STABLE AQUEOUS DISPERSIONS OF CURABLE RESINOUS COMPOSITIONS AND ADHESIVE AND COATING COMPOSITIONS PREPARED THEREFROM

Abstract: Stable aqueous dispersion of a curable resinous composition comprising a half ester of a dicarboxylic acid with the secondary hydroxyl of a vinyl ester resin, the carboxylic acid group of said half ester being at least partially neutralized with an alkaline metal hydroxide, ammonium hydroxide or a tertiary amine. These dispersions find utility in adhesive and coating compositions.

Description: STABLE AQUEOUS DISPERSIONS OF CURABLE RESINOUS COMPOSITIONS AND ADHESIVE AND COATING COMPOSITIONS PREPARED THEREFROM It is well known that many vinyl ester resins are polymerizable. This is illustrated by the disclosure in U.S. Patent Nos. 3,560,237 (RE 27,656); 3,661,576; 3,673,140 and British Patent No. 1,375,177. The disclo- sures of U.S. Patent Nos. 3,560,237 (RE 27,656) and 3,661,576 are particularly relevant to the instant invention in that they pertain to vinyl ester resins derived from resinous epoxides (i.e., epoxy resins). Many of these vinyl ester resins from resinous epoxides are commercially available and possess excellent physical and chemical properties and are particularly useful as protective coatings for a variety of substrates. In this utility, the vinyl ester resins were normally dissolved in an organic solvent or a reactive diluent, applied by any of several conventional techniques (e.g., spraying, dipping, etc.) to a substrate and then cured, with actinic radiation or other catalytic inducement. The necessity of using an organic solvent is a commercial impediment for using the compositions set forth above. Organic solvents must be recovered and recycled or disposed of for safety, environment and/or economic reasons. The recovery in many instances is difficult and/or costly. These problems can be reduced if the organic solvent reacts into the coating. Consider- able research has been directed toward the use of vinyl monomers and low viscosity vinyl resins as reactive diluents. However, many of the useful reactive diluents, e.g., 2-hydroxyethyl acrylate, are toxic and represent considerable health and environmental problems. Many resinous systems have been rendered water-soluble or water-dispersible (oil-in-water dis¬ persions) by attaching various onium groups such as, for example, sulfonium, phosphonium, and ammonium, to the backbone of the resin or by adding an onium surfac- tant to the resin as a dispersing vehicle. Many of these onium compounds are electroreducible, particularly the sulfonium and isothiuronium compounds, and have been used in cathodic electrodeposition processes. An exhaustive documentation of this is not required; however, reference is made to U.S. Patent Nos. 3,793,278; 3,936,405; 3,937,679; 3,959,106 and 3,894,922 which represents a series of cases in which certain onium- -modified epoxy resins were alleged to be useful as electrodepositable compositions. The onium-modified epoxy resins were prepared by reacting an epoxy resin with a tertiary phosphine, tertiary amine or sulfide in the presence of an acid. The acid used in this series of experiments had dissociation constants greater than 1 x 10 " and included both organic and inorganic acids. Alkenoic acids, while meeting the dissociation constant criterion in many instances, were not named or used in any of these particular references. O?..PI This invention is directed to a stable aqueous dispersion of a curable resinous composition comprising a half ester of a dicarboxylic acid with the secondary hydroxyl of a vinyl ester resin. The carboxylic acid group of said half ester being at least partially neutralized with an alkali metal hydroxide, ammonium hydroxide or a tertiary amine. The dispersions have an o average particle size of less than 2500 A (250 nm) and are curable through the vinyl groups of the vinyl ester resin. The vinyl ester resins useful herein are the reaction products of a polyepoxide with an ethylenically unsaturated monocarboxylic acid which