Curable compounds

A curable compound carrying groups containing basic nitrogen, essentially comprising structural units derived from PA0 A) a compound which contains, on average, at least one preferably terminal 2-oxo-1,3-diololane group per molecule, with PA0 B) a secondary diamine containing hydroxyl groups in the .beta.-positions to the secondary amino groups, it also being possible for this amine to contain blocked primary amino groups, and, if appropriate, PA0 C) a difunctional amine containing at least one free primary amino group and, if appropriate, at least one secondary amino group.

DESCRIPTION 
German Auslegeschrift 2,265,195 describes an electrodepositable synthetic 
resin prepared from an epoxy resin, a polyamine derivative containing 
latent primary amino groups which are blocked by ketimine groups and 
containing at least one secondary amino group, and also, if appropriate, 
another primary or secondary amine. However, the process is not very 
suitable for incorporating polyamines into the resin as flexibilizing 
chain extenders. Accordingly, the properties of these resins are 
frequently unsatisfactory under mechanical load (impact cupping, Erichsen 
cupping), in particular in the case of electrodeposited coatings on 
electroconducting substrates. 
In addition, German Offenlegungsschrift 3,644,370 proposes binders, in 
particular for water-dilutable, cathodically depositable surface coatings, 
which are products of the reaction of compounds containing 
2-oxo-1,3-dioxolane groups and certain polyamines. Coatings obtained 
therefrom are satisfactory with respect to adhesion to the so-called 
filler, but not in all cases. 
Surprisingly, it has now been found that binders obtainable by reacting 
compounds containing 2-oxo-1,3-dioxolane groups with certain secondary 
diamines and, if appropriate, further difunctional amines containing free 
primary amino groups, and, if appropriate, chain terminators produce, in 
curable mixtures, surface-coating films which are distinguished by 
particularly good properties on mechanical load and optimized inter-layer 
adhesion, in particular to PVC or filler coatings. 
The invention therefore relates to curable compounds carrying groups 
containing basic nitrogen, essentially comprising structural units derived 
from 
A) a compound which contains, on average, at least one, preferably terminal 
2-oxo-1,3-dioxolane group per molecule, with 
B) a secondary diamine containing hydroxyl groups in the .beta.-positions 
to the secondary amino groups, it also being possible for this amine to 
contain blocked primary amino groups, and, if appropriate, 
C) a difunctional amine containing at least one free primary amino group 
and, if appropriate, at least one secondary amino group. 
The invention furthermore relates to a process for the preparation of these 
curable compounds, and to curable mixtures containing these curable 
compounds, and to the use thereof, in particular in surface-coating 
preparations. 
Compound (A) can be any materials so long as they contain on average at 
least one, preferably two or three, 2-oxo-1,3-dioxolane groups per 
molecule and do not contain any other functional groups which could 
interfere with the reaction with components (B) and, if appropriate, (C). 
The molecular weight M.sub.n (number average, determined by gel 
chromatography, PS standard) should generally be between 100 and 10,000, 
preferably between 150 and 3500, and the 2-oxo-1,3-dioxolane equivalent 
weight should be between 100 and 1250. The 2-oxo-1,3-dioxolane groups are 
preferably terminal, but, in some cases, compounds which contain these 
groups randomly distributed over the molecule chain and can be prepared by 
copolymerization using olefinically unsaturated compounds containing this 
2-oxo-1,3-dioxolane group can also be employed as component (A). A 
preparation process of this type is described, for example, in German 
Offenlegungsschrift 3,644,373. 
Component (A) preferably has the general formula (I) 
##STR1## 
in which R denotes 
a z-valent radical or a polyether, polyether polyol, polyester or polyester 
polyol, which radical may, if appropriate, also contain (NR.sup.2) groups 
where R.sup.2 represents hydrogen, alkyl having 1 to 8 carbon atoms or 
hydroxyalkyl having 1 to 8 carbon atoms, or 
a z-valent hydrocarbon radical, preferably an alkylene radical having 2 to 
18 carbon atoms which may optionally carry inert or non-interfering 
groups, or 
a z-valent poly(sec.)amine radical or 
the z-valent radical of a product of the reaction of an epoxy-carbonate 
compound with polyamines, polyols, polycaprolactone polyols, OH 
group-containing polyesters, polyethers, polyglycols, hydroxyl-, carboxyl- 
and amino-functional polymer oils having mean molecular weights from 800 
to 10,000, polycarboxylic acids, hydroxyl- or amino-functional 
polytetrahydrofurans and products of the reaction of polyamines with 
glycidyl esters of .alpha.,.alpha.-dialkylalkanemonocarboxylic acids of 
the empirical formula C.sub.12-14 H.sub.22-26 O.sub.3 or with the glycidyl 
ester of versatic acid, and 
z denotes 1 to 5. 
