CA2048233A1 - Advanced epoxy compositions, curable compositions and cured products - Google Patents

Abstract

ABSTRACT

Compositions are prepared by the reaction of (A) an advanced composition resulting from reacting (1) (a) at least one diepoxyalkane or a combination of (a) and (b) a diglycidyl ether of a dihydric phenol; with (2) a dihydric phenol; (B) optionally, a monohydric phenol; (C) a nucleophilic compound; and (D) optionally a Br?nsted acid. These compositions can be cured with curing agents which react with aliphatic hydroxyl groups.

38,596-F

Description

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i ADVANCED EPOXY COMPOSITIONS, CURABLE COMPOSITIONS AND
CURED PRODUCTS
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The present invention pertains to advanced compositions prepared from polyepoxides and dihydric phenols; to curable compositions containing the-qe 5 advanced compositions and to cured products prepared `
from these curable compositions.
` .
Epoxy resins are useful in the preparation of 1~ coatings for metal containers for food and beverages.
~i Environmental concerns over coating solvent emission into the atmosphere has placed increased emphasis on water borne and powder coatings.

Wessling, Yats and Perry have taught in U.S.
Patent 4,383,073 water compatible coatings prepared from the reaction of acidified nicotinamide and an epoxy resin resulting from the advancement of bisphenol A and the diglycidyl ether of bisphenol A. Aqueous dispersions of these products are yellow and ~he resultant coating from this dispersion cured with melamine-formaldehyde resin are light brown in color~
However, the coaters prefer to employ coatings which are ~:, . .
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clear, white, buff or golden in color. Therefore, the light brown coatings prepared with the compositions of Wessling et al~ are undesirable from an aesthetics standpoint.
; 5 It would therefore be desirable to have available, coatings which have: (a) more acceptable dispersion and coating color from an aesthetics standpoint, or (b) an improvement in one or more of its thermal or physical properties, particularly blush resistance, reverse impact and/or T-bend flexibility.
. .

One aspect of the present invention concerns a composition comprising the reaction product of (A) an advanced composition resulting from reacting (1) (a) at least one diepoxyalkane or a combination of (a) and (b) at least one diglycidyl ether of a dihydric phenol; with (2) at least one dihydric phenol; (B) optionally, at least one monohydric phenol; and (C) at least one nucleophilic compound.
One aspect of the present invention concerns a composition comprising the reaction product of (A) an advanced composition resulting from reacting (1) (a) at : least one diepoxyalkane or a combination of (a) and (b) at least one diglycidyl ether of a dihydric phenol; with (2) at least one dihydric phenol; (B) optionally, at least one monohydric phenol; (C) at least one nucleophilic compound; and ~D) at least one Bronsted acid.
A further aspect of the present invention concerns curable compositions comprising (I) a composition comprising the reaction product of (A) an ` 38,596-F -2-`` 2~ fJ~3 :: -3-: advanced composition resulting from reacting ~1) (a) at least one diepoxyalkane or a combination of (a) and (b) at least one diglycidyl ether of a dihydric phenol; with (2) at least one dihydric phenol; (B) optionally, at least one monohydric phenol; and (C) at least one ' nucleophilic compound; and (II) a curing quantity of at .~ least one suitable curing agent for component (I).
A further aspect of the present invention concerns curable compositions comprising (I) a composition comprising the reaction product of (A) an ;; advanced composition resulting from reacting (1) (a) at . least one diepoxyalkane or a combination of (a) and (b) at least one diglycidyl ether of a dihydric phenol; with ~2) at least one dihydric phenol; (B) optionally, at least one monohydric phenol; (C) at least one nucleophilic compound; and (D) at least one Bronsted acid; and (II) a curing quantity of at least one suitable curing agent for component (I).
` Another aspect of the present invention .~ concerns organic solvent-borne curable compositions comprising organic solvent solutions of curable compositions comprising (I) a composition comprising the reaction product of (A) an advanced composition resulting from reacting (1) (a) at least one diepoxyalkane or a combination of (a) and (b) at least . one diglycidyl ether of a dihydric phenol; with (2) at least one dihydric phenol; (B) optionallyg at least one 3 monohydric phenol; and (C) at least one nucleophilic compound; and (II) a curing quantity of at least one suitable curing agent for component (I).
Another aspect of the present invention `; concerns water-borne curable compositions comprising :
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water dispersions or water solutions of curable ~ compositions comprising (I) a composition comprising the : reaction product of (A) an advanced composition resulting from reacting (1) (a) at least one . diepoxyalkane or a combination o~ (a) and (b) at least : 5 one diglycidyl ether of a dihydric phenol; with (2) at . least one dihydric phenol; (B) optionally, at least one ; monohydric phenol; (C) at least one nucleophilic compound; and (D) at least one Bronsted acid; and (II) a . 10 curing quantity of at least one suitable curing agent for component (I).
.`~ Another aspect of the present invention ` concerns solvent free curable compositions comprising : 15 (I) a composition comprising the reaction product of (A) an advanced composition resulting from reacting (1) (a~
~ at least one diepoxyalkane or a combination of (a) and ': (b) at least one diglycidyl ether of a dihydric phenol;
- with (2) at least one dihydric phenol; (B) optionally, at least one monohydric phenol; and (C) at least one nucleophilic compound; and (II) a curing quantity of at least one ~uitable curing agent for component (I).
.~, . A further aspect of the present invention pertains to products resulting from curing any of the aforementioned curable compositions.
:
: A still further aspect of the present invention pertains to articles coated with any of the . 30 aforementioned curable compositions which have been : cured subsequent to being coated onto said articles.
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Definitions The term "Bronsted acid" means an inorganic or organic acid that is capable of donating a proton.
The term "nucleophilic compound" means a basic electron rich compound.
The term "nucleophilic group" means a group i' which contains only one basic group which contains a pair of electrons.
The term "diepoxyalkane" means a compound having two vicinal epoxide groups with a saturated or unsaturated, straight or branched alkyl group between two vicinal epoxide groups and which does not contain ; any oxygen atoms other than the oxygen atoms contained ~ in the vicinal epoxide groups.
., .
The term "dihydric phenol" means any compound which has an average of 2 aromatic hydroxyl groups per molecule.
The term "monohydric phenol" means any compound which contains only one aromatic hydroxyl group per molecule.
.
The term "water-borne" means that the resin composition is miscible, soluble or dispersible in water.

- Preparatlon of Advanced Resin ~ompositions The advanced resin compositions employed in the present invention can be prepared by reac~ing the polyhydric phenol with the epoxy-containing compound in the presence of a suitable catalyst at a temperature of 3~,596-F -5-`:

:, -6- 2 ~ ~ r~ ~ -, , . .
from 90C to 280C, preferably from 120C to 250C, more preferably from 150C to 240C, for a time sufficient to complete the advancement reaction, usually from 0.025 to 48, preferably from 0.3 to 12, more preferably from 0.5 to 8 hours.
` At temperatures below 90C, little or no reaction occurs.
At temperatures above 280C, gelation of the reaction mixture or decomposition occurs.
The epoxide-cantaining compound and the polyhydric phenol are employed in amounts which provide a ratio of phenolic hydroxyl groups per epoxide group of from 0.01:1 to 5:1, preferably from 0.1:1 to 2:1, more preferably from 0.3:1 to 1.1:1.
When the ratio of phenolic hydroxyl groups per epoxide group is less than 1:1, the resulting advanced resin is predominately terminated in epoxy groups. When ~ the ratio of phenolic hydroxyl groups per epoxide group ; is greater than 1:1, the resulting advanced resin is .! predominately terminated in phenolic hydroxyl groups.
When the ratio of phenolic hydroxyl groups per epoxide ~ 25 group is substantially 1:1, the resulting advanced resin -~ is randomly terminated in either epoxy groups or phenolic hydroxyl groups.
The advanced epoxy resins are optionally reacted with a monohydric phenol or the advanced epoxy resin is prepared in the presence of a monohydric phenol.
The monohydric phenol is employed as a capping `- agent to reduce the epoxide content of the resulting ~ 389596-F -6-.

:- .~ .. ..
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product and thus allow independen~ control of the average molecular weight and the epoxide content of the resulting resin as desired.
The monohydric phenol is employed in amounts which pro~ide a ratio of phenolic hydroxyl groups per epoxide group of from 0;1 to 0.85:1, preferably from 0:1 ~ to 0.6:1, more preferably from 0.1:1 to 0.3 1.
.~:
- Suitable catalysts which can be employed to catalyze the reaction between a phenolic hydroxyl group and a vicinal epoxide group include, ~or example, tertiary amines such as, triethylamine, tripropylamine, tributylamine, 2-methylimidazole, N-methylmorpholine, or any combination thereof; quaternary ammonium compounds such as, benzyl trimethyl ammonium chloride, tetrabutylammonium chloride, or any combination thereof;
phosphines such as triphenylphosphine, tributylphosphine, trilaurylphosphine, trichlorobutylphosphine, trinaphthylphosphine, or any combination thereof; and phosphonium compounds such as, ethyltriphenylphosphonium chloride, ethyltriphenylphosphonium bromide, - ethyltriphenylphosphonium iodide, ethyltriphenylphosphonium phosphate, ethyltriphenylphosphonium acetate.acetic acid complex, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, tetrabutylphosphonium iodide~
tetrabutylphosphonium phosphate, tetrabutylphosphonium ~ 30 acetate.acetic acid complex, butyltriphenylphosphonium ,~ tetrabromobisphenate, butyltriphenylphosphonium bisphenate, butyltriphenylphosphonium bicarbonate, or any combination thereof; alkali metal hydroxides such '' ':
.

