Aqueous coating agent for stoving based on aqueous dispersion of epoxide resin mixtures and epoxide curing agents, process for the manufacture thereof and the use thereof

Claim 1

A process for the manufacture of an aqueous coating agent containing an aqueous dispersion of a mixture of epoxide resin as a binder and an epoxide resin curing agent which comprises reacting a mixture containing said epoxide resin and curing agent wherein the epoxide resin binder is an epoxide resin mixture of at least one epoxide resin selected from the group consisting of (a) epoxide resins of the formula I ##STR29## wherein R 1 denotes the radical ##STR30## R 2 and R 4 denote H or CH 3 and R 3 denotes the radical ##STR31## A.sup.⊖ representing the anionic radical of a monocarboxylic acid, and R 5 and R 6 having the following meanings: ______________________________________ when R.sup.5 is: R.sup.6 is: H --CH.sub.2 CH.sub.2 OH H --CH.sub.2 CH(OH)CH.sub.3 --CH.sub.2 CH.sub.2 OH --CH.sub.2 --CH.sub.2 OH --CH.sub.2 --CH(OH)CH.sub.3 --CH.sub.2 --CH(OH)CH.sub.3 ______________________________________ and n denotes values from 1.3 to 13; and solid epoxide resins of the formula V ##STR32## wherein R 4 and R 2 denote H or CH 3 and n has a value from 1.3 to 13, the resins having epoxide equivalent weights from 300 to 2,000 and the softening points by the Durrans method being between 50 and 125° C, the mixture of epoxide resins of the formula I and V having the condition that the obtained epoxide resin mixture a' of the formula II ##STR33## wherein R 1 , R 2 , R 3 R 4 , R 5 , n and A⊖ have the meaning already mentioned and the sum of n 1 and n 3 has the value 2 and the ratio of n 1 ;n 3 has values from 20 to 0.1, preferably from 10 to 0.1, and (b) an epoxide resin mixture consisting of epoxide resins of the formula I' ##STR34## when B has the value zero, and R 1' denotes the radical --(CH 2 ) 5 -CH 3 -- and R 2' denotes the radical --(CH 2 ) 7 -CH═CH-CH 2 --, n' has the value 0 to R 3' denotes the radical ##STR35## or the radical ##STR36## and wherein the last-mentioned grouping is present in at least one radical R 3' and R 5 and R 6 have the following meanings: ______________________________________ when R.sup.5 is: R.sup.6 is: H --CH.sub.2 CH.sub.2 OH H --CH.sub.2 CH(OH)CH.sub.3 --CH.sub.2 CH.sub.2 OH --CH.sub.2 --CH.sub.2 OH --CH.sub.2 --CH(OH)CH.sub.3 --CH.sub.2 --CH(OH)CH.sub.3 ______________________________________ and A⊖ represents the anionic radical of a monocarboxylic acid, and epoxide resins of the formula V' ##STR37## wherein R 3' has the meaning ##STR38## and R 1' , R 2' , R 4' , A, B and n' have the meaning already mentioned and the resins have epoxide equivlaent weights of approximately 440 to approximately 4,000, the mixture of epoxide resins of the formula I' and V' having the condition that the obtained apoxide resin mixture b' of the formula II' ##STR39## wherein R 1 , R 2' , R 4' , R 5' , R 6' , A, B and Aθ have the meaning already mentioned, wherein R 3' denotes the radical ##STR40## or the radical ##STR41## and the last-mentioned grouping is represented by a proportion of at least 10% and at most a proportion of 95%, at 50° to 100° C, while stirring, with 0.1 to 1.0 mol, relative to 100 g of the epoxide resin mixture, of an alkanolamine or dialkanolamine having the formula VI ##STR42## wherein R 5 and R 6 have the meaning mentioned above, in the presence of at least one inert organic solvent selected from the group consisting of toluene, n-butanol and mixtures of toluene and n-butanol, and 0.01 to 1.0 mol of monocarboxylic acid, relative to 100 g, of epoxide resin mixture, having a pKa value of 2 to 5 is added to the resulting reaction product, it being necessary that the equivalent ratios of monocarboxylic acid to alkanolamine or dialkanolamine is 0.7:1 to 3:1, adding water to the resulting mixture while mixing vigorously at 20 to 70° C, and removing the organic solvent present in the mixture by azeotropic distillation thereof with water under vacuum pressure at 30° to 60° C.