JPS6037131B2 - Stable aqueous dispersions of curable resin compositions - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION It is known that many vinylester resins are polymerizable.

This is US Pat. No. 3,560,237 (RE27,65
6); 3,661,576:3,673,140 and British Patent No. 1,375,177. U.S. Patent 3,560,237 (RE27,6
The disclosures of No. 56) and No. 3,661,576 are particularly relevant to the present invention in that the inventions relate to vinylester resins derived from resinous epixides (ie, epoxy resins). Many of these vinylester resins derived from resinous epoxides are commercially available and have excellent physical and chemical properties and are particularly useful as a protective layer for a variety of substrates. In this application, the vinylester resin is usually dissolved in an organic solvent or reactive diluent, applied to a substrate by conventional techniques (spraying, dipping, etc.) and then cured by actinic radiation or other catalytic means. The necessity to use organic solvents is a disadvantage for using the compositions indicated above.

Organic solvents are recovered, recycled or disposed of for safety, environmental pollution and/or economic reasons. Recovery is often difficult and/or expensive. These problems can be reduced if the organic solvent reacts within the coating. Considerable research has concerned the use of vinyl monomers and low viscosity vinyl resins as reactive diluents. However, many of the useful reactive diluents, such as 2-hydroxyethyl acrylate, are toxic and pose significant health and environmental concerns. Many resin systems are made water-soluble or water-dispersible by attaching various onium groups, such as sulfonium, phosphonium, and ammonium, to the resin backbone or by adding onium surfactants to the resin as dispersion vehicles. (oil-in-water dispersion) and boiled. Many of these onium compounds are electroreducible, and sulfonium and isothiuronium compounds in particular have been used in anodic electrolytic deposition methods. A thorough investigation of this is unnecessary. However, U.S. Patent No. 3,793,278;
,936,405;3,937,679;3,959,
No. 106 and No. 3,894,922 illustrate a series of cases in which onium-modified epoxy resins have been asserted to be useful as electrolytic deposition compositions. Onium-modified epoxy resins were made by reacting epoxy resins with tertiary phosphines: tertiary amines or sulfides in the presence of acid. The acid used in this series of experiments was 1
It has a dissociation constant of x10-5 or more and includes organic and inorganic. Although alkenoic acids meet the requirements for a dissociation constant, they were not mentioned and used in these specific references. The present invention relates to stable aqueous dispersions of curable resinous compositions comprising half-esters of dicarboxylic acids and secondary hydroxy of vinylester resins.

The carboxylic acid groups of the half-ester are at least partially neutralized by an alkali metal hydroxide, ammonium hydroxide or a tertiary amine. The dispersion is 2500A
(25M dish) or less and is curable through the vinyl groups of its vinylester resin. The vinylester resins useful in this invention are the reaction products of polyepoxides reacted with ethylenically unsaturated mono/carboxylic acids and further reacted with dicarboxylic acids or their anhydrides to form half-esters.

Such vinyl ester resins are disclosed in U.S. Patent No. 3,5M,
No. 074. Any of the known polyepoxides can be used in making the vinylester resin. Useful polyepoxides are glycidyl polyethers of polyhydric alcohols and polyhydric phenols, epoxy novolacs or mixtures thereof. Many polyepoxide modifications can be readily made within the scope of this invention.

A bisphael, dicarboxylic acid or carboxyl terminated polyene rubber which serves to link two or more polyepoxide molecules in such a way as to react with their epoxide groups and add these jepoxide molecules, and which also carries terminal epoxide groups. It is possible to increase the molecular weight of polyepoxides by polyfunctional reactants such as. When a polyhydric phenol is selected to make the polyepoxide, many structural embodiments are possible.

Polyepoxide made from polyhydric phenol has the general formula (
In the formula, R' is, for example, a divalent hydrocarbon such as 1CH2, 1CCH2, 1S-, 1S-S, or 10-
).