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~ 38,596-F _7_ ,: .
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as, sodium hydroxide, potassium hydroxide, lithium hydroxide, or any combination thereof.
These catalysts are employed in catalytic amounts and the particular amount Gepends upon the particular reactants and catalyst being employed.
However, usually the amount is from 0.0001 to 10, preferably from 0.05 to 1, more preferably from 0.1 to 0.5 percent by weight based upon the weight of the epoxy resin.
The modified epoxy resin compositions of the present invention are conveniently prepared as solvent-borne or water-borne systems. The solvent-borne systems are prepared by dissolving an epoxy resin in one or more ~uitable solvents and adding either (a) an organic solution of a mixture of a nucleophilic compound and Bronsted acid, ~b) a mixture of a nucleophilic compound and Bronsted acid or (c) an organic solution of a nucleophilic compound followed by later addition of the Bronsted acid. If desirable, additional quantities of organic solvent can be added during the reaction.
Suitable temperatures for the reaction of the epoxy resin and either an organic solution of a mixture of a nucleophilic compound and Bronsted acid or mixture of a nucleophilic compound and Bronsted acid include, for example, from 25C to 150C, preferably from ~0C to 100C and more preferably from 80C to 100C. The maximum reaction temperature depends upon the boiling 3 point of the nucleophilic compound and the Bransted acid chosen. Likewise, the duration or reaction time is also not critical so long as the reaction is conducted for a time su~ficient to complete the reaction.
Suitable reaction times include, for example, from 1 mlnute to 12 hours, preferably from 5 minute~ to 7 38,596-F -8-- . :
.

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! hours, and more preferably from 5 minutes to 1 hour.
Higher reaction temperatures require less time to complete the reaction whereas lower temperatures require more time to complete the reaction.

Suitable temperatures for the reaction of the epoxy resin and nucleophilic compound followed by later `; addition of the Bronsted acid, include, for example, from 25C to 120C, and preferably from 50C to 80C.
Since the nucleophilic compound is very reactive with the epoxy resin, especially at high temperatures, the ~ Bronsted acid should be added soon or directly after the :~ addition oP the organic solution of the nucleophilic compound to avoid gelation. Suitable reaction times include, for example, from 1 to 120, preferably from 1 to 15 minutes. Higher reaction temperatures re~,uire less time to complete the reaction whereas lower temperatures require more time to complete the reaction.
The water-borne systems are prepared by dissolving an epoxy resin in one or more suitable - solvents and adding thereto either (a) an aqueous -~ solution or aqueous dispersion of a mixture of the nucleophilic compound and Bronsted acid, or (b) an organic solution of the nucleophilic compound followed by later addition of an aqueous solution of the Bronsted acid. If desirable, additional quantities of water or organic solvent can be added during the reaction.
Suitable temperatures for the reaction of an aqueous solution or aqueous dispersion of a mixture of the nucleophilic compound and Bronsted acid, include, for example, from 25C to 110C, and preferably from 60C to 100C. The duration or reaction time is not critical so ,: :

38,596-F _g_ , c~
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long as the reaction is conducted for a time sufficient to complete the reaction. Suitable reaction times include, for example, from 1 to 48, preferabl~ from 1 to 14, more preferably from 1 to 7 hours. Higher reaction temperatures require less time to complete the reaction whereas lower temperatures require more time to complete the reactions.

Suitable temperatures for the reactions of the epoxy resin and an organic solution of the nucleophilic ; compound followed by later addition of an aqueous solution of the Bronsted acid 9 include, for example, from 25C to 120C, and preferably from 25C to 120C, and preferably from 50C to 80C. Since the nucleophilic compound is very reactive with the epoxy resin, especially at high temperatures, the Bron~ted acid should be added soon or directly after the addition of the organic solution of the nucleophilic compound to avoid gelation. Suitable reaction times include, for 2~ example, from 1 minute to 12 hours, and preferably from 5 minutes to an hour. Higher reaction temperatures require less time to complete the reaction whereas lower temperatures require more time to complete the reaction.
The nucleophilic compound is employed in amounts which provide a ratio of nucleophilic groups per epoxide group of from 0.15:1 to 1.1:1, preferably from 0.4:1 to 1:1, more preferably from 0.7:1 to O.9ol.
At ratios of nucleophilic groups per epoxide group less than 0.15:1, an unstable aqueous dispersion is usually obtained because it has a low charge density.
.
At ratios of nucleophilic groups per epoxide group greater than 1.1:1, an aqueous solution is usually .,~

- 38,59~-F -10-i., ~. : .: :

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obtained. Whether this stoichiometry results in an aqueous solution or dispersion depends upon the molecular weight of the epoxy resin. With a low ~<2,000) number average molecular weight epoxy resin, the 1.1:1 stoichiometry gives a solution in most instances. With a high (>2,000) number average molecular weight epoxy resin, the 1.1:1 stoichiometry may give a dispersion rather than a solution.
The Bronsted acid is employed in amounts which provide a ratio of moles of acid to nucleophilic group of from 0.2:1 to 10:1, preferably from 0.5:1 to 1.5:1, more preferably from 1:1 to 1.1:1.
When the ratio of moles of Bronsted acid to nucleophilic group is below 0.2:1, the resin composition is not usually miscible, soluble or dispersible in water.
~hen the ratio of moles of Bronsted acid to nucleophilic group is above 10:1, the amount of acid is much above the amount required to neutralize the nucleophilic group and larger amounts tend to ; unnecessarily dilute the product.
For water-borne systems, the charge density of the solid resin is used to determine the quantity of nucleophilic groups per epoxy group contained in the epoxy resin. The charge density is the milliequivalents of nucleophilic compound per gram of solid. A large charge density is required for a high molecular weight epoxy resin than a low molecular weight epoxy resin to obtain a dispersion. For the same molecular ~eight epoxy resin, a low charge density gives an aqueous dispersion whereas a higher charge density may give an .~
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aqueous solution. The charge density may vary from 0.08 to 1.4, preferably from ~.35 to 0.6, more preferably from 0.35 to 0.45 milliequivalents of nucleophilic compound per gram of solid.
~ 5 ; The ratio of epoxy-containing reactant/nucleophilic compound/Bronsted acid is variable so long as the reaction mixture is at neutral or acid pH. Stoichiometry of the reaction requires 1 equivalent of nucleophilic compound and 1 equivalent of acid per vicinal epoxy group to be converted. In order to form the instant cationic compounds from strong acids, an excess of the nucleophilic compounds is required. ~ith weaker acids, good results can be achieved by using substantially stoichiometric amounts of reactants although a slight excess or deficiency of the epoxy-containing reactant or nucleophilic compound can be used. With still weaker acids a slight excess of acid iq preferred to maximize the yield of nucleophilic , 20 compound salts. Good results have been achieved using a ratio of 1.1 equivalents of weak acid and one equivalent of nucleophilic group per epoxide equivalent.

The amount of water that is included in the reaction mixture, for water-borne compositions, can be varied to convenience so long as there is sufficient !' acid and water present to stabilize the nucleophilic compound salt formed during the course of the reaction.
Normally, it has been found preferably to include water in the reaction in amounts of from 10 to 30 moles per epoxy equivalent.

.
The aqueous compositions of the present invention can also contain any amount of an organic ~"~
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38,596-F -12-'`' `' '~ .

solvent such as ethylene glycol monobutyl ether. These solvents are usually employed in amounts of from 1 to 75, preferably from 4 to 35, more preferably from 6 to 18, percent by weight based upon the weight of the aqueous dispersion or solution.

Usually, the Bronsted acid is employed in amounts which provides a ratio of moles of acid to nucleophilic group of from 0.2:1 to 2:1, preferably from 0.5:1 to 1.5:1, more preferably from 1~1 to 1.1:1.

When the ratio of moles of Bronsted acid to nucl~ophilic group is less than 0.2:1, an unstable dispersion normally results.
When the ratio of moles of Bronsted acid to nucleophilic group is greater than 2~1, the properties of the uncured or cured product resin are usually undesirable.

Suitable catalysts which can be employed to ; catalyze the reaction between a phenolic hydroxyl group and a vicinal epoxide group include, for example, tertiary amines such as, triethylamine, tripropylamine, tributylamine, 2-methylimidazole, N-methylmorpholine, or any combination thereof; quaternary ammonium compounds such as, benzyl trimethyl ammonium chloride, tetrabutylammonium chloride, or any combination thereof;
phosphines such as triphenylphosphine, ! tributylphosphine, trilaurylphosphine, trichlorobutylphosphine, trinaphthylphosphine, or any ; combination thereo~; and phosphonium compounds such as, ethyltriphenylphosphonium chloride, ethyltriphenylphosphonium bromide~

` 38,596-F -13-.; , ~ . . ~ . .
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ethyltriphenylphosphonium iodide, ethyltriphenylphosphonium phosphate, ethyltriphenylphosphonium acetate.acetic acid complex, tetrabutylphosphonium chloride, tetrabutylpho~phonium bromide, tetrabutylphosphonium iodide, tetrabutylphosphonium phosphate, tetrabutylphosphonium acetate.acetic acid complex, butyltriphenylphosphonium tetrabromobisphenate, butyltriphenylphosphonium bisphenate, butyltriphenylphosphonium bicarbonate, or any combination thereof; alkali metal hydroxides such as, sodium hydroxide, potassium hydroxide, lithium hydroxide, or any combination thereof.
These catalysts are employed in catalytic amounts and the particular amount depends upon the particular reactants and catalyst being employed.
However, usually the amount is from 0.0001 to 10, preferably from 0.05 to 1, more preferably from 0.1 to 0.5 percent by weight based upon the weight of the epoxy resin.
Diepoxyalkanes .
Suitable diepoxyalkanes which can be employed herein include, for example, those represented by the following general formula I

:

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~ 38,596-F 14-~ .

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Formula I
, . .