are further reacted with a dicarboxylic acid or anhydride to form a half ester. Such vinyl ester resins are disclosed in U.S. Patent No. 3,564,074. Any of the known polyepoxides can be employed in the preparation of the vinyl ester resins. Useful polyepoxides are glycidyl polyethers of both polyhydric alcohols and polyhydric phenols, epoxy novolacs or mixtures thereof. Within the scope of this invention, a number of polyepoxide modifications can be readily made. It is possible to increase the molecular weight of the polyepoxide by polyfunctional reactants, such as bisphenols, dicarboxylic acids or carboxyl terminated polydiene rubbers, which react with the epoxide group and serve to link two or more polyepoxide molecules in such a manner so as to join those diepoxide molecules and still retain terminal epoxide groups. Where polyhydric phenols are selected to prepare the polyepoxide, many structural embodiments are possible. Polyepoxides prepared from polyhydric phenols may contain the structural group wherein R- is a divalent hydrocarbon radical such as, for example, or R 1 is 0 0 II 11 -, -S-S- , -s-, -s * It _ 0 or -0-. The choice of novolac resins leads to a separate, well recognized class of epoxy novolac resins. Other modifications are well known to those skilled in the art. While the invention is applicable to poly¬ epoxides generally, a most advantageous class of poly¬ epoxides are those glycidyl polyethers of polyhydric alcohols or polyhydric phenols having weights per epoxide group of 150 to 2000 (i.e., epoxy equivalent weight). These polyepoxides are usually made by react¬ ing at least about two moles of an epihalohydrin or glycerol dihalohydrin with one mole of the polyhydric alcohol or polyhydric phenol, and a sufficient amount of an alkali metal to combine hydroxide with the halogen of the halohydrin. The products are characterized by the presence of more than one epoxide group, i.e., a 1,2-epoxy equivalency greater than one. A preferred class of polyepoxides are those derived from a methylene bisphenol or a 2,2'-isopropy- li ene bisphenol. Suitable α,β-ethylenically unsaturated monocar- boxylic acids include, for example, acrylic, methacrylic, crotonic, and cinnamic. As another unsaturated carboxylic acid, it is possible to use a half ester formed by reaction of one mole of a hydroxyalkyl acrylate of methacrylate with a cyclic anhydride. The above reactants are incorporated in the compositions to provide essentially a stoichiometric equivalency of carboxyl function with the oxirane groups present. By that is meant that there are from 0.8 to 1.15 equivalents of carboxylic acid ingredients for each equivalent of polyepoxide and preferably 0.9 to 1.05 equivalents of carboxylic acid. The esterification reaction is preferably catalyzed with known catalysts for the esterification of carboxyl groups with oxirane groups. Such catalysts include tertiary amines, such as tris(dimethylamino- methyl) phenol, and also include chromium salts. The composition is used to prepare a curable product by mixing the mentioned ingredients and reacting the mixture preferably between 80° to 120°C under catalytic inducement. If temperatures lower than 80°C are used, the reaction is very slow. If reaction temperature exceeds 120°C, side reactions are promoted decreasing the yield of the desired product and the possibility of a difficult controllable exother is presented. Because of the presence of reactive ethyleni¬ cally unsaturated groups in the reaction mixture, it is essential to maintain an inventory of a suitable vinyl polymerization inhibitor in the reaction mixture and also in the product composition. Any of the hydroqui- nones and quinones have been found to be suitable for this purpose, although it is generally preferred to employ the quinones since the hydroquinones tend to enter into reaction with epoxy groups of the starting materials. Toluquinone and toluhydroquinones are preferred inhibitors since the reaction products appear to be clearer when toluquinone or