The index z in this formula (I) preferably represents 2 or 3, in particular 
2. 
Components (A) of this type are described, for example in German 
Offenlegungsschriften 3,624,454 and 3,644,370. to which reference is made 
here. 
The radical R in the above formula (I) may specifically have the meanings 
(Ia) to (Id) below: 
##STR2## 
in which X is hydrogen or methyl, u is 0 to 5 and v is 1 to 20, preferably 
1 to 6. The values of u and v should be regarded as a statistical mean 
since the molecular weight distribution of the glycidyl ethers can cover a 
wide range; 
##STR3## 
in which X and u have the meaning mentioned and R.sup.1 represents 
O-alkyl-O or N-alkyl-N, each having 2 to 18 carbon atoms in the alkyl 
radical, or represents the radical of polyamines, polyols, 
polycarprolactone polyols, OH group-containing polyesters, polyethers, 
hydroxyl-, carboxyl- and amino-functional polymer oils, polycarboxylic 
acids, hydroxyl- or amino-functional polytetrahydrofurans and products of 
the reaction of polyamines with glycidyl ethers or glycidyl esters of 
carboxylic acids which are branched in the .alpha.-position and have 8 to 
14 carbon atoms (so-called .RTM.Versatic acids), 
##STR4## 
in which X and u have the meaning mentioned and R.sup.2 represents 
alkylene having 2 to 18 carbon atoms or the radical of a poly(sec.)amine 
or an amino-functional polytetrahydrofuran; 
##STR5## 
in which X and u again have the meaning mentioned, but u is preferably 1, 
and R.sup.3 represents the 
##STR6## 
in which R.sup.4 is identical to R.sup.1, with the exception of the 
polycarboxylic acids and the carboxyl-functional polymer oils, and PI 
represents the radical of a polyisocyanate. 
The compounds of the formula (I), like the compounds (II) and (VII) 
described below, can be prepared by adduction of CO.sub.2 to the 
corresponding epoxide group-containing compounds. Processes of this type 
are described, for example, in PCT(WO) Patent Application 84/03 701 and in 
German Offenlegungsschriften 3,529,263 and 3,600,602. Reference is made 
here to their disclosure, including the preferred embodiments. Suitable 
initial polyepoxides are listed, for example, in Wagner/Sarx, 
"Lackkunstharze 121 [Synthetic surface-coating resins]", Carl Hansa Verlag 
(1971), pp. 174 ff, and in European Offenlegungsschrift 60,506, to which 
reference is likewise made here. 
Preferred starting materials for the preparation of the cyclic carbonates 
(I) and the mixed epoxide/carbonate compounds (II) are the polyglycidyl 
ethers of polyphenols, for example bisphenol A. The glycidyl ethers are 
obtained for example, by reacting a polyphenol with epichlorohydrin. 
Polyphenols are, for example, bis(4-hydroxyphenyl)-2,2-propane, 
bis(4-hydroxyphenyl)methane, 4,4'-dihydroxybenzophenone, 
bis(4-hydroxyphenyl) 1,1'-ether, bis(4-hydroxyphenyl)-1,1'-isobutane, 
bis(2-hydroxynaphthyl)methane and 1,5-dihydroxynaphthalene. They 
preferably contain free hydroxyl groups in addition to the epoxide groups 
in the polyglycidyl ether of the polyphenol. 
In some cases, it may be expedient to employ flexibilized compounds as 
component (A). In this case, the starting point for the preparation of 
component (A) is, for example, mixed epoxide/carbonates, such as those of 
the general formula (II) 
##STR7## 
in which R' corresponds to the meaning of R in the formula (I). These 
mixed epoxide/carbonates are reacted with compounds which exert a 
flexibilizing action on the molecule, for example the polyamines mentioned 
as component (C), aliphatic or aromatic polyols, such as diols, triols or 
tetraols, for example ethylene glycol, propylene glycol, polyalkylene 
glycols, neopentyl glycol, glycerol, trimethylolpropane, pentaerythritol 
and polycaprolactone polyols, furthermore OH group-containing polyesters, 
polyethers, polyglycols, hydroxyl-, carboxyl- and amino-functional polymer 
oils, polycarboxylic acids, hydroxyl- and amino-functional 
polytetrahydrofurans, products of the reaction of polyamines with glycidyl 
ethers or glycidyl esters of versatic acid, or polyether polyesters which 
contain terminal carboxyl groups. The reactions with these flexibilizing 
compounds are carried out under conditions under which the epoxide groups 
react very preferentially. In this way, compounds of the formula (I) which 
carry terminal cyclic carbonate groups which can be reacted with the amino 
compounds are again obtained. 