The selection of nopolac resins is guided by distinct, well-recognized classes of epoxy novolak resins. Other modifications were known to those skilled in the art. Although the present invention is applicable to polyepoxides, generally the most preferred polyepoxides are glycidyl polyethers of polyhydric alcohols or polyhydric phenols having a weight per epoxy group (ie, epoxy equivalent weight) of 150 to 2000.

These polyepoxides are usually made by reacting at least about 2 moles of epihalohydrin or glycerol dihalohydrin with 1 mole of a polyhydric alcohol or polyhydric phenol and a sufficient amount of an alkali metal to combine the halogen and hydroxyl groups of the halohydrin. The product contains more than one epoxide group, i.e. more than one 1,
It is characterized by the presence of 2-epoxy equivalents. Preferred polyepoxides are tyrene bisphenol or 2,2'-
It is a polyepoxide derived from isopropylidene bisphenol.

Suitable Q,3-ethylenically unsaturated monocarboxylic acids are, for example, acrylic acid, methacrylic acid, crotonic acid and cinnamic acid.

As other unsaturated carboxylic acids it is possible to use half-esters formed by the reaction of one molecule of hydroxyalkyl acrylate or methacrylate with a cyclic acid anhydride.

The above reactants are included in the composition to provide substantially stoichiometric equivalents of carpoxy functionality with the oxirane groups present.

It contains 0.0% carvone brewing component for each equivalent of polyepoxide.
8 to 1.15 equivalents, and preferably 0.9 carboxylic acid
This means that ~1.05 equivalents are present. The esterification reaction is preferably catalyzed with carboxyl groups and oxirane groups and known catalysts for this esterification.

Such catalysts include tertiary amino acids such as tris(dimethylaminomethyl)phenol and also include chromium salts. The composition is used to prepare a curable product by mixing the components mentioned above and reacting 80 to 120 qo of the mixture, preferably in the presence of a catalyst. If temperatures above 80°C are used, the reaction is very slow.

If temperatures above 120° are used, side reactions occur and the yield of the desired beef product is reduced, and an exotherm occurs that is difficult to control.

Due to the presence of reactive ethylenically unsaturated groups in the reaction mixture, it is necessary to maintain a suitable residual amount of vinyl polymerization inhibitor in the reaction mixture and the resulting composition.

It has been found that any of the hydroquinones and quinones are suitable for this purpose, but quinones are used because the hydroquinones have a predilection for entering during the reaction with the epoxy groups of the starting material. Generally preferred. Tolquinone and toluhydroquinone are preferred pinyl polymerization inhibitors because when tolquinone or toluhydroquinone is used as a polymerization inhibitor, the reaction product appears transparent. Other preferred inhibitors are p-quinone, 2,5-dimethyl-p-benzoquinone, 1,4 naphthaquinone, anthraquinone, and chloranil (ch
ioranil). Preferred inhibitors in the product composition are 2-chloro-2-ni-1-lophenol, phenothiazine and oxalic anhydride. The ethylenically unsaturated monocarboxylic acid-polyeboxide reaction product containing secondary hydroxyl groups is further described in U.S. Pat.
564,074 with 0.1 to 1.2 moles of dicarboxylic acid anhydride per equivalent of epoxide.

The dicarboxylic anhydride can be selected from saturated or unsaturated dicarboxylic anhydrides or mixtures thereof as disclosed in the patent. For example, Hyde. Vinyl polymerization inhibitors such as methyl ether of quinone or hydroquinone can be added. After the reaction is complete, the reaction mixture is cooled and the polymerizable monomers can be mixed therewith. A wide selection of polymerizable monomers containing >C=C ratio groups is possible from a large number of common vinyl monomers.

