (from 1 part resin, 1 part virol). A 5.571 (2 gallon) stainless steel container was charged with 2043 Grano deionized water and 86.1 grams of dimethylethanolamine. The container was placed on a hot plate and the water temperature was 50°C. After that, the contents of the resin from the 5-sided flask] 5 (l Ogura l
, was dropped into the stirring water. An emulsion was easily formed. The non-volatile content of the emulsion is 23.5%, the viscosity is 38 seconds for 4 cups of Fordna, the acid value is 34.1, and the alkaline value is 7.
It was 6.4.

adhesive composition The adhesive composition was made by mixing the following ingredients.

1200 grams of emulsion copolymer of Example 1, 8 ounces of deionized water
93 grams, 21.7 grams dimethylethanolamine, 86.8 grams deionized water, 1106.7 grams 2-butoxy-ethanol, 225.5 grams epoxy phosphate, 284.3 grams epoxy-acrylic ester from above. 11. Normal butanol 363.6 Crumb, cumel 30
32.7 grams of deionized water, 400.5 grams of deionized water, and the above formulation was evaluated as the inner coating of the can (7).

NVM was 18.8ch. The viscosity was 15 seconds for 14F4 Ford Cup. Acid value 35.5; alkaline value 2
9; Neutralization value 81.7%: Organic solvent 7/Solid content 0.9:
2-butoxy-ethanol 1/n-butanol ratio 3
0/70: and cumel was 5 cm on a solids basis.

The coating was air dried and baked to form a clean continuous coating. The coating had a 24% wedge bulge void (1) and became slightly red upon pasteurization at 75.5°C (170'F) for 10 minutes; red adhesion was excellent. The void ratio was 1 or less, MEK Masatsuke overall 24 and general film properties were excellent.

Example 22 The high molecular weight epoxy resin was Epon 828 [Cell Chemical Company, Heathon, Texas (5hell CHo
m1cal Co., Houston, Texas)
248 grams of liquid epoxy resin bisphenol A, and 248 grams of bisphenol A from 2-butogine
It was made by reacting ethanol #1125 Durum in 23 grams of xylene. Dissolve 0.32 grams of sodium acetate trihydrate in 3.6 grams of water, M 1
The diluted solution was added. The reaction mixture was charged to a 121 volume recirculating round bottom flask. The first neck is equipped with an air-driven mechanical stirrer, the second neck is equipped with a water-cooled 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 furnace. Heating was performed using a heating mantle. When the temperature reached 140°C, heating was discontinued and the temperature of the reaction mixture was brought to 75°C by external heating. The temperature was kept at 175°C for 5 hours.Then, the viscosity of the epoxy resin was
40% solution) AI-22 (Gardner-Holdt viscosity). Heating was discontinued and 484 grams of normal butanol was carefully added. The temperature after adding butanol is approximately 11
The temperature was 5°C.

114 grams of methacrylic acid 11 grams, 60 grams of styrene,
1.6 grams of ethyl acrylate, benzoylperne oxide (78% active in water) and 2-butoxy-ethanol-145g were added to the epoxy resin over a period of 2 hours.

Temperature f+2i, I: T I maintained at 5°C (and after processing A', add 25 g of the medium mixture using a pouch L,], maintained at 15°C for 1 hour) Shibuki. , streak 1/fu 888 grams, ethyl acrylate/l
-35Q Plano 1, Methacrylic Acid 186 Grano, Benzoino 1 Pero V Cyto (78% active in water) 36.
1289 grams of 1,2-butoxy-ethano/L and 18 grams of normal-butano-1 were slowly added to the epoxy-acrylic graft copolymer at 115°C.

The addition took 13 hours. The reaction mixture was heated to f at 115°C.
After 30 minutes, 719 grams of n-butanol was added. The mixture was cooled from 115°C to 85°C (7
, gradually add the epoxy resin Epon 828.450 Grat and then maintain at 90°C for 1/2 hour [2. Then 80 grams of dimethyl ethyl fluoramine and 50 grams of water were added and the reaction mixture was maintained at 80° C. for 1 hour.