The amines employed according to the invention as component (B) for 
constructing the curable compounds contain two secondary amino groups, for 
which at least one hydroxyl group is present in each case in the 
.beta.-position. These amines preferably also contain at least one primary 
amino group, preferably one to three primary amino groups, which are all 
preferably blocked by ketones as ketimine groups. These primary amino 
groups may alternatively be reacted with monocarbonates. These amines may, 
if desired, also contain further groups so long as these do not react with 
the 2-oxo-1,3-dioxolane groups under the conditions present and do not 
interfere with construction of the resin, such as, for example, tertiary 
amino groups. 
The carbon number of these amines (B) is generally 4 to 40, preferably 10 
to 20. Amines which are suitable as component (B) are described, for 
example, in German Offenlegungsschrift 3,644,371, to which reference is 
made here. They can be prepared, for example, by reacting 
1,2,3-trisubstituted propane compounds, such as epichlorohydrin, with 
primary diamines or with monoamines and primary diamines. A further way of 
preparing secondary diamines according to (B) is to react primary 
monoamines with diepoxides, the primary monoamine being employed in 
excess, usually in the molar ratio 2:1. Examples of such amines are 
1,3-bis(methyl-5-aminopentylamino)-2-propanol, 
trimethylhexyl-1,3-bis(6-aminohexyl)amino-2-propanol, 
1,3-bis(methyl-6-aminohexyl)-amino-2-propanol, and furthermore 
corresponding products of the reaction of ethanolamine, butylamine, 
2-ethylhexylamine or appropriate mixtures with .RTM.Epikote 828 or 
.RTM.Epikote 1001 (molar ratio 2:1). 
If the amines employed as component (B) contain primary amino groups, it is 
necessary that these are blocked, which can be effected in the customary 
manner by reaction with suitable ketones with removal of the water formed 
(for example by azeotropic distillation) and of any excess ketone. 
Suitable ketones are primarily those which, apart from the keto group, 
contain no further groups which are reactive towards a primary amino 
group. Examples of these are methyl ethyl ketone, methyl propyl ketone, 
methyl isopropyl ketone, methyl isobutyl ketone, methyl isoamyl ketone, 
diethyl ketone, dipropyl ketone and cyclohexanone. Preferred ketones are 
methyl isobutyl ketone and diethyl ketone. 
Preferred amines (B) for constructing the curable compounds according to 
the invention have, for example, the formulae (III) to (V) below 
##STR8## 
in which: R.sup.5, R.sup.6, R.sup.7 and R.sup.8 denote identical or 
different (C.sub.1 -C.sub.6)alkyl (branched or unbranched), or R.sup.5 and 
R.sup.6 or R.sup.7 and R.sup.8 denote part of a cycloaliphatic ring, or in 
each case one of the radicals R.sup.6 and/or R.sup.8 denotes aryl having 6 
to 12 carbon atoms; 
R.sup.9 denotes 
EQU --(CR.sup.10 R.sup.11 --.sub.n Z.sup.1 --CR.sup.12 R.sup.13 --.sub.m 
Z.sup.2 --CR.sup.14 R.sup.15).sub.1 ].sub.k 
where 
Z.sup.1 and Z.sup.2 denote O, S, N-alkyl having up to 8 carbon atoms, 
N-phenyl, N-mono-, -di- or -trialkylphenyl having 1 to 4 carbon atoms per 
alkyl group, a divalent phenylene radical which is optionally substituted 
by inert or non-interfering groups, and/or a chemical bond, 
R.sup.10 to R.sup.15 denote H, CH.sub.3, C.sub.2 H.sub.5, phenyl or mono-, 
di- or trialkylphenyl having 1 to 4 carbon atoms per alkyl group, 
n, m and l denote 0 to 12, preferably 0 to 6, where the sum of 
n+m+l.gtoreq.2, preferably.gtoreq.4 and 
k denotes 1 to 6, preferably 1 to 3, and 
n denotes 1; 
##STR9## 
in which R.sup.5, R.sup.6 and R.sup.9 have the same meaning as in the 
formula (III), 
A denotes a branched or unbranched (C.sub.1 -C.sub.6)alkyl 
B denotes hydrogen, and 
n denotes 1 to 5; 
##STR10## 
in which R.sup.5, R.sup.6 and R.sup.9 have the same meaning as in the 
formula (III), 
C denotes branched or unbranched (C.sub.1 -C.sub.8)alkyl or (C.sub.5 
-C.sub.9)cycloalkyl, optionally substituted by (C.sub.1 -C.sub.3)alkyl 
groups, and 
D denotes hydrogen. 