Typical examples include monomers such as styrene, vinyltoluene, halogenated styrenes and divinylbenzene. Other valuable monomers are e.g. methyl, ethyl,
Acidic monomers such as isopropyl, octyne, esters of acrylic or methacrylic acid, vinyl acetate, diallyl maleate, dimethallyl fumarate, acrylic acid, methacrylic acid and crotonic acid, and acrylamide and N-alkylacrylamide. amide monomers such as amide monomers and mixtures thereof.

Preferred polymerizable monomers containing >C=CH2 groups are styrene, vinyltoluene, ortho, meta and parahalostyrenes, vinylnaphthalenes, various Q-substituted styrenes, and acrylic, methacrylic and crotonic esters.

A non-reactive solvent can be used to replace all or a portion of the reactive solvent. Such non-reactive solvents include glycol ethers; alcohols such as butanol; ketones and methylene chloride. The resulting acid-functionalized vinylester is then reacted with an amount of alkali metal hydroxide, ammonium hydroxide, or tertiary amine to render the resin water-dispersible.

Although all alkali metal hydroxides are useful,
NaOH and KOH are preferred.

Suitable tertiary amines include, for example, trimethylamine, triethylamine, triethanolamine, dimethylethanolamine and methyldiethanolamine. Neutralization is preferably between 20 and 8000, most preferably 20
Performed at a temperature of ~7y0.

After neutralization, the resin can be dispersed in water to the desired solids content and viscosity. The dispersion of this invention is 1-1% by weight.
, preferably 1.5 to 7% by weight carboxyl.
Advantageously, the dispersion has an average particle size of less than 2500 Angstrom units. The polymer of the particles can be cured by free radical catalysis at somewhat elevated temperatures and/or by pendant carboxyl groups. Dispersions thereof are useful or can be mixed with aminoplasts or phenoplasts such as melamine or urea-formaldehyde. Since the dispersion can be water-based, problems caused by organic solvents in coatings are eliminated or minimized. The dispersion can be mixed with colorants, fillers, waxes or other customary additives for its desired effect.

The dispersions are useful in adhesives and coatings.

For example, the dispersions are useful as tire cord adhesives, glass sizes and wood product adhesives. As coatings, the dispersions are metallurgical primers and finishes, internal and external can coatings, drum linings and other industrial and commercial coatings. A suitable tire cord adhesive for bonding the tire cord to the rubber is a mixture of the dispersion of this invention and a suitable latex such as styrene/butadiene/vinylpyridine (15/70/15% by weight). Made by curing with free radical initiators.

Suitable free radical initiators include, for example, tertiary butyl benzoate. Mixtures of the dispersions of this invention and LAAX can also be cured with acid catalyzed phenolprost or aminoplast resins. Suitable coating compositions are made from the dispersions of this invention and aminoplast or phenoplast resins with acid catalysts.

Suitable aminoplast resins include hexamethoxymethyl melamine and methylated melamine formaldehyde resins.

Suitable acids as catalysts include carboxylic acids or sulfonic acids, such as para-toluenesulfonic acid or amine salts of para-toluenesulfonic acid. The concept of the invention is made clearer in the following non-limiting examples which demonstrate the best method of making and utilizing the dispersion.

Example 1 A reaction product of methacrylic acid and a polyeboxide having an epoxy equivalent weight (EEW) of 361 was prepared in a 1 to 5 neck round bottom flask equipped with a condenser, calorimeter, air sparge tube, and barrel. added.

The polyepoxide was a diglycidyl ether resulting from the reaction of the diglycidyl ether of bisphenol A with bisphenol A. The vinyl ester base resin was heated to 11,000 °C and 26.80 °C of maleic anhydride and 0.03 °C of hydroquinone were added. The mixture is heated for 1-2 hours or its acid content is 4.0%.
The reaction was allowed to occur until . Styrene (44.97 ml) was added and the mixture was cooled to 70°C. Phenothiazine (0.08 hours) and monomethyl ether of hydroquinone (0.11 hours) were added. The rope was continued until the resin and styrene were completely mixed. Then the temperature dropped to 40 qo and triethylamine 32.
Add 46 Evenings, worship the lights for 30 minutes, then Wednesday 37
2.6 minutes were added at a rate of 15 minutes/minute. This dispersion contains 35% solids and has a particle size of 1700 A (17 m) and a specific ps (0.2 sa.
It had a viscosity of s). Example 2 To a two-way, five-necked round bottom flask equipped as in Example 1 was added 500 g of the vinyl ester base resin of Example 1.