toluhydroquinone is employed as the inhibitor. Other successful inhibitors include p-quinone, 2,5-dimethyl-p-benzoquinone, 1,4-napthaquinone, anthraquinone and chloranil. Pre- ferred inhibitors in the product composition are 4-chloro-2-nitrophenol, phenothiazine, and oxalic acid dihydrate_ The ethylenically unsaturated monocarboxylic acid-polyepoxide reaction product containing secondary hydroxyl groups is further reacted with 0.1 to 1.2 mole proportions of dicarboxylic acid anhydride per equiva¬ lent of epoxide in a manner as disclosed in U.S. Patent No. 3,564,074. The dicarboxylic acid anhydride may be selected from either saturated or unsaturated dicarboxy¬ lic acid anhydrides or mixtures thereof as disclosed in that patent. A vinyl polymerization inhibitor such as, for example, the methyl ether of hydroquinqne or hydro- quinone may be added. Following completion of the reaction, the reaction mixture is cooled and the polym- erizable monomer may be blended therewith. A wide selection of polymerizable monomers containing the >C=CH 2 group is available from the many known classes of vinyl monomers. Representative species are the vinyl aromatic compounds which include such monomers as styrene, vinyl toluene, halogenated styrenes, and divinylbenzene. Other valuable monomers include, for example, the methyl, ethyl, isopropyl, octyl, etc., esters of acrylic or methacrylic acid, vinyl acetate, diallyl maleate, dimethallyl fumarate, acidic monomers such as acrylic acid, methacrylic acid, crotonic acid and amide monomers such as acrylamide and N-alkyl acrylamides and mixtures thereof. Preferred polymerizable monomers containing the >C=CH 2 groups are styrene, vinyl toluene, ortho-, meta- and para-halostyrenes, vinyl napthalenes, the various α-substituted styrenes, and acrylic, methacrylic and crotonic acid esters. * *■ ' . ' A nonreactive solvent can be used to replace all or a part of the reactive solvent. Such nonreactive solvents include glycol ethers; alcohols, such as butanol; ketones and methylene chloride. The resulting acid functionalized vinyl ester resin is next reacted with an alkali metal hydroxide, ammonium hydroxide or a tertiary amine in an amount to provide water dispersibility to that resin. While all of the alkali metal hydroxides are useful, sodium hydroxide and potassium hydroxide are preferred. Suitable tertiary amines include, for example, trimethylamine, triethylamine, triethanolamine, dimethyl- ethanolamine and methyldiethanolamine. The neutralization is carried out at a tempera¬ ture preferably between 20° to 80°C, most preferably between 20° and 75°C_ After neutralization, the resin can be dispersed in water to the desired solids content and viscosity. The dispersions of this invention contain from 1 to 13 weight percent carboxyl, preferably 1.5 to 7 percent. The dispersions advantageously have an average particle size of less than 2500 Angstrom units. The polymer of the particles is curable by free radical catalytic inducement generally at somewhat elevated temperatures and/or may be cured through the pendant carboxyls. The dispersions are useful as such or may be blended with aminoplasts, such as melamines or urea-formaldehyde or phenolplasts. Because the disper¬ sion can be water based, the problems associated with organic solvents in coatings can be eliminated or minimized. The dispersion may be formulated with color¬ ants, fillers, waxes or other conventional additives used for its expected effect. The dispersions find utility in adhesives and coatings. For example, they are useful as tire cord adhesives, glass sizings and adhesives for wood products. As coatings, they are metal decorative primers and finishes, interior and exterior can coatings, drum linings and other industrial and commercial coatings. Suitable tire cord adhesives for bonding the cord fiber to rubber are made by curing a blend of the dispersions of this invention with a suitable latex such as, for example, a styrene/butadiene/vinyl pyridine (15/70/15 weight percent) latex with a