It is also possible to employ mixtures of various amines as component (B). 
As component (C) which can optionally also be employed, it is possible to 
use bifunctional amines containing at least one free primary amino group 
and optionally containing at least one secondary amino group. 
For example, such polyamines may be diprimary and contain no further basic 
groups. Alternatively, they may additionally contain tertiary amino groups 
or secondary amino groups; however, the reaction conditions here must be 
chosen so that the latter do not react with the 2-oxo-1,3-dioxolane 
groups, since otherwise gelling occurs. Suitable polyamines are described, 
for example, in German Offenlegungsschrift 3,624,454, to which reference 
is made here. 
Further suitable amines here are those which contain a primary amino group 
and a secondary amino group activated by a .beta.-hydroxyl group. 
Examples of amines appropriate for (C) are those of the formula (VI) below 
##STR11## 
in which R.sup.16 denotes a divalent hydrocarbon radical, preferably a 
straight-chain or branched alkylene radical having 2 to 18 carbon atoms 
which may optionally carry inert or non-interfering groups, 
R.sup.17 and R.sup.18 are identical or different and denote hydrogen, alkyl 
having 1 to 8 carbon atoms or hydroxyalkyl having 1 to 8 carbon atoms in 
the alkyl radical, it also being possible for R.sup.17 and R.sup.18 to 
produce a cyclic ring compound, and 
F denotes a chemical bond or --(R.sup.16 --NH).sub.r --R.sup.16 --NH-- in 
which r denotes zero or an integer from 1 to 6 and R.sup.16 has the above 
meaning. 
Specific representatives of these amines which may be mentioned are the 
following: ethylenediamine, propylenediamine, 
2-methylpentamethylenediamine, hexamethylenediamine, octamethylenediamine, 
triacetonediamine, dioxadecanediamine, dioxadodecanediamine and higher 
homologs, cycloaliphatic diamines, such as 1,4-cyclohexanediamine; 
4,4'-methylene-bis-cyclohexylamine, 4,4'-isopropylene-biscyclohexylamine, 
isophoronediamine, m-xylylenediamine, N-methylethylenediamine, 
hydroxyethylaminoethylamine, hydroxyethylaminopropylamine, 
N-aminoethylpiperazine, N,N-diethylethylenediamine, 
N,N-diethylpropylenediamine, N,N-dihydroxyethylethylenediamine, 
diethylenetriamine, dipropylenetriamine, bishexamethylenetriamine, 
triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, 
heptaethyleneoctamine and the like; furthermore products of the reaction 
of diamines, such as, for example, ethylenediamine, propylenediamine, 
hexamethylenediamine, trimethylhexamethylenediamine and m-xylylenediamine, 
with terminal epoxides, such as, for example, propylene oxide or hexene 
oxide, or with glycidyl ethers, such as phenyl glycidyl ether, ethylhexyl 
glycidyl ether or butyl glycidyl ether, or with glycidyl esters, such as 
"Cardura E10", or with unsaturated compounds, such as acrylonitrile or 
methacrylonitrile. In this case, the reaction must take place in a manner 
such that only one of the two primary amino groups present is alkylated, 
i.e. reacted with the epoxides or unsaturated compounds mentioned. To this 
end, the appropriate polyamino compound is employed in excess. Of course, 
it is also possible to use mixtures of the amines. 
As component (C), it is also possible to use amines containing additional 
amide groups, as are obtained, for example, by condensation of primary 
diamines with dicarboxylic acids, such as adipic acid, sebacic acid, or 
dimeric fatty acid. It is also possible to use other amine adducts for 
this purpose, for example imides. 
Other polyamines which can be employed as component (C) are, for example, 
also those corresponding to the above formula (III), but where the two 
terminal primary amino groups are not blocked. In this case, these 
polyamines are not used until the second step of the resin construction 
(first step: reaction of (A) and (B); in this respect, see below), where, 
through choice of suitable reaction conditions, only the primary amino 
groups, which are more reactive towards the 2-oxo-1,3-dioxolane groups, 
are reacted with the latter. 