The resin was heated to 110 qC and 0.06 g of hydroquinone and 49.05 g of maleic anhydride were added and 1. Allow to react for 1 hour (acid ratio = 4.4), then add 109.9 g of styrene, and add the mixture to 700 g.
Cooled to 0. Then 0.15 hours of monomethyl ether of hydroquinone and 0.20 hours of phenothiazine were added and incubated for 1 hour. Begin cooling to 4,000 ml, add 83 ml of triethanolamine and 10 ml of monobutyl ether of diethylene glycol, and add 30 ml of monobutyl ether of diethylene glycol.
Mix thoroughly for minutes.

Then 1079 g of water was added at a rate of 10 to 20 minutes. This dispersion has a solids content of 30%, 2yo of 22,
Viscosity of 70 ps (22.7 pa·s) and 1340
It had a particle size of Δ (134 nm). 770F
Gel time at (25° C.) was determined by curing the dispersion 509 with 1% pesozoyl peroxide and 0.2% dimethylaniline to obtain a white solid mass.

The gel time was 17 minutes. 49 g of this dispersion and 0.23 g of tertiary butyl benzoate were mixed. The pH of the system was adjusted to above 10 using triethylamine. The dispersion was then mixed with a 41% solids styrene/butadiene vinylpyridine latex (15/7
0/15% by weight) 24.4 evening was added as usual. 12 inches of untreated polyester cord (305 ribs)
was measured and weighed. The cord was slightly soaked in the above mixture and hung from the crumb. The cord was diluted to 190 qo for 2 minutes and removed. The cord was weighed to determine the amount of resin coverage and then cut into four pieces 1.5 inches (38 sides) long. The pieces were folded together with four pieces of control cord (commercially available polyester tire cord) onto a piece of uncured rubber. Another piece of hardened rubber was placed over the cord. The rubber was then cured for 10 minutes at 16 pi and 80 psi (5.52 MPa). Its adhesion was tested as follows. The rubber mat was precisely cut to 1'4 inches (6.35 skins) from the point of tire cord insertion just deep enough to cut the cord. That mat is 30
The load required to place in a 110°C oven for minutes and then pull to remove the cord from the rubber was measured for each individual cord. Adhesion is uneven. The adhesion of the control was 40.32 pounds/inch (7061 N/m). Example 3 A five-necked round bottom flask equipped as in Example 1 was charged with 300 g of vinylester base resin.

Its vinyl ester resin has 20% acid content up to 4.7%.
It was a reaction product of fine EW resin (bisphenol A epoxy resin and epoxy novolac), methacrylic acid and maleic anhydride. It was heated to 70°C and 0.12° of phenothiazine and 5.3° of styrene were added. The mixture was allowed to stand for 1 hour and cooled to 40°C. Then triethanolamine 48.9% and monobutyl ether of diethylene glycol 5.89%
and mixed thoroughly for 3 minutes. Then 589 g of water was added at a rate of 15-20 g/min. The dispersion has a solids content of 30% and a specific ps of 27,50 at 25 qo.
Viscosity of (27. tsubo a・s) and 685A (porridge. Immediate blood)
It had a viscosity of 5A (68.5 mm) and a spot size of 5A (68.5 mm). 7
A gel time of 7F (2500) was determined for this dispersion according to Example 2.

The gel time was 7 minutes. A tire cord adhesive according to the procedure of Example 2 was made from this dispersion.