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Z' CH - CH - Z - CH - CH - Z' ; 10 wherein Z is a direct bond, a divalent saturated or unsaturated aliphatic or cycloaliphatic hydrocarbon group having from 1 to 30, preferably from 4 to 30, more preferably from 14 to 30 carbon atoms; and each Z' is independently hydrogen, an alkyl or alkene group having ~rom 1 to 20, preferably from 1 to 2, more preferably 1, carbon atom(s). Particularly suitable diepoxyalkanes include, for example, 1,2:3,4-diepoxybutane, 1,2:5,6-diepoxyhexane, 1,2:7,8-diepoxyoctane, 1,2:8,9-diepoxynonane, 1,2:9,10-diepoxydecane, 1,2:13,14-diepoxytetradecane, 4,5:9,10-diepoxy-1-decene, or any ~ combination thereof.
:, The diepoxyalkanes are prepared by epoxidizing the reactive olefin groups of olefins. The olefin group can be epoxidized with any number of peracids, especially perbenzoic, peracetic, m-chloroperbenzoic and trifluoroperacetic acid as described in l'Advanced Organic Chemistry" 2nd edition by Jerry March, McGraw-Hill Book Company, 1977, pO 750 and in U.S. Patent3,488,404 by Phillip Parker, which are incorporated herein by reference. The olefin group may also be ; epoxidized with very dilute hydrogen peroxide in the presence of the two-component association consisting of tungstate and phosphate (or arsenate) ions according to .
38,596-F -15-;~

. . , . ,. ~ : , . - , , the technique of phase transfer catalysis as described in the J. Org. Chem. 1983, vol. 48, pp. 3831-3833 by C.
Venturello, E. Alneri and M. Ricci.
The epoxidation of the olefin group can be carried out at a temperature suitably from 0C to 70C, preferably from 25C to 50C for a time sufficient to complete the reaction, usually from 15 minutes to 20 hours.
Dihydric Phenols Suitable dihydric phenols which can be employed herein include any compound having two aromatic hydroxyl groups per molecule. Exemplary of such dihydric phenols include those represented by the following general formulas II or ;II

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Formula II
(X)4 HO ~ - OH

Formula III
`' 10 HO ~ (A)n ~ OH

wherein each A is independently a divalent hydrocarbyl group having suitably from 1 to 12, more suitably from 1 to 6, most suitably from 1 to 4, carbon atoms, -S-, -S-S-, -SO-, -S02-, CO- -O-, -O-CO-O-; each X is independently hydrogen, a hydrocarbyl or hydrocarbyloxy ~ group having suitably from 1 to 12, more suitably from 1 :`- to 6, most suitably from 1 to 4, carbon atoms or a halogen atom, preferably chlorine or bromine; and n has a value of zero or 1.
The term hydrocarbyl as employed herein means any aliphatic~ cycloaliphatic, aromatic, aryl substituted aliphatic or cycloaliphatic, or aliphatic or ~ 3 cycloaliphatic substitute~ aromatic groups. Likewise, i the term hydrocarbyloxy means a hydrocarbyl group having . an oxygen linkage between it and the carbon atom to which it is attached. The term divalent hydrocarbyl :: group refers to the aforementioned hydrocarbyl groups . minus an additional hydrogen atom. Particularly ' 38,596-F -17-. .
. ~
' , suitable dihydric phenols include, for example, hydroquinone, resorcinol, catechol, bisphenol A, bisphenol F, bisphenol K, brominated or Cl-C4 alkyl derivatives thereof, or any combination thereof.
Di~l~cidyl Ethers of Dihydric Phenols Suitable diglycidyl ethers of dihydric phenols which can be employed herein include the diglycidyl ethers of the aforementioned dihydric phenols.
Particularly suitable diglycidyl ethers of dihydric phenols include, for example, the diglycidyl ethers o~
bisphenol A, bisphenol F, bisphenol K, brominated and C1 to C4 alkyl derivatives thereof, or any combination thereof.

Monohydric Phenols ; Suitable monohydric phenols which can be employed herein include, for example, any compound having only one aromatic hydroxyl group per molecule.
20 Exemplary of such monohydric phenols include, for - example those represented by the following general formula IV
i '.'~
Formula IV
.

(X')5 ~ OH

:, :
wherein each X' is independently hydrogen, a hydrocarbyl ; or hydrocarbyloxy group having suitably from 1 to 16, s more suitably from 1 to 6~ most suitably from 1 to 4, ~ carbon atoms, a nitro (-N02) group or a halogen atom, ~, . -38,596-F -18-.,.-.

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~, ~

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preferably chlorine or bromine. Particularly suitable monohydric phenols include, for example, phenol, o-cresol, p-cresol, nonylphenol, chlorophenol, dichlorophenol, trichlorophenol, pentachlorophenol, bromophenol, dibromophenol, tribromophenol, trifluoro-m-cresol, 3-ethylphenol, 4-ethylphenol, 3-isopropylphenol, 4-n-propylphenol, 4-isopropylphenol, 3-tert-butylphenol, 4-sec-butylphenol, 4-tert-butylphenol, p-tert-amylphenol, 4-n-butoxyphenol, 4-heptyloxyphenol, 3,5-tert-butylphenol, 4-(tert-octyl)phenol, 3-n-pentadecylphenol, o-methoxyphenol, m-methoxyphenol, 2-methoxy-4-methylphenol, 4-ethyl-2-methoxyphenol, 3,4-methylenedioxyphenol, or any combination thereof.
Reaction Solvents Suitable solvents which can be employed in the : reaction of the advanced epoxy resin with the nucleophilic compound and Bronsted acid include, for example, glycol ethers, glycol esters, alcohols, ketones or any combination thereo~. Particularly suitable such solvents include, ~or example, 2-butoxyethanol, diethylene glycol monopropyl ether, diethylene glycol ~ monobutyl ether, diethylene glycol monohexyl ether, - 25 propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol tertiary butyl ether, propylene glycol isopropyl ether, dipropylene glycol : monobutyl ether, ethylene glycol phenyl ether, propylene glycol phenyl ether, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, n-pentyl propionate, C6 to C13 alkyl : acetates, butanol, acetone, methylethyl ketone, methyl ; isobutyl ketone, or any combination thereof.

''' 38,596-F -19-' .

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; -20-Nucleophilic Compound The nucleophilic compound can be either a monopyridine or a polypyridine, quinoline, isoquinoline, secondary amine or tertiary amlne compound.
Suitable monopyridines include those having one pyridine group per molecule represented by the following ` formula V

tO
Formula V ~
~C~ (Ra)5 N

wherein each Ra is independently selected from hydrogen, a halogen atom, particularly chlorine or bromine, a hydrocarbyl or hydrocarbyloxy or a hydroxy substituted ~ 20 hydrocarbyl group having from 1 to 10, preferably from 1 ;~ to 6, carbon atoms~ a carbamoyl group (-C0-NH~), or a ;3', hydroxyl group. Particularly suitable monopyridine compounds include nicotinamide, pyridine, 2-picoline, 3-picoline, 4-picoline, 4-ethylpyridine, 3,4-dimethylpyridine, 3,5-dimethylpyridine, 4-phenylpyridine, 4-propanolpyridine, or any combination thereof. The preferred monopyridine is nicotinamide.
:~' Suitable polypyridines which can be employed 3 includé any compound having more than one pyridine group per molecule. Particularly suitable such pyridine-~ containing compounds include those represented by the f; following formulas VI, VII and VIII

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38,596-F -20--. , : ~ : ~-:
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~b~

Formula VI (Ra)3 {~

Formula VII
~, ~Ra)3 (RQ~4 _ ~ ( CH~ Rb~ ( C~2 ) ~ ~ (Ra~

Formula VIII (Ra)3 (Ra~4 ~ ~b ~ (Ra~

wherein each Ra is independently hydrogen, a halogen atom, particularly chlorine or bromine, a hydrocarbyl or hydrocarbyloxy or a hydroxy substituted hydrocarbyl group having from 1 to 10, preferably from t to 4, carbon atoms, a carbamoyl group (-CO-NH2), or a hydroxyl group; and each x and y independently has a ~ value from 1 to 5; Rb is an alkyl group having ~rom 1 to .; 3 10 carbon atoms, an amine group, a urea group, a thiourea group, a carbonyl group, -S-S- group, -S-CH2 CH2-S- group, -C(OH)H-CO-group, or an amide group.
Partieularly suitable polypyridines include, ~or ~ example, 1,2~bis(4-pyridyl)ethane, 4,4'-i trimethylenedipyridine, 3~3'-bipyridine, 4,4'- :
.
, :., 38,596-F -21-., .' ~ -, . . .

: , 2 ~

bipyridine, 4,4'-bipyridinehydrate, 2,3'-bipyridine, 2,4'-bipyridine, 4,4'-dimethyl-2,2'-bipyridine. 1,3-di-(3-picolyl)urea, 1,3-di-(3-picolyl)thiourea, di-(2-picolyl)amine, 2,2'-(3,6-dithiaoctamethylene)dipyridine, trans-1,2-bis(4-pyridyl)ethylene, 2,2',6',2't-5 terpyridine, aldrithiol-4, 2,2'-pyridil, alpha-methyl-1,2-di-3-pyridyl-1-propanone, alpha-pyridoin, or any combination thereof.

Suitable quinoline and isoquinolines which can be em?loyed are represented by the following formulas IX
and X.

Formula IX ~
(~b)4 ~ ~ (Ra)3 :
Formula X ~
(Rb)4 ~ ~ (~a)3 wherein each Ra and Rb is independently selected from hydrogen, a halogen atom, particularly chlorine or bromine, a hydrocarbyl or hydrocarbyloxy or a hydroxy substituted hydrocarbyl group having from 1 to 10, ; 3 preferably from 1 to 6, carbon atoms, a carbamoyl group (-C0-NH2), or a hydroxyl group. Particularly suitable quinoline and isoquinoline compounds include quinoline, 4-methylquinoline, 2,2'-biquinoline, 4-chloroquinoline, ;. 3-bromoquinoline, 5-hydroxyquinoline, isoquinoline, 4-:`
38,596-F -22-.~ ~

, ~ . :

.~
bromoisoquinoline, 5-hydroxyisoquinoline, or any combination thereof.
.
Suitable secondary and tertiary amines which can be employed include those represented by the .
following formula XI.