The mixing ratios of components (A), (B) and, where appropriate, (C) can 
vary within broad limits. In general, the amount of component (A) is 25 to 
70 mol-%, preferably 30 to 60 mol-%, that of component (B) is 8 to 60 
mol-%, preferably 10 to 15 mol-%, and that of component (C) is 0 to 60 
mol-%, preferably 20 to 50. These components are preferably employed in 
amounts such that the ratio between the 2-oxo-1,3-dioxolane equivalents 
and the reactive amine equivalents of components (B)/(C) is between 0.8 
and 1.2 mol-%, preferably 1.0 and 1.1 mol-%.

In order to limit the molecular weight of the curable compounds according 
to the invention, so-called chain terminators (D) are used in a preferred 
embodiment of the invention. In the case of terminal amino groups, i.e. 
when an excess of amine equivalents from (B)/(C) compared with the 
2-oxo-1,3-dioxolane equivalents is present, these are, for example, 
monocarbonates, monoepoxide compounds and partly blocked polyisocyanates, 
it being possible to carry out the reactions simultaneously or in several 
separate steps. 
Suitable monocarbonate compounds for this purpose are those of the formula 
(VII) 
##STR12## 
in which R.sup.19 denotes hydrogen, alkyl having 1 to 18, preferably 1 to 
10, carbon atoms, or radicals of the glycidyl ester of versatic acid, 
glycidyl esters or glycidyl ethers in which the epoxide group has been 
converted in the abovementioned fashion into cyclic carbonates. 
Besides the monocarbonates and monoepoxides, it is also possible to employ 
partially blocked polyisocyanates since these compounds react first with a 
free NH.sub.2 group. In principle, any amine reaction can be employed 
which preferentially commences at the primary amino group before the 
secondary amino groups present in the molecule react. The compounds 
employed for chain termination can additionally serve for flexibilization 
of the resultant surface coating material if appropriate long-chain 
compounds, which are known in practice, are incorporated. 
In the case of terminal 2-oxo-1,3-dioxolane groups, amines which are 
monofunctional under the reaction conditions can be employed as chain 
terminators. Suitable as such are, for example, primary monoamines or 
secondary monoamines, such as methylamine, ethylamine, propylamine, 
butylamine, octylamine, laurylamine, stearylamine, ethanolamine, 
isononyloxypropylamine, N-methylaminopropylamine, 
diethyl(methyl)aminopropylamine, aminoethylethanolamine, neopentanolamine, 
dimethylaminopentanolamine, 3-aminopropanol, amidamines made from primary 
diamines and monocarboxylic acids, monoketimes of primary diamines and the 
like. 
In addition, amines of the above formula (IV) (but in this case the radical 
B=alkyl or (HO).sub.n A) or of the formula (V) (but D is identical to C) 
are suitable for this purpose. 
In addition, it is also possible to employ amines of the formula (VIII) 
below for this purpose 
##STR13## 
in which R.sup.5, R.sup.6 and R.sup.9 have the same meaning as in the 
formula (III), and 
E denotes (C.sub.2 -C.sub.8)alkoxy, linear or branched, or (C.sub.5 
-C.sub.15)acyloxy, preferably branched having C.sub.4 -C.sub.15. 
Finally, all amines according to (B) and (C) are, in principle, suitable as 
chain terminators, so long as they have been rendered monofunctional by 
means of blocking agents, such as monoepoxides and, in some cases, also 
monocarbonates, and partially blocked polyisocyanates, or by ketimine 
formation. 
The amount of chain terminator (D) is generally 10 to 70 mol-%, preferably 
20 to 40 mol-%, relative to the total molar mass of (A) to (D). 
The molecular weight M.sub.n (number average; determined by means of gel 
chromatography, polystyrene standard) of the curable compounds according 
to the invention, is generally between 500 and 2000, preferably between 
1000 and 10,000. The Staudinger index [.eta.] usually has values from 0.5 
to 2.0 [dl/g], determined in methoxypropanol. The amine numbers are 
usually between 10 and 300 mg of KOH/g, preferably between 20 and 100 mg 
of KOH/g. If the curable compounds are to have self-curing properties, 
some of the hydroxyl and/or primary or secondary amino groups present are 
reacted with a partially blocked polyisocyanate which still contains an 
average of about one free isocyanate group in the molecule. Another 
possibility is, for example, to introduce .beta.-hydroxyalkylcarbamate 
groups by reacting some of the amino groups with a cyclic carbonate, such 
as ethylene carbonate. This method is described, for example, in German 
Offenlegungsschrift 3,246,812 and European Offenlegungsschrift 119,769. 