Next, add 29 grams of dimethyl ethanol and add 20 grams of dimethyl ethanol.
A dispersion of M was obtained. The resulting copolymer is believed to be an epoxy-acrylic graft copolymer containing quaternary ammonium functionality. Film boiling joys and voids have been significantly improved.

Example 23 ＾ (a) A round bottom turning flask with contents of 5 tons was filled with 2 parts deionized water.
I prepared 211 grams. The flask is filled with nitrogen gas.
A thermometer, water-cooled condenser, and air-driven mechanical stirrer are provided. water t'.

After heating to 60°C, Vinol 523 (
Air Product and Chemical (polyvinyl alcohol from Uaine, Paa)
and Chemical, Wayne, Pa.)
110 grams were added, and it took about 20 minutes to dissolve (7).
64 grams of BMA monomer (Isopuku, Harno [[Vi85]) and 13 grams of Lauroy/L Par71 Kid were added to the aqueous solution at about 70°C and the polymerization was carried out at 70°C for about 5 hours and 9 hours. At the end of this time, the polymerization mixture was cooled to room temperature, the non-volatile fraction of the suspension was 29.2%, and the viscosity was 25 seconds at 4 cups of liquid.

suspension polymer, epoxy-acrylic graft copolymer (Example 14a) and epoxy phosphate (Example 1)
5) mixture as follows [2. I made it.

Polymer (a) suspended in a 5 ton rotating round bottom flask containing 10
00 grams, and 754.5 grams of deionized water. The flask was equipped with a nitrogen gas inlet, temperature needle, water-cooled condenser, and air-driven mechanical stirrer. The mixture was heated to 38° C. and 18 grams of Tumekunoviamin ethanol and 83.6 grams of deionized water were added.

The temperature rose to 48°C. Mixing continued for 15 hours. Next, 155.9 grams of 2-ethoxy-butanol was added, followed by 2.8 grams of deionized water. The mixture is 43
The mixture was stirred at ℃ for 40 minutes. Epoxy-phosphate (Example 15) 3 grams of 200° was added over 30 minutes, followed by 68.2 grams of deionized water over 15 minutes. Next, epoxy-acrylic graft copolymer 378
．． 1 gram over 30 minutes, then 77 mL of deionized water.
．． 1 gram was added over 5 minutes. Next, 168.4 grams of normal butanol was added over a period of 10 minutes. An additional 29.1 grams of Shimel 303 was added. An additional 55.2 grams of normal butanol was added over 15 minutes, followed by 205.4 grams of deionized water. The non-volatile content of the formulation was 15.1% and the viscosity was 13 seconds at 7 ordna and 4 cups. The film was drawn onto a glass plate and then baked on a pot plate for 5 minutes at 194°C (380'F) to give a smooth coverage.

Example 24 In a 5 ton flask equipped with a stirrer, thermometer, condenser and nitrogen gas inlet, 434 ml of 2-butoxyshetanol was added.
5 grams were charged and heated to 150°C. temperature is 150℃
solid epoxy resin (Epon 10 (19
F) 1000 grams were 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 puknol was slowly added, maintaining the temperature at 115°C. Methacrylic acid 1
59.1 grams, 83.2 grams of styrene, 2.3 grams of ethyl acrylate, 25.6 grams of glycidyl methacrylate phosphate, 21 grams of benzoyl peroxide.
．． A mixture of 7 grams of epoxy solution and 62.4 grams of 2-butoxyshetanol was added over a period of 172 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. The resin was then charged to a stirred reduction vessel containing a mixture of 2550 grams of deionized water and 3 grams of DMEAI O.