Formula XI R3-N-R4 ~ I

wherein R3 and R4 individually are lower alkyl, hydroxy lower alkyl, a .. / R7 `'.' -R6-N=C
.` \ R8 group or R3 and R4 are combined as one alkylene radical having from 3 to 5 carbon atoms, R6 is an alkylene group '. having from 2 to 10 carbon atoms, R7 and R8 individually `: are lower alkyl and R5 is hydrogen or lower alkyl, aralkyl or aryl, except that when R3 and R4 together are an alkylene group then R5 is hydrogen, lower alkyl or ~ s ., . , .
,:
.j ~ 38,596-F -23-' `

~, . .
.

' ,,'. ; : , ,: . ~ , , 3 ~
-2~-hydroxyalkyl and when either or both of R3 and R4 is a -R6-N=C
\ R8 radieal then R5 is hydrogen.

Particularly suitable secondary and tertiary amines include dimethylamine, diethylamine~ dlbutyl amine, N-methylethanolamine, diethanolamine and the ketimine derivatives of polyamines containing secondary and primary amino groups such as those produced by the reaction of diethylenetriamine or N-aminoethylpiperazine with acetone, methyl ethyl ketone or methylisobutyl ketone; N-methylpiperidine, N-ethylpyrrolidine, N-hydroxyethylpyrrolidine, trimethylamine, triethylamine, ~ tri-n-propylamine, triisobutylamine, ; 20 hydroxyethyldimethylamine, butyldimethylamine, trihydroxyethylamine, N,N,N-dimethylphenethylamine and or any combination thereof.

Suitable secondary and tertiary polyamines include those represented by the following formulas XII, XIII, XIV, XV, XVI or XVII
Formula XII
Rb Rb 3 Ra-N-(R"-N)X-Ra , :
:

38,596-F -24-.~

- . . ~ :. . - :

;: .. ;:

, ., ;
. . .

Formula XIII
Rb - Ra-N-~R~-N~y-Ra R"
, I
N - Rb Ra . .

Formula XIV CR'2-CR'2 /
Ra - N N - Ra \
CR ' 2-CR ' 2 Formula XV
CR'2-CR'2 Rb '' / \ I
Ra - N N-(R~-N)~-Ra CR'2-CR'2 '.
~ Formula XVI Rb CR'2-CR'2 Rb ' I / \ I
~ ^ Ra-(N-R"-N N)X-R'l-N-Ra ~ \ /
CR'2-CR'2 .~
38,596-F -25-.:

~ , , :

Formula XVII
/ CR'2-CR'2 / CR 2-cR 2 Ra - N CH-R"-CH N - Ra CH'2-CR'2 CR'2-CR'2 wherein each Ra and Rb are independently hydrogen or an alkyl group having from 1 to 10 carbon atoms, pref?rably . 10 from 1 to 4 carbon atoms provided that both Ra and Rb are not a hydrogen at the same time; each R' i5 independently hydrogen or an alkyl group having 1 to 4 carbon atoms, preferably 1 carbon atom; R" is a . 15 hydrocarbyl or hydrocarbyloxy group having from 1 to 10 .
carbon atoms; x has a value from 1 to 10, preferably from 1 to 2; and y has a value from 2 to 10, preferably from 2 to 4.
.
Preferably, secondary and tertiary polyamines include 4,4'-bipiperidine, 4,4'-ethylenedipiperidine, -~. 4,4'-trimethylenedipiperidine, N,N,N',N'-; tetramethylethylenediamine, N,N,N',N'-tetramethyl-1,3-propanediamine, N,N,N',N'-tetramethyl-1,4-butanediamine, N,N,N',N'-tetramethyl-1,6-hexanediamine, N,N,N',N'-tetramethyldiaminomethane, bis-(2-dimethylaminoethyl)methylamine, 4,4'-trimethylenebis(1-`~ methylpiperidine), 1,4-dimethylpiperazine, or any combination therof.

`` Although the pyridine~, polypyridines, quinolines, isoquinolines, secondary amines and tertiary amines are nucleophilic compounds, they undergo different reactions giving different products. The reaction of pyridines, polypyridines, quinolines and . .
38,596-F -26-` :
:' .. . ~ ~ . . .

.

.f;~

isoquinolines with an epoxide group gives conjugated 3,5-dienes, cyclic amide or pyridone comp~unds as described in Die Angewante Makromolekulare Chemie. 1986, volume 142, pp 17-27 by G. Xue, H. Ishida and J.L.
Koenig. The reaction oP secondary and tertiary amines with an epoxide group does not form 3,5-dienes, cyclic amides or pyridone compounds.
Bronsted Acids Suitable Bronsted acids which can be employed include any such acid or combination of acids which promotes the reaction between the nucl~ophilic compound and the epoxide group and provides a compatible anion in the final product. By "compatible anion", it is meant one which exists in close association with the cationic nitrogen of the nucleophilic compound for an indefinite period. Monobasic acids are usually preferred. The Bronsted acids can be inorganic or organic acids.
Preferred inorganic acids which can be employed include, for example, phosphoric acid, hydrochloric acid, hydrobromic acid, nitric acid, sulfuric acid, or any combination thereof. Organic acids which can be employed herein include, for example, those saturated or unsaturated carboxylic or sulfonic acids having from 2 to 30, preferably from 2 to 6, more prePerably from 2 to 3 carbon atoms. The preferred organic acids include, for example, acetic acid, propionic acid, acrylic acid, methacrylic acid, itaconic acid, methanesulfonic acid, ethanesulfonic acid, decanoic acid, triacontanoic acid, lactic acid, glycolic acid, or any combination thereof.
Curin~ Agents Those compositions which contain epoxy groups can be cured with conventional epoxy curing agents which cure by reaction with the epoxy groups. Suitable such 38,596-F -27-curing agents include, aromatic or aliphatic or - cycloaliphatic compounds containing an average of more than two primary or secondary amino hydrogen atoms per molecule; compounds having an average of more than two carboxyl groups per molecule; anhydrides of compounds containing two or more carboxyl groups per molecule;
biquanides; guanadines; guanimines, amides and polyamides, imidazoles, aromatic hydroxyl-containing compounds; or any combination thereof. Particularly suitable such curing agents include, for example, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, isophoronediamine, N-aminoethylpiperazine, methanediamine, 1,3-diaminocyclohexane, xylylenediamine, m-phenylenediamine, 1,4-methylenedianiline, metaphenylenediamine, diaminodiphenylsulfone, ` diaminodiphenyl ether, 2,4-toluenediamine, 2,6-diaminopyridine, bis(3,4-diaminophenyl)sulfone, resins prepared from aniline and formaldehyde, aminated polyglycols, oxalic acid, phthalic acid, maleic acid, ~` aconitic acid, carboxyl terminated polyesters, phthalic anhydride, succinic anhydride, citraconic anhydride, itaconic anhydride, dodecenylsuccinic anhydride, Nadic Methyl Anhydride (methylbicyclo(2.2.1)heptene-2,3-dicarboxylic anhydride isomers), pyromellitic dianhydride, cyclopentanetetracarboxylic dianhydride, benzophenonetetracarboxylic dianhydride, dicyandiamide, 2-methylimidazole; or any combiration thereoY. These compositions can also be cured with the following : enumerated curing agents for curing compositions containing secondary aliphatic hydroxyl groups.
Those compositions which do not contain epoxy groups but only the secondary hydroxyl groups resulting 38,596-F -28-:
. .

. ~ :
, 2~3d~3,:~

from the reaction between the epoxy groups and the dihydric phenol can be cured with such curing agents as melamine-aldehyde resins, alkylated melamine-aldehyde resins, urea-aldehyde resins, alkylated urea-aldehyde resins, phenol-aldehyde resole resins, alkylated phenol-aldehyde resole resins, blocked polyisocyanates, or any combination thereof. Particularly suitable such curing agents include, for example, hexamethoxymethylmelamine, highly methylated melamine-formaldehyde resin, highly alkylated ethoxy methoxy melamine-formaldehy~e resins~
; and highly alkylated methoxymethyl isobutoxymethyl melamine-formaldehyde resin commercially available from American Cyanamide Co. as CYMELTN303, CYMEL~U325, CYMELT~1116, AND CYMEL~H1161 respectively; melamine-formaldehyde resins commercially available from Monsanto Co. as RESIMENE~730 and RESIMENEr~735; urea-formaldehyde resins commercially available from American Cyanamide Co. as BEETLEr~60 and BEETLErY65; a mixture of the allyl ` ethers of mono-, di- and tri-methylol phenols, and a mixture of the allyl ethers of methylol phenol partlally polymerized and phenol-formaldehyde synthetic resole resin commercially available from BTL Specialties Corp.
as METHYLONT~75-108, METHYLON~75-121 and VARCUM
SYNTHETIC RESIN 29-101, respectively; 2-ethylhexanol blocked prepolymer of toluene diisocyanate and trimethylol propane; 2-ethylhexanol blocked prepolymer of diphenyl methane 4,4-diisocyanate; C3-CIo ketoxime ; blocked aromatic, aliphatic or cycloaliphatic polyisocyanates; or any combination thereof.
If desired, promoters or accelerators can be employed with the urea-aldehyde resins, alkylated urea-aldehyde resins, melamine-aldehyde resins, alkylated ` melamine-aldehyde resins, phenol-aldehyde resole resins, .

38,596-F -29-" , ' ' .