Its adhesion was 34.6 lb/inch (605 eggs/m) compared to 32.4 lb/inch (567 eggs/m) for the control.
/m). Example 4 To a 2-5 neck round bottom flask equipped as in Example 1 was added 500 g of the vinyl ester base resin of Example 1.

The resin was heated to 110°C and maleic anhydride 2
7.9 hours and 0.04 hours of hydroquinone were added. The reaction was continued for 1 hour to an acid concentration of 3.25% and 75.57 g of styrene was added and the mixture was mixed with 70 ml of styrene.
Cooled to . Then 0.15 mol of hydroquinone monomethyl ether and 0.12 mol of phenothiazine were added and stirred for 1 hour and cooled to 4000 ml.
Then, 50.75 parts of triethanolamine and 10 parts of putanol were added and mixed thoroughly for 30 minutes.
Then 863 g of water was added at a rate of 15-20 bars/min. This dispersion has a mass content of 30% and 1680A (
It had a particle size of 16 sleeves). 77F (25q
The gel time in o) was determined for the dispersion according to the procedure of Example 2.

The gel time was 21 minutes. Example 5 455.8 mm of the vinyl ester base resin of Example 1 was added to a 2-hole, 5-neck round bottom flask equipped as in Example 1.

The resin was heated to 110 °C and 0.05 °C of hydroquinone and 44.75 °C of maleic anhydride were added and 1. The reaction was carried out for a period of time (acid ratio = 4.60). The mixture was cooled to 70° C. and then 0.13 hours of phenothiazine and 0.13 hours of monomethyl ether of hydroquinone were added. Triethylamine (62.1
3 evenings) and mixed thoroughly for 30 minutes. Then 970.2 hours of water was added at a rate of 15-20 minutes.
The resulting dispersion had a solids content of 33% and 25o
It had a viscosity of 907&ps (9.07 a·s) of o. Example 6 To a five neck round bottom flask equipped as in Example 1 was added 273 mL of the dimethacrylate of 361 EEW bisphenol-A-epoxy based resin of Example 1.

Heat the resin to 110q and add 11.9 q of maleic anhydride and 0.03 q of hydroquinone,
The reaction was then continued for 1 hour to an acid concentration of 2.2%. Then 0.06 oxalic anhydride and 42.74 styrene
Added evening. The mixture was cooled to 70°C and 0.06 g of phenothiazine was added. After cooling to 50 CO, dimethylethanolamine (15.02 pm) was added and mixed thoroughly for 30 minutes.

While rinsing, 472 g of water was added at a rate of 15-20 m/min. The dispersion has a solids content of 35% and 22
It had a particle size of 40Δ (224 nm). The above dispersion 22.87% was mixed with hexamethoxymethylmelamine (
Simil R303) was mixed with a 50% solids solution of para-toluene sulfonic acid for 1.2 days, which was neutralized with dimethylethanolamine and deionized water for 356 days. The barrier of this mixture was adjusted to 10.5 with triethylamine. This dispersion has a styrene/butadiene vinylpyridine content of 41% solids (15/70/15
) M%) Latex 12. Added a group saw. The coat was first slightly soaked in water to saturate and then slightly soaked in the adhesive mixture described above.

The cord was placed in the oven and the adhesive was secured to the cord. The curing time and temperature are shown in Table 1.
The amount of adhesive in the cord was 4 to 5 percent.
The cord was placed on a rubber pad as described in Example 2. The results are shown in Table 1. Table I Commercial - 53% Resosyl, Formaldehyde, Triallyl Cyanurate 47% Styrene/Butadiene/Vinylpyridine Latex (15/70/15) Commercial Adhesive at 3000F (149q0) 49 Sand and 4750
At F (24 is 0), there was two-stage hardening between 6-top sand and 6-top sand.

Example 7 2 and 5 equipped in the same manner as in Example 1
Epoxy resin (diglycidyl ether of bisphenol A (EEW=182-190)) in a round-bottom flask
50 pieces (1.60 equivalents) were added.