The temperature of the resulting formulation was 50°C. Maintain this temperature for approximately 1 hour, then mix the formulation with 100% of chilled deionized water.
gram and cooled below 32°C. The phosphated epoxy-acrylic graft copolymer was mixed with the emulsion copolymer from Example 1 to make an excellent spray can interior coating.

Example 25 125 grams of the emulsion copolymer from Example 1 was added to a 51 content flask along with 112.5 grams of deionized water. This mixture was stirred frequently for about 5 hours. 1.3 grams of dimethylaminoethanolamino and 12.5 grams of deionized water
Add the grano while stirring constantly. Then add 9.5 grams of 2-buto coconut ethanol and then add Example 15
and 56.4 grams of epoxy acrylic melamine graft polymer made by the method of Example 1 of U.S. Pat. No. 4,289,811.
Added grams.・Then, normal-butanol 28
．． 5 grams, 3.7 grams of aminoplast resin, and 3.3.7 grams of Cumeno L30 were added and mixed well.

Next, DMEAo, 5 grams 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 Formulation Hydroxy-terminated polybutadiene (Hiker) 300 X 29 B.F.

Goodrjch) 184 parts and 79 parts of 2-butoxycetanol were added. Heating and stirring were performed by blowing nitrogen gas. At 50 DEG C., a mixture of 1.84 parts of superphosphoric acid and 44 parts of 2-butoxycetanol was slowly added over a period of 11 minutes. The temperature of the reaction mixture was kept at 125° C. for 25 minutes. Thereafter, 3.7 parts of water were added and the reaction mixture was maintained at a temperature of 125° C. for 2 parts. The temperature was then lowered to 75° C. and 3.7 parts of dimethylamineethanolamine were added, followed by 303.2 parts of water. Next, 110 parts of 2-butoxyshetanol were added, followed by 25 parts of butanol. 26 parts of DMEA was added followed by 200 parts of water to adjust the solids to the desired amount.

Formulated Composition: To a 51 reaction flask was added 1000 grams of the water-dispersed copolymer from Example 13 along with 754 grams of water. The mixture was slowly stirred for 15 minutes. Two pre-mixed mixtures of 18 grams of DMEA and 200 grams of water were added, stirring constantly. Next, 341.7 grams of polypucdiene phosphate from the previous example was added and Zk17 Grano. Thereafter, 379.1 grams of Evogysia acrylic copolymer from Example 14 was added, and 19 grams of water was added (7
Ta. Next, 228.7 grams of normal-butanol was added to Xu K, followed by a mixture of 8.73 grams of butanol and 30,329.1 grams of cumel. 63.4 grams of water was added to adjust the resulting mixture to the desired solids content. The resulting mixture produced a good film of spray coating.

Example 27 Tall oil fatty acid (silfat V-18) (5ylfat V-18) was charged into a conventional polymerization reactor equipped with a stirrer, a cooler, a water separator, a thermometer and a nitrogen inlet, and heated to 80°C. . When the temperature reached 80°C, resinous polyol (Monzant R, J-101) (Mo
n5anto) was added and heated to 125°C. Eighteen inches of vacuum was required to draw off the water trapped in RJ-1-Ol. The reaction mixture was heated to 240°C;
Xylene was added as needed to assist in water removal. The temperature was maintained at 240 DEG C. for 2-1/2 hours and the acid value of the solids was 3.9. Heating was discontinued and the reaction mixture was heated to 120°C.
cooled down to. When the temperature reaches 120℃, acetone 1
567 grams were 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. At 25°C 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-butoxycetanol. 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 Coalescence An epoxy phosphated acrylic copolymer was prepared as follows. 828.1141 grams of 95 thievonoid, 614 grams of bisphenol 8, and 310 grams of 2-butoxyethanol in xylene with a stirrer, temperature side, nitrogen inlet,
A 51 volume flask was equipped with a condenser and a dropper. The mixture was heated at 90° C. with nitrogen bubbling. When the temperature reaches 90℃ (7, sodium acetate 0.5
Add a mixture of 2 grams and 3 grams of water and heat to 1
Continued in a 40℃ trench. 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 is 17
It was maintained at 5°C for 5 hours, then 360 grams of 2-butoxycetanol was added and cooled to 125°C. When the temperature reached 125 DEG C., a mixture of 7.32 grams of polyphosphoric acid and 20 grams of 2-butoxycetanol 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-butoxycetanol was added over a period of 2 hours, then the reaction mixture was It was maintained for an additional 2 hours at °C. The resulting resin was then dropped into a mixture of 3867 grams of deionized water and 162 grams of dimethylethanolamine. The irisated epoxy acrylic graft copolymer was mixed with latex (Example 13). The resulting emulsion was hardened with Chikumel 303 (7) and was a stable milky white emulsion, providing an excellent pus-retaining coating for steel cans used for soft drinks.