2 ~ 'J

~3~
.~

and alkylated phenol-aIdehyde resole resins. Suitable such promoters or accelerators include, for example, phosphoric acid, polyphosphoric acid, maleic acid, citric acid, organic sulfonic acids, such as, ben7ene sulfonic acid, p-toluene sulfonic acid, or any combination thereof.
The curing agents are employed in amounts which will generally cure the advanced resin, i.e. that amount - which is sufficient to render the resultant cured coating composition non-tacky. In those instances where the curing agent cures by reacting with the epoxide groups, they are employed in amounts which provide a ratio of equivalents of curing agent per epoxide group of from 0.01:1 to 10:1, preferably from 0.1:1 to 5:1, more prePerably from 0.5:1 to 1.5:1. In those instances where the advanced resin cures through the secondary hydroxyl groups along the backbone, the curing agent is employed in amounts which provide a ratio of squivalents of curing agent per secondary hydroxyl group o~ from 0.05:1 to 5:1, pre~erably from 0.1:1 to 3:1, ~ore : preferably from 0.3:1 to 2:1.
If desired, the coating composition can be ` 25 formulated with conventional additives. Suitable such additives include, for example, antifoam agents, flow control agents, slip agents, adhesion promoters, flexibility promoters, surface tension modifiers, stress release agents, gloss reducing materials, rheology 3 modifiers, stabilizers, surfactants, coalescing solvents, reactive diluents, plasticizers or any combination thereof. A partial list of suitable additives, include for example, methacrylamide functional amine adduct of neopentyl(diallyl)oxy, tri(dioctyl)pyro-phosphato titanate which is 38,596-F _30_ '' . ~

: ~i ,.. . .
- : . , .,. ~, .

- . , commercially available from Kenrich Petrochemicals, Inc. as LICArM 38J; methacrylamide functional amine adduct of neopentyl(diallyl)oxy, tri(dioctyl)pyro-phosphato zirconate which is commercially available from Kenrich Petrochemicals, Inc. as LZ 38J; a solution oP
polyether modified methyl alkyl polysiloxanes which is commercially available from BYK~-Chemie as BYK'M-321; a solution of polyether modified dimethyl polysiloxanes which is commercially available from BYKT~-Chemie as BYK~M-306; and a silicone resin solution which is commercially available as SR882M from General Electric.
The amount of additive depends on the additive type, formulation, crosslinker (curing agent) concentration and type, and many other variables. As a consequence, the Applicants do not wish to be bound by ` any particular concentration range. Typically additives ar~ usually employed in amounts from-0.00001 to 10, preferably from 0.001 to 5, more preferably from 0.1 to 0.5 percent by weight based upon the weight of total solids. Plasticizers may be added in quantities of 10 to 40 percent by weight.
In the water-borne coatings, the resin and curing agent and other additives, if desired, are blended together with a sufficient amount of water to provide the composition with the desirable application viscosity. The amount of water employed will depend upon the viscosity of the blended components without the 3 water. The higher viscosity compositions will require more water to reach the desired application viscosity than those compositions with lower viscosities.
,.
The coating compositions can be pigmented and/or opacified with known pigments and opacifiers. For many .

38,596-F -31-.~

-' ' ' , ~ ....

. ~

~: ~
2 ~

uses, including food uses, the preferred pigment is ; titanium dioxide. Generally, the pigment is used in a pigment to binder ratio of from 0.1:1 to 1:1 by weight.
Other pigments include, antimony oxide, zinc oxide, white lead, calcium carbonate, silica, aluminum silicate, or any combination thereof.
The coating compositions can be applied by any conventional method in the coating industry. Therefore, spraying, rolling, dipping, flow control or electrodeposition applications can be employed for both clear and pigmented films. Spraying is the preferred technique for the aqueous coating compositions. After application onto the substrate, the coating is thermally cured at temperatures of from g50C to 235C or higher, for periods in the range of from 1 to 60 minutes. The resultant films can be dried at ambient temperatures for ` longer periods of time.

The following examples are illustrative of the invention, but are not to be construed as to limiting the scope thereof in any manner.
"

.

,~

. . , ~ 38,596-F -32-., . . .. ;
. ; ~ . ~ . ./ . -, , . , ~

- ,~

PREPARATION OF ADVANCED EPOXY RESINS

CgH1402 DIEPOXIDE
A CgH1402 diepoxide having an epoxide equivalent weight (EEW) of 73.31 (49.8 grams, o.70 equivalent), bisphenol A (71.3 grams, 0.625 e~uivalent) and 0.1067 grams ethyltriphenylphosphonium acetate.acetic acid complex catalyst (70% solids in methanol) were added to a four neck 500 milliliter round bottom ~lask equipped with a means for stirring and temperature control. The contents were heated with stirring to a temperature of 170C over a period of 65 minutes. The contents were then allowed to exotherm to a temperature of 210C after 15 which the contents were cooled to a temperature of 185C
and maintained at a temperature of about 185C for a ~ period of 90 minutes. A sample was taken and an ; analysis revealed it to have an EEW of 2083. The - resultant product was poured onto a sheet of aluminum 20 foil and allowed to cool at room temperature.

CloHIgO2 DIEPOXIDE
A CIoHl8o2 diepoxide having an epoxide equivalent weight of 86.38 ( 100 grams, 1.158 equivalents), bisphenol A ( 119.5 grams, 1.046 equivalents) and 0.2143 grams ethyltriphenylphosphonium acetate.acetic acid ` 30 complex (70% solids in methanol) were added to a reactor of the type described in Example 1. The contents were ~ heated with stirring to a temperature of 170C over a ; period of 65 minutes. The contents were then allowed to exotherm to a temperature o~ 190C after which the contents were cooled to a temperature of 1 85C and 38,596-F ~33_ . ~

. -~. .

., :
- maintained at a temperature of about 185C for a period of 90 minutes. A sample was taken and an analysis revealed it to have an EEW of 1931. The resultant product was poured onto a sheet of aluminum foil and allowed to cool at room temperature.

; C14H2602 DIEPOXIDE
A C14H2602 diepoxide having an epoxide equivalent ~; 10 weight of 112.61 (111.0 grams, 0.99 equivalents), - bisphenol A (91.65 grams, 0.803 equivalents) and 0.2895 grams ethyltriphenylphosphonium acetate.acetic acid ; complex catalyst (70% solids in methanol) were added to a reactor of the type described in Example 1. The contents were heated with stirring to a temperature of 170C over a period of 65 minutes. The contents were then allowed to exotherm to a temperature of 190C after which the contents were cooled to a temperature of 185C
and maintained at a temperature of about 185C for a ~ period of 90 minutes. A sample was taken and an - analysis revealed it to have an EEW of 1445. The resultant product was poured onto a sheet o~ aluminum foil and allowed to cool at room temperature.
` E~AMPLE 4 PREPARATION OF ADVANCED EPOXY RESIN FROM
` C14H2602 DIEPOXIDE, BISPHENOL A AND THE
DIGLYCIDYL ETHER OF BISPHENOL A
`~ 30 A C14H2602 diepoxide having an epoxide equivalent weight of 130.18 (50 grams, 0.38 equivalent), bisphenol A (65.98 grams, 0.58 equivalent) and 0.2143 grams of ethyltriphenylphosphonium acetate.acetic acid complex catalyst (70~ solids in methanol) were added to a reactor o~ the type described in Example 1. The 38,596-F -34_ .
, . . . . ; .

-2 ~3 contents were heated with stirring to a temperature of 185C over a period of 90 minutes. A diglycidyl ether of bisphenol A having an epoxide equivalent weight of 180.14 ~50 grams, 0.28 equivalent) was then charged into the reactor. The contents were heated l~ith stirring to a temperature of 185C over a period of 45 minutes and maintained at 185C ~or a period of 150 minutes. A
sample was taken and an analysis revealed it to have an EEW of 2112 and a weight average molecular welght of 10,800. The molecular weight was determined by gel permeation chromatography. The resultant produot was poured onto a sheet of aluminum foil and allowed to cool at room temperature.

PREPARATION OF AQUEOUS DISPERSIONS AND SOLUTIONS

The advanced epoxy resin from Example 2 having an epoxide equivalent weight of 1931 ( 110 grams, 0.0570 equivalents) and 22.02 grams (0.186 moles) of 2-butoxyethanol were added to a four neck 500 mL round bottom flask equipped with a means for purging nitrogen, temperature control, stirring, condensing and reactant addition. The epoxy resin was slowly dissolved by heating to 125C. Then the resin was cooled to 80C. In a two ounce (59.1 mL) bottle was mixed 25.7 grams (1.42 moles) deionized water, 5.22 grams (0.0427 mole) nicotinamide and 4.83 grams (0.0456 mole) of an aqueous solution of 85% lactic acid. This solution was then added dropwise over a period of 31 minutes while maintaining the reaction temperature at 80C. The mixture was stirred at 90C for an additional 125 minutes. Then 259 grams deionized water was added to the gray reactor contents over a thirty minute period : 38,596-F -35-2~8~

;' '~
~- while maintaining the reaction temperature between 85C
and 90C. The white aqueous dispersion with a non-volatile content of 28 percent and charge density of 0.36 milliequivalent/gram resin was allowed to cool to ambient temperature with stirring. The pH of the stable aqueous dispersion was 3.5. The viscosity as measured with a No. 4 Ford Cup was 38 seconds. The volatile organic content of the dispersion was 1.37 pounds per gallon (164 grams/liter). The a~ueous solution was further diluted with deionized water to give an aqueous dispersion with a non-volatile content of 25 percent.
Then ethylene glycol n-butyl ether (14.7 grams) and n-butanol (7.5 grams) were added to the resulting aqueous dispersion (278.7 grams).