Heat it to 11 psi and ice methacrylic acid 19376
(1.6 eq.) and 0.11 eq. of hydroquinone were added. Mix these ingredients thoroughly for 18 minutes,
, 6-tri(dimethylaminomethyl)phenol (DM
P-30) Add 0.53 hours and slowly heat to 118℃
(30-60 minutes). The reaction was continued until the daily percent COO was below 1.0. Then 23.20 g (0.2367 mol) of maleic anhydride was added and allowed to react for 1.5 hours, yielding a percent COO equal to 2.40. Then 0.11 hours of 4-chloro-2-nitrophenol was added and the mixture was cooled to 8,500 ml. Then 0.08 mm of phenothiazine was added, the mixture was cooled to 55 mm, and 30.41 mm (0.3417 equivalents) of dimethylethanolamine was added and mixed thoroughly between strokes. Water while thick azusa 6
21 minutes were added at a rate of 15-20 minutes/minute. Example
8 Following the same procedure as in Example 7, a dispersion with the following composition was synthesized.

The diglycidyl ether of Example 7 (350 min, 1.
8460 eq), hydroquinone (0.12 eq), glacial methacrylic acid (158.76 eq, 1.8460 eq),
DM Enichi 30 (0.53 evening), 4. Maleic anhydride (48.62, evening,
0.4961 eq), phenothiazine (0.08, 4
-chloro-2nitrophenol (0.11 hours), dimethylethanolamine (60.61 hours, 0.681 eq.) and water (1150.5 hours).

The percent solids was 29.0. The Blockfield viscosity at 2500 was 160 specific ps (1.A·s).

Example 9 Two, five-necked, round-bottomed flasks equipped as in Example 1 were charged with 228.6 g of the epoxy resin of Example 7 (1.
2057 equivalents), bisphenol-A 23.88 equivalents (0
．． 2095 equivalents) and No. ika (trademark of BEF Goodrich Chemical Company) 1300
23.88 (0.2095 equivalents) of 8 (carboxy-terminated butadiene/acrylonitrile polymer) were added.

The resin mixture was heated to 80 qC and the resin molecular weight increase catalyst tetrabutylphosphonium acetate 0.4
4 hours were added with a nitrogen purge. then 150
Heat it up to 20 degrees while pressing the rope, and then 1. It was held immediately. The mixture was cooled to 110° C. and an air purge was started, 0.12 kg of hydroquinone and 79.02 kg (0.91 kg) of glacial methacrylic acid were added, and the mixture was allowed to stand for 15 minutes and 1.30 kg of DMP was added. (0.36
evening) was added. The charge was slowly heated to 118° C. over 6 G minutes and allowed to react until the acid percentage was below 1.0. Then maleic anhydride 182 hours (
0.1856 mol) and reacted for 1.5 hours,
We obtained a COO day percentage equal to 2.79. Then add 73.70 g of styrene and heat the mixture to 85°C.
Cooled to . Then 0.05 ml of phenothiazine was added and the mixture was cooled to 60°C. Then 27.65 liters (0.3107 equivalents) of dimethylethanolamine were added and mixed thoroughly for 30 minutes. While worshiping the candles, 18 drops of water were added at a rate of 15 to 20 minutes. Its final percent solids is 20.3 and 25°C
The brutskfield viscosity at 1 & ps (0.01 rudder a
・s). The particle size was 1950A (19 orbital plate). Example 10 Using the same procedure as Example 9, the following dispersion was made.