Example 29 An alkyl hydroxyphosphate was prepared by reacting superphosphoric acid and an alkyl epoxide according to the method described in US File 713, No. 487.130. By using 1,2-epoxyhexadecane, 240 parts of 1,2-epoxyhexadecane and 105 parts of superphosphoric acid dissolved in 200 parts of tetrahydrofuzin were added dropwise to Liquid K with 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 entire batch, and the solution was washed with 2 parts of 200 milliliters of saturated sodium chloride solution. The organic layer was dried over sodium sulfate and the solvent was evaporated to yield about 300 parts of hexadecane hydroxyphosphate. 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 hydroxy phosphate as a surfactant, 115 parts of deionized water and 0.10 parts of hexadecane hydroxy 71 phosphate were charged into a reactor and heated to 752°C. The pn of the solution was adjusted to 85-9.0 at 50°C by addition of dimethylethanolamine, and then heated at 76°C to 78°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 reacted for at least 20 minutes before starting to feed the single pieces.

The monomers supplied consisted of 55.0 parts of styrene, 26.0 parts of ethyl acrylate, 5.0 parts of methacrylic acid, and 12.0 parts of N-isobutoxymethylacrylamide. The monomers were added to the reactor at a constant rate over a period of 4.5 to 5.0 hours while the batch was maintained at a temperature of 76°C to 78°C]. The batch was then maintained at reaction temperature for an additional 2 hours before cooling and filtration.

Example 30 A monomer containing a phosphate functional group is prepared by reacting phosphorus pentoxide with hydroxydiethyl acrylate.
It was made by the method described in Publication No. 86.371. In this method, 140 parts of phosphorus pentoxide is mixed with 350 parts of hydroxyegol acrylate and 0.0 parts of phosphorus pentoxide.
The solution with 5 parts was stirred vigorously and added gradually. The reaction temperature was maintained at 35° C. by external cooling. After the addition of phosphorus pentoxide is completed, the reaction temperature is 30°C.
Stir for 5 hours and then heat at 45° C. for 2 hours to complete the reaction (Also, mono and geste 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 is best carried out in a 1:2 mixture of butoxy-ethanol and normal butanol. Emulsion polymerization can be carried out in aqueous liquids with additional addition of organic solvents.

Thermosetting emulsion copolymer containing phosphate monomer is made of 110 parts of deionized water and 0.10 parts of sodium dihexyl sulfosuccinate,! : was charged into the reactor. The solution is 76
Heated in a stream of nitrogen gas at temperatures between 78°C and 78°C. At equilibrium reaction temperature nitrogen gas is removed and ammonium bicarbonate, 0.
Added 10 parts. Next, 1.2 parts of styrene and 0.80 parts of ethyl acrylate were added to the reactor and emulsified for 10 minutes. In each case 0.30 part of ammonium persulfate was added and the monomers were allowed to react for 20 minutes before starting the feed.