~ Coatings were prepared by blending 43.159 grams `~ of the aqueous solution prepared in Example 5, with 1-439 gra~s ~f CYMELrM325 to give a formulation containing 15.0 parts per hundred resin (phr) CYMELrY325. CYMELTM325 was a highly methylated melamine-` formaldehyde resin which was commercially available from the American Cyanamid Co. The formulation was applied to 24 gauge X 4 inches X 12 inches (0O66 mm X 101.6 mm X
304.8 mm) unpolished clean-treated cold rolled steel - panels and degreased 7.5 mils X 4.5 inches X 9.0 inches (0.19 mm X 114.3 mm X 228.6 mm) tin free steel panels with a No. 22 wire wound rod according to ASTM D 4147-3 82. The tin free steel panels were degreased by washing the panels in methyl ethyl ketone and drying in an oven at 400F (204.4C) for ten minutes. The coated panels were baked in an oven at 400F (204.4C) for 10 minutes.
The thickness o~ the coating was between Q.28 and 0.30 mils (0.00711 mm and 0.00762 mm).
.
.~

38,596-F -36-. :

.,: .
. , - . :~ . . , - : , ,, . , ~,: , ... . .
;

Coatings were prepared by blending 34.440 grams of the aqueous solution prepared in Example 5, wi th 1.539 grams oP CYMEL~M325 to give a formulation containing 20.1 phr CYMELrM325. The formulation was applied and cured as described in Example 6. The thickness oP the coating was between 0.27 and 0.30 mil (0.00686 mm and 0.00762 mm).

Coatings were prepared by blending 48.161 grams of the aqueous solution prepared in Example 5, with 2.722 grams of CYMELIM325 to give a formulation containing 25.4 phr CYMEL~M325. The ~ormulation was applied and cured as described in Example 6. The thickness oP the coating was between 0.29 and 0.31 mil (0.00737 mm and 0.00787 mm).

The advanced epoxy resin from Example 3 having an epoxide equivalent weight of 1445 (110 grams, 0.07612 equivalents) and 22.03 grams (0.186 moles) of 2-butoxyethanol were added to a reactor of the type described in Example 5. The epoxy resin was slowly dissolved by heating to 125C. Then the resin was cooled to 80C. In a two ounce (59.1 mL) bottle was mixed 34.27 grams (1.90 moles) deionized water, 6.97 grams (0. 0571 mole) nicotinamide and 6.45 grams (o.o609 mole) of an aqueous solution of 85% lactic acid. This solution was then added dropwise over a period oP 48 ; minutes while maintaining the reaction temperature at 80C . The mixture was stirred at 90C for an additional 38,596-F -37-,:

.
~;

245 minutes. Then 155.5 grams deionized water was added to the yellowish brown reactor contents over a fourteen minute period while maintaining the reaction temperature between 88C and 94C. The light brown transparent aqueous solution had a non-volatile content of 36.5 percent and charge density of 0.466 milliequivalent/gram resin was allowed to cool to a~bient temperature with stirring. The pH of the stable aqueous dispersion was 4~0. The viscosity which was measured with a Ford Cup No. 4 was 36 seconds. The volatile organic content of the solution was 1.34 pounds per gallon (160.6 grams/liter).

Coatings were prepared by blending 43.519 grams of the aqueous solution prepared in Example 9, with 1.615 grams of CYMEL r~ 325, 3.225 g~ams ethylene glycol n-butyl ether, 0.804 grams n-butanol and 2.404 grams water to give a formulation containing 10.2 parts per hundred resin (phr) CYMEL~M325. The ethylene ~lycol n-butyl ether and N-butanol were added to lower the surface tension of the coating. The formulation was applied to 24 gauge X 4 inches X 12 inches (o.66 mm X
101.6 mm X 304.8 mm) unpolished clean-treated cold rolled steel panels and 7.5 mils X 4.5 inches X 9.0 inches (0.19 mm X 114.3 mm X 228,6 mm) degreased tin free steel panels with a No. 12 wire wound rod according to ASTM D 4147 82. The tin free steel panels ~ere 3 degreased by washing the panels in methyl ethyl ketone and drying in an oven at 400F (204.4C) for ten minutes.
The coated panels were baked in an oven at 400F
(204.4C) for 10 minutes. The thickness of the golden colored coating was between 0.17 and 0.20 mil (0.00432 mm and 0.00508 mm).

38,596-F -38-: , ~
, -;; .
. . ~ ~ :. ...
. . : .

.

Coatings were prepared by blending 51 ~ 334 grams of the aqueous dispersion prepared in Example 9, with 4.708 grams of CYMELrM325, 3.943 grams ethylene glycol n-butyl ether, 1.000 gram n-butanol, and 3 ~ 003 grams water to give a formulation containing 25.1 phr CYMELrY325. The formulation was applied and cured as described in Example 10. The thickness of the coating was between 0.17 and 0~31 mil (0~00432 mm and 0.00787 ~ mm).
:

Coatings were prepared by blending 43.519 grams of the aqueous solution prepared in Example 9, with 1 ~ 615 grams of CYMELr~ 325 ~ 3 ~ 225 grams ethylene glycol n-butyl ether, 0.804 gram N-butanol and 2.404 grams water to give a formulation containing 10~2 parts per hundred resin (phr) CYMELTM325. The formulation was applied with a No. 16 wire wound rod as described in Example 10. However, the coated panels were baked in an oven at 400F (204~4C) for 20 minutes. The thickness of the coating was between 0~27 and 0~36 mil (0~00686 mm 25 and 0.00914 mm).
.:

Coatings were prepared by blending 44. 346 grams 30 of the aqueous solution prepared in Example 9, with 3 ~ 244 grams of 5YMEL~ 325 ~ 3 ~ 374 grams ethylene glycol n-butyl ether, 0. 872 grams n-butanol and 1. 777 grams ;
water to give a formulation containing 20 ~ 0 phr CYMEL~325. The formulation was applied and cured as described in Example 12~ The thickness of the coating , ;
38~596-F ~39~

.

. . ~

2~?,~

was between 0.26 and 0.30 mil (0.00660 mm and 0.00762 mm).

Coatings were prepared by blending 51.334 grams of the aqueous solution prepared in Example 9, with 4.708 grams of CYMEL~N325, 3.943 grams ethylene glycol n-butyl ether, 1.000 gram N-butanol, and 3.003 grams water to give a formulation containing 25.1 phr CYMELrN325. The formulation was applied and cured as described in Example 12. The thickness of the coating was between 0.30 and 0.34 mil (0.00762 mm and 0.00864 mm).

The advanced epoxy resin from Example 3 having an EEW of 1445 (34.9 grams, 0.0241 equivalents), a bisphenol A epoxy resin with an epoxide equivalent weight of 1755 (56.0 grams, 0.0319 equivalsnt) and 25.15 grams (0.2128 mole) of 2-butoxyethanol were added to a reactor of the type described in Example 5. The epoxy resin was slowly dissolved by heating between 120C and 137C. Then the resin was cooled to 80C. In a two ounce bottle was mixed 25.9 grams deionized water (1.43 moles), 5.27 grams nicotinamide (0.04315 mole) and 4.835 grams of an aqueous solution of 85% lactic acid (0.0456 mole). This solution was then added dropwise over a period of 56 minutes while maintaining the reaction temperature at 80C. Then the mixture was stirred at 90C for an additional four hours. Then 182.2 grams deionized water was added to the reactor contents over a nineteen minute period while maintaining the reaction temperature at 90C. The white aqueous dispersion with .` :
38,596-F -40-.

, - - , , ., ,, ,.

. :. .; . . . :

a non-volatile content of 30 percent and charge density of 0.430 milliequivalent/gram resin was allowed to cool to ambient temperature with stirring. The pH of the stable aqueous dispersion was 4.46. The viscosity which was measured with a Ford Cup No. 4 was 15.5 seconds.
The volatile organic content of the dispersion was l. 76 pounds per gallon (211 grams/liter).

Coatings were prepared by blending 44. 681T grams of the aqueous solution prepared in Example 15, with 2.047 grams of CYMEL'~325 to give a formulation ` containing 15.3 phr CYMELT~325. The formulation was applied to 24 gauge X 4 inches X 12 inches (0.66 mm X
5 101.6 mm X 304.8 mm) unpolished clean-treated cold rolled steel panels and 7.5 mils X 4.5 inches X 9.0 inches (0.19 mm X 114.3 mm x 228.6 mm) degreased tin free steel panels (s) with a No. 16 wire wound rod according to ASTM D 4147-82. The tin free steel panels were degreased by washing the panels in methyl ethyl ketone and drying in an oven at 400F (204.4C ) . The coated panels were baked in an oven at 400F (204. 4C ) for 10 minutes. The thickness of the coating was 0.24 ~ 25 mil (O.006096 mm).
:

Coatings were prepared by blending 58.183 grams 30 of the aqueous dispersion prepared in Example 15, with ` 3.521 grams o~ CYMELTU325 to give a formulation containing 20.2 phr CYMELT~325. The formulation was applied and cured as described in Example 16. The thickness of the coating was between 0.24 and 0.26 mils (0.006096 mm and 0.00604 mm).
,.~

38, 596-F -41-"

. . .
.: . , . :. . : .

,, :
;'': -Coatings were prepared by blending 52.431 grams of the aqueous dispersion prepared in Example 15, with 3.989 grams of CYMEL~M325 to give a formulation containing 25.4 phr CYMELrM325. The ~ormulation was , applied and cured as described in Example 16. The thickness of the coating was between 0.25 and 0.26 mil (0.00635 mm and 0~006604 mm).
' 10 The advanced epoxy resin from Example 4 having an EEW of ~112 (100 grams, 0.0474 equivalents) and 21.34 ; 15 grams (0.180 moles) of 2-butoxyethanol were added to the : reactor of the type described in Example 5. The epoxy resin was slowly dissolved by heating to 125C. Then the resin was cooled to 83C. In a two ounce (59.1 mL) bottle was mixed 2 t . 42 grams (1.19 moles) deionized 20 water, 6.97 grams (0.0571 mole) nicotinamide and 4.08 grams (0.0385 mole) of an aqueous solution of 85% lactic acid. This solution was then added over a period of 14 minutes while maintaining the reaction temperature between 77C and 86C. The mixture was stirred at 88C
25 for 242 minutes. Then 280.2 grams deionized water was added to the yellowish brown reactor contents over a twenty-seven minute period while maintaining the reaction temperature between 77C and 88C. The yellow brown opaque aqueous dispersion had a non-volatile content of 25 percent and a charge density of 0.517 milliequivalents/gram resin was allowed to cool to ambient temperature with stirring. The pH of the stable :; aqueous dispersion was 4.5. The viscosity which was ;; measured with a Ford Cup No. 4 was 19 seconds. The `;' ;, 1 38,5~6-F -42-. .
;
-`

..
.
.