In order to prepare the curable compounds according to the invention, 
components (A), (B) and preferably (D), and, if appropriate, additionally 
(C) are reacted in the stoichiometric ratios or amounts necessary at 
elevated temperatures and preferably in the presence of catalysts and 
inert solvents. The reaction is generally carried out until, for example, 
a constant amine number or the theorectical amine number is reached. 
Elevated temperature here is taken to mean the range from about 50.degree. 
to 140.degree. C., preferably 70.degree. to 120.degree. C. 
Whereas it is generally not necessary to use a catalyst for the reaction of 
the primary amino groups of component (C) with the 2-oxo-1,3-dioxolane 
groups of component (A), catalysis is expedient for the reaction of the 
less reactive secondary amino groups of component (B). Suitable catalysts 
for this purpose are strongly basic compounds, such as quaternary ammonium 
compounds, for example alkyl-, aryl- and/or benzylammonium hydroxides and 
carbonates. Specific representatives of quaternary ammonium compounds in 
this case are alkylbenzyldimethylammonium hydroxide (alkyl=C.sub.16 
-C.sub.22), benzyltrimethylammonium hydroxide and tetrabutylammonium 
hydroxide. 
Preferred catalysts are strongly basic amines, for example 
diazabicyclooctane (DABCO), guanidine, etc. . 
So-called supranucleophilic catalysts, for example 4-pyrrolidinopyridine 
and poly-(N,N-dialkylaminopyridine), are also suitable here; in this 
respect, cf. the article by R. A. Vaidya et al. in Polymer Preprints, Vol. 
2 (1986), pp. 101-102. 
Inert solvents for the above reaction which may be mentioned here are, for 
example: halogenated hydrocarbons (less suitable when used as dip 
coatings), ethers, such as diethyl ether, 1,2-dimethoxyethane, 
tetrahydrofuran or dioxane; ketones (if a component (C) is used), such as, 
for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, 
cyclohexanone and the like; alcohols, such as methanol, ethanol, 
2-butoxyethanol, propanol, isopropanol, 2-methoxy-1-propanol, butanol and 
benzyl alcohol; esters (less suitable when used as dip coatings), such as 
butyl acetate, ethyl glycol acetate and methoxypropyl acetate; 
(cyclo)aliphatic and/or aromatic hydrocarbons, such as hexane, heptane, 
cyclohexane, benzene, toluene and the various xylenes, and aromatic 
solvents in the boiling range from 150.degree. to 180.degree. C. 
(higher-boiling mineral fractions such as .sup.(R) Solvesso). The solvents 
can be employed here individually or as mixtures. 
On stoichiometric assessment of the starting materials and also of the 
reaction products with respect to the progress of the reaction, the amine 
number, which can be determined in a customary manner by titration with 
perchloric acid, is taken as the basis for components (B)/(C), and the 
cyclocarbonate equivalent number, which can be determined in a customary 
manner by titrating with potassium hydroxide solution, is taken as the 
basis for components (A)/(D). 
Various routes can be followed in the preparation of the curable compounds 
according to the invention. Thus, the polyamino compounds (B)/(C) 
according to the invention can be introduced into the reaction 
individually or as mixtures or at successive points in time, optionally 
dissolved in non-interfering, organic solvents. In an analogous manner, 
individual or different modified cyclic carbonates of component (A) can be 
introduced into the reaction individually or as mixtures or at successive 
points in time, preferably mixed with organic solvents which are inert to 
cyclocarbonate groups. Furthermore, it is possible, for example, to 
initially react component (A) with component (B) in the presence of 
suitable catalysts and then to further react, in a second step, the 
reaction product thus obtained with component (C)--if appropriate with 
addition of more of component (A), and if appropriate with addition of 
chain terminators (D)-without catalysis to form the final product. 
Alternatively, the reaction of components (A) to (D) can also be carried 
out in a one-step reaction, where it should be ensured, by choice of 
reaction components (B)/(C) and/or the reaction conditions, that 
components (B)/(C) are only able to react bifunctionally. 
If it is desired to obtain a self-curing product, component (A) can, for 
example, initially be reacted with the partially blocked isocyanate and 
the resin construction can then take place by reaction with component (B) 
and, where appropriate (C) and (D). Component (A) can be employed for this 
purpose in unflexibilized or flexibilized form. The reaction of the 
hydroxyl and/or secondary amino groups present in component (A) with the 
partially blocked isocyanate is carried out here under conditions such 
that the cyclic carbonate groups are not attacked. On the other hand, it 
is also possible to initially construct the curable compound in its 
entirety and then to subsequently introduce the blocked isocyanate groups 
into the final product. 