The monomer mixture consisted of 35.5 parts of styrene, 50.0 parts of ethyl acrylate, 4.0 parts of methacrylic acid, 10.0 parts of N-isobutoxymethylacrylamide, and 0.0 parts of 2-phos-7ate ethyl methacrylate. Contained 50 copies. Monomer was added to the reactor at a constant rate over a period of 4.5 to 5.0 hours. During this time, the reaction temperature was maintained at 76-78°C. The batch was then maintained at reaction temperature for an additional VC of 2 hours, during which time an additional 400 parts of deionized water was added to reduce the viscosity.

Example 31 Thermosetting Copolymer Containing Alkyl Phosphate An alkyl phosphate was made by reaction of perphosphoric acid and an aliphatic alcohol. The method used was the same as that used for phosphate hydroxyalkyl acrylate as described in Example 29.

A thermosetting emulsion copolymer containing an alkyl phosphate was prepared by charging 115.0 parts of deionized water and 0.10 parts of octyl phosphate into a reactor and heating the mixture to 50 to 52°C. At 50°C to 52°C, the pH of the aqueous phase was adjusted to pH 7 to 7.5 with dimethylethanolamine.

Next, while blowing in nitrogen gas and stirring,
heated to ℃. At equilibrium reaction temperature, the nitrogen gas blowing was discontinued 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 1°, then 0.30 part of ammonium persulfate was added to the reactor, and the monomer feed initiator was 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-imbutoxymethylacrylamide were used. Monomer was added to the reactor over a period of 35 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 to reduce viscosity while feeding the monomers. The batch was maintained at reaction temperature for 3 hours before being cooled and filtered.

The 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 A 51 capacity flask equipped with a thermometer, condenser, stirrer, and nitrogen gas inlet was charged with a mixture of 10 Q grams of deionized water and 114.6 grams of dimethylaminoethanol.

The mixture was heated to 85°C. The half-moon temperature compound contains 548 grams of styrene, 487.1 grams of ethyl acrylate, 121.7 grams of methacrylic acid, 24.3 grams of benzine, 379.5 grams of butyl chloride, 379.5 grams of normal butano/L, and 379.5 grams of N(in). 60.9 grams of (butoxymethyl)acrylamide and 34.8 grams of tert-butyl hydroperoxide were added over a period of 4 hours]7. Once the addition of the monomer mixture was complete, the reaction mixture d 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 the polymerization.

Formulated Composition To a 5 ton 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. Mixture was mixed for 15 minutes 1
7. Then epoxy phosphate 20 from Example 15
0.3 grams were 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 30329.1 grams of Shimel 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 To a Content 51 flask with condenser and stirrer was added 1000 grams of the latex from Example 1 along with 1000 grams of deionized water. Dimethylethanolamine 18.1
gram and 50 grams of deionized water was slowly added.

Then 76.6 grams of butyl selenium and 222.8 grams of n-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. 1.33 grams of ammonium phosphate was then added and stirring continued for an additional hour, and the resulting mixture was mixed with 5 Chicumel 303. The coating cured to a clean film with good film properties.

Agent: Masao Miyake and 1 other person Procedural Amendment (Voluntary) September 2, 1982] Patent Office, 1st Licensor: Mr. Kazuo Wakasugi II Indication of Matters 1981 Special Patent Application No. 14f'i74. 1 No. 2,
Title of the invention Aqueous dispersion coating composition J6.1 Process for its production 3 Relationship with the case of the person making the amendment 'I! J'nT fishing trip per person 4,000
Administrator 〒l (1(, 16 Number of inventions increased by amendment () 7 Target of amendment 8, Contents of amendment (1) The handwritten specification is amended to be typewritten as shown in the attached sheet. (About the content) Correction Hana X, 1.) (
2) Supplement the power of attorney and its translation as shown in the attached sheet.

(3) Replenish three copies of the priority certificate and its translation as shown in the attached sheet.