Epoxy resin of Example 2 (228.6 m, 1.2057
equivalent), pisphenol-A (23.9 evening, 0.209
5 equivalents), /.
944 equivalents), tetrabutylphosphonium acetate (
0.44 eq.), hydroquinone (0.13 eq.), glacial methacrylic acid (79.229, 0.9212 eq.), DMP
Maleic anhydride (38.13 evenings) to give a COO day percent equal to -30 (0.36 evenings), 4.80
0.3891 mol), phenothiazine (0.05 mol),
Styrene (77.3 evenings), dimethylethanolamine (
0.5604 eq.) and deionized water (
1186 evening). The final product is 15% mass and 8
It had a particle size of 0.05A (80.m toughness). EXAMPLE 11 The following dispersions were made using the same procedure as Example 9: Epoxy resin of Example 7 (254 mm, 1, 17 equivalents), bisphenol-A (55 mm, 0.482 mm).
2 equivalents), tetrabutylphosphonium acetate (0.
22 evenings), hydroquinone (0.09 evenings), glacial methacrylic acid (72.44 evenings, 0.8423 equivalents), DMP-3
0 (0.462), maleic anhydride (17.43 m, 0.1
778 mol), phenothiazine (0.07 mol), 4-chloro-2-nitrophenol (0.09 mol), styrene (70.6 mol), dimethylethanolamine (23.7 mol),
3 evenings, 0.2666 eq) and water (i486 evenings).

At 20.2% solids this product was 2500*ps(0
．． 00 had a Plookfield viscosity of a.s.

The particle size was 2280A (22 nodes m). Example 12 The following dispersion was made using the same procedure as Example 9: Epoxy resin of Example 7 (254 molar, 1.3417 eq), Bisphenol-A (55 molar, 0.4822 eq) , tetrabutylphosphonium acetate (0.22 hours), hydroquinone (0.09 minutes), glacial methacrylic acid (
72.44 pm, 0.8423 eq), DMP-30 (0
．． 46 min), maleic anhydride (17.43 min, 0.1778 min) to give a COO day percent equal to 2.5
mole), phenothiazine (0.07 mole), 4-chloro-
2-Nitrophenol (0.09 mm) Styrene (44 mm)
4 evenings), dimethylethanolamine (23.73 evenings, 0
．． 2666 eq) and water (1513 eq).

At 20.2% solids this product was
．． It had a Pluckfield viscosity of 00 units a.s).

The particle size was 2280 people (22 m). The above dispersion was made to 15% solids with water.

This was supplemented with 15M% Cymel R and 0.5
% para-toluene sulfonic acid was added. A 2 inch by 4 inch (102 ribs by 305 ribs) sized panel of untreated, clean cold rolled steel was immersed in an electrolytic coating bath consisting of the composition 2 described above and the electrolyte was coated with a carbon cathode. was electrolytically coated using a 2 inch (51 skin) panel as the anode. A voltage of 50V was applied for 2 minutes.

The panels were removed from the rack, rinsed with deionized water and fired at 15,000 for 3 minutes. The resulting panel was a smooth, hard, uniform film with a methyl ethyl ketone double rub of 10-15. Example
13 Using the same procedure as Example 9 and using a 5Z, 5-neck round bottom flask, the following dispersion was made: epoxy resin of Example 7 (413.9 mm, 2.183 equivalents), bisphenol. A (89.4 hours, 0.784 equivalents), tetrabutylphosphonium acetate (0.35 hours), hydroquinone (0.14 hours), glacial methacrylic acid (119 hours, 0.784 hours),
1.3951 eq.), DMP-30 (0.75 eq.), 4
．． maleic anhydride (59.61 molar, 0.6 molar), phenothiazine (0.11 molar), 4-chloro-2-nitrophenol (0.15 molar), and water to give a COO day percent equal to 57. (3730's.

At 15% solids, this product has a temperature of 304 ps at 25°C.
．． It had a Brookfield viscosity of 0 a.s.

Example 14 Using the same procedure as in Example 1, the following dispersions were made: Vinylester (273) of Example 1, 4.55
maleic anhydride (to give a COO day percent of
26.8 evening), monoethyl ether of hydroquinone (
0.11 pm), phenothiazine (0.08 pm), dimethylethanolamine (32.49 pm) and water (480 pm).