free radical initiator. Suitable free radical initiators include, for example, tertiary-butyl perbenzoate. The blend of a dispersion of this invention with a latex may also be cured with a p * henolplast or an aminoplast resin which is catalyzed by an acid. Suitable coating compositions are made from dispersions of this invention and aminoplast or phenol- plast resins with an acid catalyst. Suitable aminoplast resins include hexamethoxy- methyl melamine and methylated melamine formaldehyde resins. Suitable acids as catalysts include carboxylic or sulfonic acids such as, for example, para-toluene¬ sulfonic acid or the amine salt of para-toluenesulfonic acid. The inventive concept is more apparent in the following nonlimiting examples which illustrate the best mode for preparing and utilizing the dispersions. Example 1 To a 1-liter, 5-neck, round-bottom flask equipped with a condenser, thermometer, air sparge tube and a stirrer, there was charged 273 g of the reaction product of methacrylic acid and a polyepoxide having an epoxy equivalent weight (EEW) of 361 and which was the diglycidyl ether resulting from reaction of the digly¬ cidyl ether of bisphenol-A with bisphenol-A. The vinyl ester base resin was heated to 110°C and 26.80 g of maleic anhydride and 0.03 g of hydroquinone were added. The mix was reacted 1 to 2 hours or until the acid content was 4.0 percent. Styrene (44.97 g) was added and the mixture was cooled to 70°C. Phenothiazine (0.08 g) and monomethyl ether of hydroquinone (0.11 g) were added. Stirring was continued until resin and styrene were completely miscible. The temperature was then lowered to 40°C and 32.46 g of triethylamine was added and stirred for 30 minutes, then 372.6 g of water was added at a rate of 15 ml/minute. This dispersion contained 35 percent solids, had a particle size of o 1700 A (170 nm), and a viscosity of 220 cps (0.22 Pa-s) at 25°C. Example 2 To a 2-liter, 5-neck, round-bottom flask, which was equipped as in Example 1, was charged 500 g of the vinyl ester base resin of that example. The resin was heated to 110°C and 0.06 g of hydroquinone and 49.05 g of maleic anhydride were added and reacted for 1.5 hours (percent acid = 4.4) after which 109.9 g of styrene was added and the mix cooled to 70°C. Then 0.15 g of monomethyl ether of hydroquinone and 0.20 g of phenothiazine were added and stirred for 1 hour. Cooling to 40°C was started, 83 g of triethanolamine and 10 g of the monobutylether of diethylene glycol were added and were mixed well for 30 minutes. Then 1079 g of water were added at a rate of 10-20 ml/- minute. This dispersion had a solids level of 30 percent, a viscosity of 22,700 cps (22.7 Pa-s) at 25°C and a particle size of 1340 A (134 nm). A 77°F (25°C) gel time was measured for this dispersion by curing 50 g of the dispersion with 1 percent benzoyl peroxide and 0.2 percent dimethylaniline to give white solid masses. The gel time was 17 minutes. 49 Grams of this dispersion and 0.23 g of tertiary butyl perbenzoate were mixed. The pH of the system was adjusted to greater than 10 using triethyl- amine. Next, *-to the dispersion was added 24.4 g of 41 percent solids styrene/butadiene/vinyl pyridine latex (15/70/15 weight percent) with gentle agitation. Twelve inches (305 mm) of untreated polyester cord were measured and weighed. The cord was dipped into the above mixture and hung from a clamp. The cord was placed into a 190°C oven for 2 minutes and removed. The cord was weighed to determine the amount of resin pick up and then was cut into 4 sections 1.5 inches (38 mm) long. The sections were placed on top of a piece of uncured rubber in a mold along with 4 control cords (which were commercial polyester tire cords). Another piece of uncured rubber was placed on top of the cords. The rubber was then cured at 160°C and 800 psi (5.52 MPa) for 10 minutes. The adhesion was tested as follows. The rubber mat was cut exactly 1/4 inch (6.35 mm) from the point of insertion of the tire cord just deep enough to cut the cord. The mat was