.

2 t~

volatile organic content of the dispersion was 1.42 pounds per gallon (170 grams/liter).

Additional 2-butoxyethanol (3.1 grams, 0.026 moles) and deionized water (16.8 grams, 0.933 moles) were added to 141.9 grams o~ the dispersion. The resulting dispersion had a non-volatile content of of 21.9 percent and a Ford Cup No. 4 viscosity of 17 seconds.

, .

, :, , ;~
~ 38,596-F -43-: ' :
: ; , 2 ~

Coatings were prepared by blending 49.92 grams of the aqueous dispersion prepared in Example 19 with 0.591 grams CYMELrM325 to give a formulation containing 5.4 parts per hundred resin (phr) CYMELrU325. The formulation was applied to 24 gauge X 4 inches X 12 inches (0.66 mm X 101.6 mm X 304.8 mm~ unpolished -. clean-treated cold rolled steel panels and 7.5 mils X
4,5 inches X 9.0 inches (0.19 mm X 114.3 mm X 228.6 mm) degreased tin free steel panels with a No. 22 wire wound rod according to ASTM D 4147-82. The tin free steel ; panels were degreased by washing the panels in methyl ethy~ ketone and drying in an oven at 400F (204.4C) for ten minutes. The coated panels were baked in an oven at 400F (204.4C) for ten minutes. The thickness of the coating was between 0.25 and 0.29 mil (0.0064 mm and 0.0074 mm).

; Coatings were prepared by blending 34.70 grams of the aqueous dispersion prepared in Example l9 with 0.775 grams CYMELT~325 to give a formulation containing 25 10.2 phr CYMEL~U325. The formulation was applied and cured as described in xample 20. The thickness of the coating was between 0.26 and 0.29 m.il (C.066 mm and ` 0.0074 mm).
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38~596-F -44-:

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Coatings were prepared by blending 53.32 grams of the aqueous dispersion prepared in Example 19 with 2.026 grams CYMEL~325, 6.15 grams water and 1.18 grams 2-butoxyethanol to give a formulation containing 15.2 phr CYMELIM325. The formulation was applied and cured as described in Example 20. The thickness of the coating was between 0.26 and 0.30 mil (0.066 mm and 0.0076 mm).

COMPARATIVE EXPERIMENT A
A bisphenol A based advanced epoxy resin prepared by reacting a diglycidyl ether of bisphenol A
having an epoxide equivalent weight of 182-192 with bisphenol A in a ratio of moles of bisphenol A per mole of diglycidyl ether of bisphenol A of 0.78:1 said advanced epoxy resin having an epoxide equivalent weight o~ 1755 (110.0 grams, 0.0627 equivalent) and 22.02 grams (0.0186 mole) of ethylene glycol n-butyl ether were added to a reactor of the type described in Example 5.
The epoxy resin was slowly dissolved by heating to 125C. Then the resin was cooled to 80C. In a two ounce bottle was mixed 28.40 grams (1.58 moles) deionized water, 5~76 grams (0.0472 mole) nicotinamide and 5.31 grams (0.0501 mole~ of an aqueous solution of 85% lactic acid. This solution was then added dropwise over a period of thirty minutes while maintaining the reaction temperature at 80C. The mixture was stirred at 90C for an additional 118 minutes. Then 229.5 grams deionized water was added to the yellow reactor contents over a seventeen minute period while maintaining the reaction temperature between 85C and 90C~ The yellow aqueous dispersion with a non-volatile content of 30 ;
, ' 38,596-F -45-. .

, .: .

percent and charge density of 0.39 milliequivalent/gram resin was allowed to cool to ambient temperature with stirring. The pH o~ the stable aqueous dispersion was 5.25. The viscosity which was measured with a Ford Cup No. 4 was 13.7 seconds. The volatile organic content o~
the dispersion was 1.36 pounds per gallon (163 grams/liter).

COMPARATIVE EXPERIMENT B
Coatings were prepared by blending 47.971 grams of the aqueous solution prepared in Comparative Experiment A, with 1.452 grams oP CYMELr~325 to give a formulation containing 10.1 parts per hundred resin (phr) CYMELTU325. The formulation was applied to 24 gauge X 4 inches X 12 inches (0.66 mm X 101.6 mm X 304.8 mm) unpolished clean-treated cold rolled steel panels and degreased tin ~ree steel panels with a No. 16 wire wound rod according to ASTM D 4147-82. The 7.5 mils X
4.5 inches X 9.0 inches (0.19 mm X 114.3 mm X 228.6 mm) tin free steel panels were degreased by washing the panels in methyl ethyl ketone and drying in an oven at 400F (204.4C). The coated panels were baked ln an oven at 400F ~204.4C) for 10 minutes. The thickness of the coating was between 0.25 and 0.28 mil (0.00635 mm and 0.007112 mm).

COMPARATIVE E~PERIMENT C
Coatings were prepared by blending 53.514 grams ,~ of the aqueous solution prepared in Comparative Experiment A, with 2.425 grams of CYMELT~325 to give a formulation containing 15.1 phr CYMELT~325. The formulation was applied and cured as described in Comparative Experiment B. The thickness of the brown ,~
38,596-F -46-:

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colored coating was between 0.23 and 0.27 mil (0.00584 mm and 0.00686 mm).

COMPAR~TIVE EXPEQIMENT D
Coatings were prepared by blending 63.075 grams o~ the aqueous dispersion prepared ln Comparative Experiment A, with 3.815 grams of CYMELr~325 to give a - formulation containing 20.2 phr CYMEL'~325. The formulation was applied and cured as described in -- 10 Comparative Experiment B. The thickness of the coatings were between 0.23 and 0.27 mil (0.00584 mm and 0.00686 ~ mm).
.~ ..
: COMPARATIYE EXPERIMENT E
, 15 Coatings were prepared by blending 47.74 grams of the aqueous dispersion prepared in Comparative - Experiment A, with 3.55 grams of CYMELT~325 to give a ` formulation containing 24.8 phr CYMEL7N325. The formulation was applied and cured as described in ,l Comparative Experiment B. The thickness of the coatings ~' were between 0.23 and 0.24 mil (0.00584 mm and 0.006096 mm).
. ~ .
EVALUATION OF COATINGS
The following tests were employed in evaluating . the coating compositions.
, METHYL ETHYL KETONE (MEK) RESISTANCE
The resistance of the cured coating on a cold rolled steel panel to removal with methyl ethyl ketone - was determined by rubbing across the baked panels a two pound ball pien hammer with the ball end covered with ` eight layers of cheesecloth which had been saturated .

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with methyl ethyl ketone (MEK). No force was applied to the hammer other than that necessary to guide the hammer back and forth over the same area. A twelve inch ruler clamped into place was used to guide the hammer in the same path. The coated panels after rubbed were dipped into a mixture of 20% CuS04oSH20 and 10% concentrated hydrochloric acid in water for 30 seconds and then dipped into deionized water to determine breakthrough.
A forward and reverse stroke returning to the starting point was considered as being one MEK double rub.

T-BEND
T-bend was used as a measure of the flexibility of the coating on the panel at a slow rate of deformation. The edges of the cold rolled steel panel were cut to leave a two inch wide specimen of uniform ` thickness. A bend was made in the panel at approximately 0.75 inches from the end of the coated ' 20 panel by using a fingerbrake. The bend was squeezed tight with the palm of the hand. Then the bent specimen ` was 3laced in a vice, which was previously taped with plastic tape to prevent scratching the substrate, and the panel was bent back on itself to form a 180 degree ; 25 bend. The stressed area was then tested for adhesion by taping with Scotch 610 tape. The tape was applied in such a manner where no air bubbles were trapped under the tape. The tape was then pulled with a rapid and ; forceful fashion at a 90 degree angle 'n an attempt to 3 pull the coating away from the substrate. Next the bend was dipped into a solution of copper sulfate (lO grams) in l.0 N hydrochloric acid for 30 seconds and then dipped into deionized water. The purpose of this step was to oxidize an~ resulting bare metal in order to more ,~ accuratel~,~ observe adhesion failures. The specimen was 38,596-F -48-, J

- examined under a magnifying glass to determine failure.
The first bend was noted as T0 (T zero) because there was no panel sandwiched between the bend. The proce~s of bending the panel by using the finger~rake and vice was continued until there was no sign of cracking or adhesion loss. Each successive bend was noted as T1, T2, T3, T4, etc. because of the number of layers of panel sandwiched between plys. The lower the number of T-bends, the better the flexibility.