Polyisocyanates employed, after appropriate partial blocking, for the 
preparation of self-curing compounds may be any desired polyisocyanates 
known from the area of polyurethanes or surface coatings, for example 
aliphatic, cycloaliphatic or aromatic polyisocyanates. Some of the 
isocyanate groups may have been reacted in a known manner, with customary 
blocking agents. Typical examples of the polyisocyanates used are xylylene 
diisocyanates, diphenylmethane 4,4'-diisocyanates, triphenylmethyl 
4,4'-triisocyanate, triphenylmethane triisocyanate, polyphenylpolymethyl 
isocyanate, 2,2,4(2,4,4)-methycyclohexyl diisocyanate, dicyclohexylmethyl 
diisocyanate, diethylfumarohexyl isocyanate, 
bis(3-methyl-4-isocyanatocyclohexyl)methane, 
2,2-bis(4-isocyanatocyclohexyl)propane, the methyl ester of lysine 
diisocyanate, the biuret of hexamethylene diisocyanate, diisocyanates of 
dimeric acids, 1-methylbenzene 2,4,5-triisocyanate, biphenyl 
2,4,4'-triisocyanate, the triisocyanate made from 3 moles of hexamethylene 
diisocyanate and 1 mole of water and having an NCO content of 16%, and 
further compounds containing at least two NCO groups per molecule, 
preferably isophorone diisocyanate, hexamethylene diisocyanate and tri- 
and tetramethylhexamethylene diisocyanate, but in particular 2,4- or 
2,6-toluylene diisocyanate, or mixtures of these compounds. The 
polyisocyanates on which the PI radical is based in the compounds may be 
identical or different. 
Besides these simple polyisocyanates, those are also suitable which contain 
heteroatoms in the radical linking the isocyanate groups. Examples of 
these are polyisocyanates containing carbodiimide groups, allophonate 
groups, isocyanurate groups, urethane groups, acylated urea groups or 
biuret groups. 
Finally, suitable polyisocyanates are also the known prepolymers containing 
terminal isocyanate groups, as are accessible, in particular, by reacting 
the abovementioned simple polyisocyanates, above all diisocyantes, with 
excess amounts of organic compounds containing at least two groups which 
are reactive to isocyanate groups. However, these prepolymers are 
preferably employed as external curing components in co-reacting systems. 
Suitable blocking agents are aliphatic, cycloaliphatic or alkylaromatic 
(monohydric) alcohols, for example lower aliphatic alcohols such as methyl 
alcohol, ethyl alcohol, various propyl, butyl and hexyl alcohols, heptyl 
alcohol, octyl alcohol, nonyl alcohol, propargyl alcohol, decyl alcohol 
and the like; furthermore unsaturated alcohols such as allyl alcohols, 
cycloaliphatic alcohols such as cyclopentanol and cyclohexanol, 
alkylaromatic alcohols such as benzyl alcohol, methylbenzyl alcohol and 
p-methoxy- and p-nitrobenzyl alcohol, and monoethers of glycols, such as 
ethylene glycol monoethyl ether, monobutyl ether and the like. Further 
blocking agents are ketoximes, expediently having 3 to 20 carbon atoms, 
preferably 3 to 10 carbon atoms, such as acetone oxime, methyl ethyl 
ketone oxime (=butanone oxime), hexanone oxime (such as methyl butyl 
ketone oxime), heptanone oxime (such as methyl-n-amyl ketone oxime), 
octanone oxime and cyclohexanone oxime, CH-acidic compounds such as alkyl 
malonates, esters of acetoacetic acid and esters of cyanoacetic acid, in 
each case having 1 to 4 carbon atoms in the ester group, NH-acidic 
compounds, such as caprolactam, and amino alcohols, such as 
diethylethanolamine. Phenol, which is known as a blocking agent, can be 
employed in cases where the reaction product is used for the production of 
solvent-containing surface coating materials. 