placed into an 110°C oven for 30 minutes and then the load necessary to pull the cord out of the rubber was measured for each individual cord. Adhesion was measured at 38.4 lbs/in (6720 N/m); adhesion for the control is 40.32 lbs/in (7061 N/m). Example 3 To a 1-liter, 5-neck, round-bottom flask, which was equipped as in Example 1, was charged 300 g of a vinyl ester base resin, which was the reaction product of a 208 EEW resin (mixture of bisphenol-A epoxy resin and epoxy novolac), methacrylic acid, and maleic anhydride to 4.7 percent acid. That was heated to 70°C and 0.12 g of phenothiazine and 53 g of styrene were added. The mix was stirred for 1 hour and cooled to 40°C. Then 48.9 g of triethanolamine and 5.89 g of monobutyl ether of diethylene glycol were added and mixed well for 30 minutes. Then 589 g of water were added at a rate of 15-20 ml/minute. The dispersion contained 30 percent solids with a viscosity of 27,500 cps (27.5 Pa-s) at 25°C and had a particle size o of 685 A (68.5 nm). A 77°F (25°C) gel time was measured for this dispersion following the procedure in Example 2. The gel time was 7 minutes. A tire cord adhesive was prepared from this dispersion following the procedure in Example-2_; . The adhesion was measured at 34.6 lbs/in (6059 N/m) compared with 32.4 lbs/in (5674 N/m) for the control. OMPI Example 4 To a 2-liter, 5-neck, round-bottom flask, which was equipped as in Example 1, was charged 500 g of vinyl ester base resin of that example. The resin was heated to 110°C and 27.9 g of maleic anhydride and 0.04 g of hydroquinone were added. Reaction was con¬ tinued for 1 hour to an acid level of 3.25 percent and 75.57 g of styrene added and the mix was cooled to 70°C. Then 0.15 g of monomethyl ether of hydroquinone and 0.12 g of phenothiazine were added, stirred for 1 hour and then cooled to 40°C. Then 50.75 g of tri- ethanolamine and 10 g of butanol were added and mixed well for 30 minutes. Then 863 g of water were added at a rate of 15-20 ml/minute. The dispersion had a soolids content of 30 percent and a particle size of 1680 A (168 nm). A 77°F (25°C) gel time was measured for this dispersion following the procedure in Example 2. The gel time was 21 minutes. _ Example 5 To a 2-liter, 5-neck, round-bottom flask, which was equipped as in Example I, was charged 455.8 g of vinyl ester base resin of that example. The resin was heated to 110°C and 0.05 g of hydroquinone and 44.75 g of maleic anhydride were added and allowed to react for 1.5 hours (percent acid = 4.60). The mix was cooled to 70°C and 0.13 g of phenothiazine and 0.13 g of monomethyl ether of hydroquinone were added.;. Triethyl- amine (62.13 g) was added and mixed well for 30 minutes. Then 970.2 g of water was added at 15-20 ml/minute. The resulting dispersion had a solids level of 33 percent and a viscosity of 9075 cps (9.075 Pa-s). OΛ.PI Example 6 To a 1-liter, 5-neck, round-bottom flask, which was equipped as in Example 1, was charged 273 g of the dimethacrylate of a 361 EEW bisphenol-A epoxy base resin of that example. The resin was heated to 110°C and 11.9 g of maleic anhydride and 0.03 g of hydroquinone were added and reaction continued for 1 hour to an acid level of 2.2 percent. Then 0.06 g of oxalic acid dihydrate and 42.74 g of styrene were added. The mix was cooled to 70°C and 0.06 g of phenothiazine was added. After cooling to 50°C, dimethylethanolamine (15.02 g) was added and mixed well for 30 minutes. With stirring, 472 g of water was added at a rate of 15-20 ml/minute. The dispersion had a solids content of 35 percent and a particle size of 2240 A (224 nm). An amount of 22.87 g of the above dispersion was mixed witt^ 1.2 g of hexamethoxymethylmelamine (Cymel @ 303), 0.1 g of a 50 percent solids para-toluene- sulfonic acid solution which was neutralized with dimethylethanolamine, and 35.6 g of deionized water. The pH of this mixture was adjusted to 10.5 with triethyl- amine. This dispersion was added to 12.93 g of a 41 percent solids styrene/butadiene/vinyl pyridine (15/70/15 