Using the procedure of Example 6, the following tire cord adhesive compositions were made using the above dispersion (21.15 minutes): Cymel R303 (1.11 hours), deionized water (32 hours).
．． 92) and styrene butadiene novinylpyridine latex (15/70/15wt%) (12.02
evening).

Polyester cords were coated and tested according to the method of Example 6. The adhesive is 6 cyric acid, 375?
(191°C). The resulting adhesion was 42.
0 lb/inch (736 sail/m). Example
15 The following dispersion was made using the same procedure as in Example 6.

Vinyl ester base resin of Example 1 (273 mm), maleic anhydride (41.0 mm), oxalic acid dihydrate (0.0 mm).
0M), phenothiazine (0.06 m), dimethylethanolamine (43.47 m) and water (678 m).
Using the procedure of Example 6, the following tire coat adhesive compositions were made using the above dispersion (27.57 mm): Cymel R303 (1.2 mm), deionized water (30 mm).
8 days) and styrene butadiene/pinylpyridine latex (15/70/15wt%) (12.93 days)
.

Polyester cords were coated and tested according to the method of Example 6. The adhesive is heated to 37° F (
19ro). The resulting adhesion was 48.3
It was lb/inch (8460 N/m). Example
To a 16,500 ml round bottom flask was added 27.0 ml of the reaction product used in Example 3.

Then 13.5 tons of styrene was added. In this mixture,
7.87 g of 5% NaOH solution was added with stirring. 3
After 0 minutes of rope worship, 339.2 hours of deionized water was added at a rate of 17 minutes/minute.

The product was a good stable dispersion. The above dispersion 4
0 parts were mixed with 3.0 parts of Cymel R325 (methylated melamine formaldehyde resin).

Then 10% neutralized with dimethylethanolamine
Add 0.44 g of p-toluenesulfonic acid to 17.0 g of deionized water.
Added with the 83rd evening. The resulting dispersion was mixed with 12.9 g of 41% styrene/butadiene/vinylpyridine (15/70/15 wt%) latex to form an adhesive. Polyester cords were coated and tested according to the method of Example 6.

The amount of adhesive adhered was 5%. The adhesive was cured at 17500 for 10 minutes. The resulting adhesive was 40 pounds/inch (700 sails/m). Examples 1-15
Similar results were obtained when the polymers were neutralized with ammonium hydroxide, sodium hydroxide or potassium hydroxide instead of the amines mentioned in this invention.

Claims (1)

[Scope of Claims] 1. Consisting of a half ester of dicarboxylic acid and a secondary hydroxyl group of a vinyl ester resin, the carboxylic acid group of the half ester is at least partially treated with an alkali metal hydroxide, ammonium hydroxide or a tertiary amine. A stable aqueous dispersion of a curable resin composition which is neutralized. 2. The dispersion of claim 1, wherein the half ester contains 1 to 13 wt% of carboxylic acid. 3. The dispersion according to claim 1, wherein the vinyl ester resin is an esterification product of a monounsaturated monocarboxylic acid and a polyglycidyl ether of a polyhydric alcohol or a polyglycidyl ether of a polyhydric phenol. 4. The dispersion of claim 1, wherein the vinyl ester resin is a diester of diglycidyl ether of bisphenol A. 5. The vinyl ester resin is the reaction product of a diglycidyl ether of bisphenol-A with a combination of an unsaturated monocarboxylic acid and a liquid carboxy-terminated polydiene rubber, in which at least 80% of the acid equivalents are derived from the monocarboxylic acid. 4. The dispersion of claim 3, wherein the dispersion is an acid and the remainder from 0.01 to 20% consists of said polydiene, with the proviso that the polydiene rubber content is at least 4 wt%. 6. The dispersion of claim 5, wherein the polydiene rubber is a copolymer of acrylonitrile and butadiene. 7. The dispersion of claim 4, wherein the polyglycidyl ether is a novolak polyglycidyl ether.