IMPACT RESISTANCE
This test was used as a measure of the formability of the coating on the panel at a rapid rate of deformation.
; 15 Coated, cold rolled, steel panels were subjected to the impact of a falling weight from a Gardner Impact Tester at different calibrated heights ranging from 0 to 160 inch-pounds. The impacted area ` 20 was then tested for adhesion by taping with Scotch brand 610 tape. The tape was applied in such a manner that no air bubbles were trapped under the tape. The tape was then pulled with a rapid and forceful fashion at a 90 degree angle in an attempt to pull the coating away from the substrate. Next, a solution of copper sulfate (10 grams) in 1.0N hydrochloric acid (90 grams) was applied to the impacted area to check for failure. The specimen was examined under a table-top illuminated magnification i 30 system with lenses having a total of 11 diopter power to - determine failure.
, .
WEDGE BENDS
Wedge bend was used as a measure of the flexibility of the coating on the panel at a rapid rate .~

~ 38,596-F -49-'~

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of deformation. The coated tin free steel panels were cut to give specimens 4 inches by 2 inches. The specimens, coated side down, was placed under the 1/8 inch cylindrical mandrel of a Gardner Impact Tester. The specimen was slid to the rear of the mandrel platform ; 5 until the edge was flush with two studs located at the rear of the platform. The remainder of the panel was raised at a uniform velocity to bend the specimen 170 to 180 degree in a time not to exceed 5 seconds. The spacer located under the impact platform was slid to the extreme front of the tester and tighten in place with the adjustment screws provided. This allows the impact plat~orm to create a wedge that provides stress angles between 170 and 180 degrees. The bent specimen was placed under the impact platform. The longest segment of the specimen was placed downward. The specimen was subjected to the impact of the flat end o~ the impacter rod dropped from a calibrated height of 60 inch-pounds.
The bent area was then tested for adhesion by taping with Scotch 610 tape. The tape was pulled with a rapid and forceful fashion from the edge o~ the most extreme bending at a 90 degree angle in an attempt to pull the coating away from the substrate. The bend was dipped into a solution of copper sulfate (10 grams) in 1.0 N
hydrochloric acid and then dipped into deionized water.
The distance oE removed coating from the edge of the most severe bend outward to the edge with the least - severe bend was measured in millimeters. Four replicate specimens were tested and averaged.

WATER PASTEURIZATION RESISTANCE
Water pasteurization resistance was performed on a single specimen for each coating to determine the ; permeability of the coating to water with pressure and ~, 38,596-F _50_ .

. ~

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heat. The coating substrate was tin free steel. The width of each specimen was about 12 centimeters while the length was about 6 centimeters. A mold and the Gardner Impacter Tester were used to form a semi-circular bend in each specimen. The semi-circular bend was used to simulate a stressed area. The dart impacter rod was dropped from 56 inch-pounds (6.3 J) for all the i specimens when forming the bend. The specimens were then placed in a Model 8100-TD NORCO Autocla e with deionized water for 90 minutes at 121C (250F) and 1 bar (15 psi) pressure. The clock was only started after both the desired temperature and pressure were reached.
After the specimens were pasteurized ~or the prescribed conditions, the heat was turned off, the pressure bled off and the panels removed for testing. The coated specimens were submerged in deionized water after removal from the autoclave. The specimens were blotted dry after removal from the water with a paper towel.
They were rated for blush and adhesion. The tested coatings were rated for blush by placing the specimens ~, next to the panels from which the specimens were cut.
The coatings were rated for blush according to the following scale:

Rating Description B1 No blush B2 Dull, loss of luster B3 Total loss of luster 3 B4 Blush, cloudy, starting to loose transparency.
B5 Cloudy, expanded coating, few bubbles, a little roughness.
B6 No longer clear, rough surface, bubbles.

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; B7 Very rough or cracked surface~ many bubbles.

Adhesion was determined by using the tape test described in method A of ASTM 3359-83. The tape was ;~ 5 Scotch 610 tape. X-cuts were made in the stressed and non-stressed areas of each specimen. The adhesion of the non-stressed specimen was listed first while the adhesion in the stressed area was listed second. The j 10 coatings were listed for adhesion according to the following scale:

Descri~tion 5A No peeling or removal.
4A Trace peeling or removal along the incisions.
3A Jagged removal along most of incisions up to 1/16 inch (1.6 mm) on either side of the incision.
2A Jagged removal along most of the incisions up to 1/8 inch (3.2 mm) on either side of the incision~
1A Removal from most of the area of the X
under the tape.
OA Removal beyond the area of the X.

The following T~ble I shows the tests performed on the resultant coated panels and the result of the 3 tests.

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38,596-F -52-.~

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:' Table I
..~ . . . . , ....
BASE CYMEL rU

DISPERSION phr .. . . .
5 Ex. 6 15.0 18 T3 ;~ Ex. 7 20.1 36 T3 . _ , Ex. 8 25.4 42 T4 Ex. lO 10.2 4 T2 . .. . .. . __ Ex. 11 25.1 15 T2 ;; lO Ex. 12 io;2 30 T2 Ex. 13 20.0 40 T2 . . . . ~
Ex. 14 25.1 50 T2 Ex. 16 15.3 30 T2 Ex. 17 20.2 50 T2 -- . r - .
Ex. 18 25.4 75 T2 , Ex. 20 5,4 17 T2 ' , . , .
, Ex. 21 10.2 ~ 30 ~
Ex. 22 15.2 60 T3 C.E. B lO.l 31 T3 C.E. C 15.1 164 T6 . ..... , C.E. D 20.2 174 T4 25C.E. E 24 a >301 TlO

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-: -54-Table I (contd.) ~ ~ WEDGE
. IN - J (mm) ADHESION BLUSH

Ex. 6 88 9.9 33 5A,5Aa B1 . . . . . . . .. ~
Ex . 7 64 7.2 38 5A,5A B 1 Ex . 8 64 7.2 34 5A,5A B 1 Ex. 10 14015.8 15 5A,5A Bl . -- . .. __ __ Ex. 11 11212.6 18 5A,5A B1 Ex. 12 12814.5 15 5A,5A B1 . . . .
Ex. 13 10011.319.5 5A,5A B1 Ex. 14 92 10.4N.D.b 5A,5A B1 Ex. 16 11613- ' 17 5A,5A B1 ~ r __ Ex . 17 I 0011.3 16 SA, SA B l Ex . 18 96 10.8 23 5A,5A B 1 Ex. 20 10812.2 19 5A,5A B1 . . . .
Ex . 21 92 10.4 11 5A,5AB - T .
Ex. 22 64 7.2 21 5A,5A B4 C . E . B 88 9.9 l 9 5A,5A BL~
.. . .. .. . . ~ __ C . E . C 68 7.7 3 SA,4A B2 C . E . D 40 4.5 27 4 A, OAB 4 C . E . E 4 O ~ 4 51 OA, OA B 4 ~` a First value is unstressed part of coupon, second value is stressed part o~ coupon.
3 b N.D. refers to not determined.

38,596-F _54_ , .:

Claims (12)

1. A composition comprising the reaction product of (A) an advanced composition resulting from reacting (1) (a) at least one diepoxyalkane or a combination of (a) and (b) at least one diglycidyl ether of a dihydric phenol; with (2) at least one dihydric phenol; (B) optionally, at least one monohydric phenol;
and (C) a nucleophilic compound.

2. A composition comprising the reaction product of (A) an advanced composition resulting from reacting (1) (a) at least one diepoxyalkane or a combination of (a) and (b) at least one diglycidyl ether of a dihydric phenol; with (2) at least one dihydric phenol; (B) optionally, at least one monohydric phenol;
(C) a nucleophilic compound; and (D) a Bronsted acid.

3. A curable composition comprising (I) a composition comprising the reaction product of (A) an advanced composition resulting from reacting (1) (a) at least one diepoxyalkane or a combination of (a) and (b) at least one diglycidyl ether of a dihydric phenol; with (2) at least one dihydric phenol; (B) optionally, at least one monohydric phenol; and (C) a nucleophilic compound; and (II) a curing quantity of at least one suitable curing agent for component (I).

38,596-F -55-

4. A curable composition comprising (I) a composition comprising the reaction product of (A) an advanced composition resulting from reacting (1) (a) at least one diepoxyalkane or a combination of (a) and (b) at least one diglycidyl ether of a dihydric phenol; with (2) at least one dihydric phenol; (B) optionally, at least one monohydric phenol; (C) a nucleophilic compound; and (D) a Br?nsted acid; and (II) a curing quantity of at least one suitable curing agent for component (I).

5. Any of Claims 1, 2, 3 or 4 wherein (a) said diepoxy alkane is 1,2:7,8-diepoxyoctane, 1,2:8,9-diepoxynonane, 1,2:9,10-diepoxydecane, 1,2:13,14-diepoxytetradecane, or any combination thereof;
(b) said diglycidyl ether of a dihydric phenol, when present, is a diglycidyl ether of bisphenol A, a diglycidyl ether of bisphenol F, a diglycidyl ether of bisphenol K, bisphenol AP, or any combination thereof;
(c) said dihydric phenol is bisphenol A, bisphenol F , bisphenol K, bisphenol AP, or any combination thereof;
(d) said monohydric phenol, when present, is 4-tert-butylphenol, nonylphenol, or any combination thereof;
(e) said nucleophilic compound is nicotinamide, pyridine, 3-picoline, 4-picoline, 4,4'-trimethylenedipyridine, 1,2-bis(4-pyridyl)ethane, N,N-dimethylethanolamine, triethylamine, N,N,N',N'-tetramethyl-1,6-hexanediamine 4,4'-trimethylenebis(1-methylpiperidine) or any combination thereof;

38,596-F -56-(f) said Br?nsted acid is lactic acid, acetic acid, or a combination thereof; and (g) said curing agent is a highly methylated melamine-formaldehyde resin, hexamethoxymethylmelamine, or any combination thereof.

6. A water-borne curable composition comprising a curable composition of Claim 4 or 5 dispersed or dissolved in water.

7. A solvent-borne curable composition comprising a curable composition of Claim 3, 4 or 5 dissolved in at least one organic solvent.

8. A product resulting from curing a curable composition of Claim 3, 4 or 5.

9. A product resulting from curing a curable composition of Claim 6.

10. A product resulting from curing a curable composition of Claim 7.

11. An article coated with a curable composition of Claim 6 which has been cured subsequent to being coated onto said article.

12. An article coated with a curable composition of Claim 7 which has been cured subsequent to being coated onto said article.

38,596-F -57-