weight percent) latex with gentle agitation. A cord was first dipped into water to. ' saturate and then into the adhesive mixture described above. The cord was then placed into an oven to set the adhesive to the cord. Cure times and temperature are as shown in Table I. The pickup of adhesive onto the cord was Trademark of American Cyanamid Company 4-5 weight percent. The cords were then placed onto a rubber pad as described in Example 2. The results are shown in Table I. TABLE I Cure Adhesion Time Temp °F lbs/in. Cord Type Adhesive sec. (°C) (N/m) Polyester Example 6 60 375 45.6 (191) (7990) 6 60 410 50.5 (210) (8840) Polyester Commercial* 45 300 (149) 60 475 49.5 (246) (8670) Nylon 6,6 Example 6 60 375 52.9 (191) (9260) Nylon 6 Example 6 60 375 47.0 * . (191) (8230) * Commercial - 53 percent resorcinol, formaldehyde, triallylcyanurate 47 percent styrene/butadiene/vinyl pyridine latex (15/70/15) The commercial adhesive is a two-stage cure of 45 seconds at 300°F (149°C) and 60 seconds at 475°F (246°C). Example 7 To a 2-liter, 5-neck, round-bottom flask, which was equipped as in Example 1, was charged 350 g (1.8460 equivalents) of epoxy resin (diglycidyl ether of bisphenol A (EEW = 182-190)). It was heated to 110°C, 158.76 g (1.8460 equivalents) of glacial meth¬ acrylic acid and 0.11 g of hydroquinone were added. Those ingredients were mixed well for 15 minutes, 0.53 g of 2,4,6-tri(dimethylaminomethyl)phenol (DMP-30) were added and slowly heated to 118°C (30-60 minutes). The reaction continues until the percent COOH was less than 1.0. Then 23.20 g (0.2367 mole) of maleic anhydride was added and reacted for 1.5 hours to obtain percent COOH equal to 2,40. Then 0.11 g of 4-chloro-2-nitrophenol was added and the mixture cooled to 85°C. Then 0.08 g of phenothiazine was added; the mixture cooled to 55°C and 30.41 g (0.3417 eq) of dimethylethanolamine was added and mixed well for 15 minutes. With stirring, 621 g of water was added at a rate of 15-20 ml/minute. Example 8 Using the same procedure as Example 7, a dispersion having the following composition was synthe¬ sized: the diglycidyl ether of that example (350 g, 1.8460 eq), hydroquinone (0.12 g), glacial methacrylic acid (158.76 g, 1.8460 eq), DMP-30 (0.53 g), maleic anhydride (48.62 g, 0.4961 eq) to give a percent COOH equal to 4.58, phenothiazine (0.08 g), 4-chloro-2- nitrophenol (0.11 g) dimethylethanolamine (60.61 g, 0.681 eq), and water (1150.5 g). The percent solids was 29.0. Brookfield viscosity at 25°C was 1600 cps (1.6 Pa-s). Example 9 To a 2-liter, 5-neck, round-bottom flask equipped as in Example 1, was charged 228.6 g (1.2057 eq) of epoxy resin of Example XI, 23.88 g (0.2095 eq) of bisphenol-A and 67 g (0.0944 eq) of Hycar* 1300 X 18 *Trademark of B. F. Goodrich Chemical Company Q (carboxy-terminated butadiene/acrylonitrile polymer). The resin mixture was heated to 80°C and 0.44 g of resin advancement catalyst tetrabutylphosphonium acetate was added with a nitrogen purge after which it was heated with stirring to 150°C and held for 1.5 hours. The mix was cooled to 110°C and an air purge was started. Then 0.12 g of hydroquinone and 79.02 g (0.9188 eq) of glacial methacrylic acid were added and the mix was stirred for 15 minutes and 0.36 g of DMP-30 was added. The charge was slowly heated to 118°C over 60 minutes and reacted until percent acid is less than 1.0. After which 18.2 g (0.1856 mole) of maleic anhydride was added and reacted for 1.5 hours to obtain a percent COOH equal to 2.79. Then 73.70 g of styrene was added and the mixture cooled to 85°C. Then 0.05 g of pheno¬ thiazine was added and the mixture cooled to 60°C. Then 27.65 g (0.3107 eq) of dimethylethanolamine was added and mixed well for 30 minutes. With stirring 1538 g of water was added at a rate of 15-20 ml/minute. The final percent solids was 20.3 and Brookfield viscosity at 25°C was 16 cps (0.016 Pa-s). The particle o size was 1950 A (195 nm). Example 10 Using the same procedure as in Example 9, the following dispersion was made: epoxy resin of