563-

Claims (1)

[Scope of Claims] (1) Ethylenically unsaturated alkylolacrylamide monomers, ethylenically unsaturated functional monomers containing reactive functional groups, and other ethylenically unsaturated monomers, based on the weight of the polymer solids. An aqueous dispersion coating composition comprising: 5% to 99% of a stoichiometric copolymer, 5% to 70% of an epoxy-acrylic copolymer, and 0% to 50% of a phosphated polymer. (2) Phosphated polymers are 3% based on the weight of polymer solids.
%. (3) The composition further comprises an aminoplast resin of not 1% L I O'16 based on the weight of polymer solids.
ritFJ and the composition according to any one of the above items. (4) The composition according to any one of the claims and the preceding items, wherein the alkylolacrylamide component of the self-curing water-dispersed polymer is an alkylated alkylolacrylamide. (5) The composition according to any one of the claims and each of the above items, wherein the functional monomer contains a carboxy, hydroxy, amino, or amide group. (6) The composition according to claim 1 or any one of the above items, wherein the epoxy acrylic copolymer is a graft copolymer and is mixed with a non-epoxy resin and a non-grafted acrylic mixed polymer. (7) The composition according to any one of the claims and each of the above items, wherein the epoxy acrylic is a phosphated epoxy-acrylic polymer. (8) The composition according to any one of the claims and each of the above items, wherein the epoxy-acrylic copolymer is a quaternary ammonium polymer. (9) The composition according to any one of the claims and each of the above items, wherein the self-curing water-dispersed polymer is produced by copolymerizing its constituent monomers in the presence of a phosphate or phosphoric acid. . (10) The composition according to any one of the claims and each of the above items, which is an epoxy acrylic copolymer t and an epoxy acrylic ester copolymer. (11) The epoxy-acrylic copolymer is produced 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. A composition according to any of the claims and preceding paragraphs. (+2) If the IJ phosphate polymer is present and the phosphate polymer contains epoxy phosphate;
p7 and the composition according to any one of the above items. (13) IJ-acidated polymers exist, and a)
Ethylenically unsaturated monomers containing carboxy or hydroxy monomers in water containing ionizing agents. b) a phosphated epoxy resin; C) a phosphated epoxidized butadiene copolymer; d) a polymer comprising a copolymerized phosphated monomer; and e) a phosphated polyester. A composition according to any of the items. (14) Copolymerized ethylenically unsaturated alkylolacrylamide monomers, ethylenically unsaturated functional monomers containing reactive functional groups, and other ethylenically unsaturated monomers in which the self-curing polymer is a phosphate. A water-dispersed coating composition comprising a water-dispersed self-curing polymer that includes a saturated monomer. (15) The composition according to the above item 14, which is a 7-alkyl phosphate ester monomer copolymerized with a 7-alkyl phosphate ester monomer. (16) Ethylenically unsaturated alkylolacrylamide Monomers, ethylene-type lower t containing reactive functional groups;
Polymerization in a fi1 mixture compound (step 7) to prepare a self-curing water-dispersed polymer, then mixing the obtained self-curing water-dispersed polymer and an epoxy acrylic copolymer, and [
7. The above self-curing properties can be obtained by mixing with a phosphated polymer.
1% to 99% of the epoxy-acrylic copolymer and 0% to 50% of the phosphated polymer. A method for producing an aqueous dispersion coating composition according to any one of Item 12. (17) The monomer of the self-curing polymer is polymerized in the presence of an ionizing agent and F to form a resin-like polymer electrolyte water dispersion.
17. The method of claim 16 for making a curable polymeric f+. (18) The method according to any one of the above items 16 and 17, in which the argyroll acrylamide monomer is co-merged preferentially on the surface of the self-curing water-dispersed polymer. (19) The method according to any one of Items 16, 17, and 18, wherein the monomer is polymerized in the presence of a phosphate surfactant. (20) The composition is sprayed onto a substrate (7) and then the functional group is crosslinked with the alkylated acrylamide group and thermally cured. How to use the composition.