Example 2 (228.6 g, 1.2057 eq), bisphenol-A (23.9 g, 0.2095 eq), Hycar* 1300 X 18 (67 g, 0.0944 eq), tetrabutylphosphonium acetate (0.44 g) hydroquinone (0.13 g), glacial methacrylic acid (79.22 g, 0.9212 eq), DMP-30 (0.36 g), maleic anhydride (38.13 g, 0.3891 mole), to give a percent COOH equal to 4.80, phenothiazine (0.05 g), styrene (77.3 g), dimethylethanolamine (49.88 g, 0.5604 eq) and deionized water (1186 g). The final product contained o 15 percent solids and had a particle size of 805 A (80.5 nm). Example 11 Using the same procedure as in Example 9, the following dispersion was made: epoxy resin of Example 7 (254 g, 1.3417 eq), bisphenol-A (55 g, 0.4822 eq), tetrabutylphosphonium acetate (0.22 g), hydroquinone (0.09 g), glacial methacrylic acid (72.44 g, 0.8423 eg), DMP-30 (0.46 g), maleic anhydride (17.43 g, 0.1778 mole) to give a percent COOH egual to 2.5, phenothiazine (0.07 g), 4-chloro-2-nitrophenol (0.09 g), styrene (70.6 g), dimethlethanolamine (23.73 g, 0.2666 eg), and water (1486 g). At 20.2 percent solids this product had a Brookfield viscosity at 25°C of o 3 cps (0.003 Pa-s). Particle size was 2280 A (228 nm). Example 12 Using the same procedure as in Example 9, the following dispersion was made: epoxy resin of Example 7 (254 g, 1.3417 ϊeg), bisphenol-A (55 g, 0.4822 eg), tetrabutylphosphonium acetate (0.22 g), hydroguinone (0.09 g), glacial methacrylic acid (72.44 g, 0.8423 eq), DMP-30 (0.46 g), maleic anhydride (17.43 g, 0.1778 mole) to give a percent COOH egual to 2.5, phenothiazine (0.07 g), 4-chloro-2-nitrophenol (0.09 g), styrene (44.4 g), dimethylethanolamine (23.73 g, (0.2666 eg), and water (1513 g). At 20.2 percent solids the disper¬ sion had a Brookfield viscosity at 25°C of 3 cps o (0.003 Pa- s ) and the average particle size was 2240 A (224 nm) . _ OA-PI The dispersion above was reduced to 15 percent solids with water. To this was added 15 weight percent Cymel _ 303 and 0.5 percent para-toluenesulfonic acid. 2 Inch x 4 inch (102 mm x 305 mm) panels of untreated, cleaned, cold rolled steel were electrocoated by immers¬ ing the panels into an electrocoating bath consisting of 2 liters of the above formulation and using the panel as an anode 2 inches (51 mm) from a carbon cathode in this electrocoating bath. A voltage of 50V was applied for 2 minutes. The panels were removed from the bath, rinsed with deionized water and baked for 30 minutes at 150°C. The resulting panel had a smooth, hard, uniform film with methyl ethyl ketone double rubs of between 10 and 15. Example 13 Using the same procedure as in Example XIII, and a 5-liter, 5-neck, round-bottom flask, the following dispersion was made: epoxy resin of Example 7 (413.9 g, 2.183 eg), bisphenol-A (89.4 g, 0.784 eg), tetrabutyl- phosphonium acetate (0.35 g), hydroguinone (0.14 g), glacial methacrylic acid (119.98 g, 1.3951 eg), DMP-30 (0.75 g), maleic anhydride (59.61 g, 0.6083 mole) to give a percent COOH equal to 4.57, phenothiazine (0.11 g), 4-chloro-2-nitrophenol (0.15 g), styrene (76.0 g), dimethylethanolamine (71.67 g, 0.8053 eg), and water (3730 g). The dispersion had a Brookfield viscosity at 25°C of 3040 cps (3.04 Pa-s) at 15 percent solids. Example 14 Using the same procedure as in Example 1, the following dispersion was prepared: vinyl ester base resin of Example 1 (273 g), maleic anhydride (26.8 g) to give a percent COOH of 4.55, styrene (44.97 g), monoethyl ether of hydroguinone (0.11 g), phenothiazine (0.08 g), dimethylethanolamine (32.4 g) and water (480 g). Using the same procedure as in Example 6, the following tire cord adhesive formulation was prepared using the above dispersion (21.15 g); Cymel 303 (1.11 g); deionized water (32.92 g); and styrene/- butadiene/vinyl pyridine latex (15/70/15 weight percent) (12.02 g). A polyester cord was coated and tested by the method of Example 6. The adhesive was cured at 375°F (191°C) for 60 seconds. The resulting adhesion was 42.0 lbs/in (7360 N/m). Example 15 Using the same procedure as in Example 6, the following dispersion was prepared: vinyl ester base resin of Example 1 (273 g), maleic anhydride (41.0 g), oxalic acid dihydrate (0.06 g), phenothiazine (0.06 g), dimethylethanolamine (43.47 g) and water (678 g). Using the same procedure as in Example 6, the following tire cord adhesive formulation was prepared using the above dispersion (27.57 g), Cymel 303 (1.2 g), deionized water (30.8 g), and styrene/butadiene/vinyl pyridine latex (15/70/15 weight percent) (12.93 g) . A polyester cord was coated and tested by the method of Example 6. The adhesive was cured at 375°F _(191°C) for 60 seconds. The resulting adhesion was 48.3 lbs/in (8460 N/m). ' , " '■ ■ Example 16 To a 500-ml, round-bottom flask, there was charged 27.0 g of the reaction product used in Exam- pie 3. Then, 13.5 g of styrene was added. To this mixture, 7.87 g of a 50 percent NaOH solution was added with stirring. After 30 minutes of stirring, 339.2 g of deionized water was added at a rate of 17 ml per minute. The product is a good stability dispersion. Forty grams of the above dispersion were mixed with 3.0 g of Cymel 325 (a methylated mela ine formaldehyde resin). Next, 0.44 g of a 10 percent para-toluenesulfonic acid solution neutralized with dimethylethanolamine was added as well as 17.83 g of deionized water. The pH of the mixture was adjusted to 10.5 with triethylamine. The resulting dispersion was added with gentle agitation to 12.93 g of a latex, 41 percent styrene/butadiene/vinyl pyridine (15/70/15 weight percent) making an adhesive. A polyester cord was coated and tested by the method of Example 6. Adhesive pickup was 5 percent. The adhesive was cured at 175°C for 10 minutes. The resulting adhesion was 40 lbs./m (7000 N/m). Similar results were obtained when the polymers of Examples 1 through 15 were neutralized with ammonium hydroxide, sodium hydroxide or potassium hydroxide in place of the amine noted therein. OMPI

Claims: 1. A stable agueous dispersion of a curable resinous composition comprising a half ester of a dicarboxylic acid with the secondary hydroxyl of a vinyl ester resin, the carboxylic acid group of said half ester being at least partially neutralized with an alkali metal hydroxide, ammonium hydroxide or a tertiary amine. 2. The dispersion of Claim 1 wherein said half ester contains from 1 to 13 percent carboxylic acid by weight;. 3. The dispersion of Claim 1 wherein said vinyl ester resin is the esterification product of a monounsaturated monocarboxylic acid and a polyglycidyl ether of a polyhydric alcohol or phenol. 4. The dispersion of Claim 1 wherein said vinyl ester resin is a diester of a diglycidyl ether of bisphenol-A. 5. The dispersion of Claim 3 wherein said vinyl ester resin is the reaction product of a diglycidyl ether of bisphenol-A and a combination of an unsaturated monocarboxylic acid and a liguid carboxy terminated polydiene rubber wherein at least 80 percent of acid eguivalents is said monocarboxylic acid and the balance between 0.01 and 20 percent comprises said polydiene, provided that the polydiene rubber content is at least 4 weight percent. 6. The dispersion of Claim 10 wherein said polydiene rubber is a copolymer of acrylonitrile and butadiene. 7. The dispersion of Claim 4 wherein said polyglycidyl ether is a polyglycidyl ether of a novolac. 8. A tire cord fiber to rubber adhesive composition made by curing a blend of the dispersion of Claim 1 and a styrene/butadiene/vinyl pyridine latex with a free radical initiator. _ 9. A cord tire fiber to rubber adhesive composition made by curing a blend of the dispersion of Claim 1 and a styrene/butadiene/vinyl pyridine latex with a phenolplast or aminoplast resin which is catalyzed by an acid. 10. A coating composition made from the dispersion of Claim 1 and an aminoplast or phenolplast resin with a carboxylic acid catalyst.

Inventors: DAVIS RHETTA Q, STEVENS MICHAEL G, DAVIS, RHETTA, Q., STEVENS, MICHAEL, G.
Applicants: DOW CHEMICAL CO, THE DOW CHEMICAL COMPANY
Application year: 1983
Main classification: C08G59
IPC codes: C08G59, C08J5, C08L63