On the other hand, it is also possible, for example, to add a customary 
curing agent, as used for co-reacting 2-component surface coating 
materials, to the aminourethanes according to the invention. The 
following, for example, are suitable for this purpose: blocked 
polyisocyanates, such as described above for the self-curing 
aminourethanes, furthermore .beta.-hydroxy esters of at least bifunctional 
polycarboxylic acids, products of the reaction of dialkyl malonates with 
aldehydes and ketones which react, with elimination of water, to form 
unsaturated dicarboxylates (Knoevenagel synthesis), transesterification or 
transamidation curing agents, Michael addition products, for example as 
described in German Offenlegungsschriften 3,315,469, 3,417,441 and 
3,602,981. Reference is hereby made to these literature references, 
including the preferred embodiments. In addition, amino resins (urea, 
melamine) and phenolic resins and .beta.-hydroxyalkyl carbamate 
crosslinking agents should also be mentioned here. 
Suitable curing components for the aminourethanes according to the 
invention, preferably in non-aqueous surface coating materials, are also 
epoxide group-containing compounds, such as, for example, 
low-molecular-weight polyepoxides, epoxide group-containing copolymers and 
di- or polyglycidyl ethers of aliphatic or aromatic alcohols. In addition, 
curing components which should be mentioned here are also oligomeric or 
polymeric compounds which contain at least two 1,3-dioxolan-2-one groups 
or at least one 1,3-dioxolan-2-one group and one epoxide group per 
molecule; these incude, for example, the compounds (I) and (II). 
The amount of these crosslinking agents depends on the type and number of 
the mutually reactive groups in the binder and crosslinking agent and on 
the crosslinking density desired. The weight ratio between the binder and 
crosslinking agent is usually between 1:10 and 10:1, preferably between 
1:5 to 5:1 and very preferably 1:1. 
It is also possible to incorporate into the system the flexibilization 
which is necessary for some applications, if appropriate in addition to 
the flexibilization caused by components (A) and/or (B)/(C), via the 
admixed curing agent or via the incorporated curing agent 
(=self-crosslinking systems). 
The curable compounds according to the invention are preferably employed as 
binders in solvent-based or, preferably, water-based surface-coating 
preparations which produce coatings having very good properties. Such 
coatings can be produced by customary methods, such as brushing, spraying, 
dipping, pouring, knife-coating or preferably by cathodic deposition on a 
very wide variety of substrates, such as wood, plastic or, preferably, 
metal. 
In order to obtain aqueous systems, which are preferably used as 
electrocoating materials, it is advantageous to neutralize all or some of 
the basic amino groups in order to obtain coating compositions which can 
be electrodeposited from aqueous solution at a bath pH between about 3 and 
9. 
The basic groups are generally neutralized using water-soluble acids, for 
example formic acid, acetic acid, lactic acid or phosphoric acid, or 
appropriate mixtures. In the individual cases, the amount of acid depends 
on the properties of the resin used and is generally only carried out 
until the resin is solubilized or converted into a stable, aqueous 
emulsion (or dispersion). In general, degrees of neutralization (DN) from 
20 to 70% are necessary for this. The meq values (mmol of acid/100 g of 
solid) given in the examples are related to the former by the following 
equation: 
##EQU1## 
The solids contents of the electrocoating materials are generally 10 to 
30% by weight. 
Aqueous preparations which have a particularly low content of volatile 
organic solvents, for example 0.5 to 5% by weight, relative to the total 
solids content (determined at 125.degree. C./60 min), are obtained--as 
described, for example, in German Offenlegungsschrift 3,602,980--by 
distilling off the solvents present in the binders due to the preparation 
or solution. This process step is preferably carried out on the partially 
neutralized resin under reduced pressure. 
The ketimine structures obtained during construction of the resin--if the 
amine components employed contained ketimine groups--deblock by acidic 
hydrolysis to form the corresponding primary amino groups after or (on) 
conversion of the "neutralized" resin into an aqueous emulsion with 
elimination of the blocking ketone. Surface-coating baths (clear or 
pigmented) produced in this way should be stirred for a sufficient period 
of time (generally a few hours to several days) until the deblocking is 
complete and the bath data (pH, conductivity) have stabilized; only then 
should testing take place. Any residual content of ketimine which may be 
present no longer has an interfering effect here since the binders 
generally have sufficient basicity for adequate neutralization and 
ketimine structures are to a certain extent also capable of curing with 
blocked polyisocyanates. 
The surface coating preparations containing the binders according to the 
invention may additionally--depending on the purpose of use--contain 
customary surface-coating additives. As such, the following may be 
mentioned here: pigments (iron oxides, lead oxides, lead silicates, 
titanium dioxide, barium sulfate, zinc oxide, zinc sulfide, phthalocyanine 
complexes etc.), pigment pastes, antioxidants, (UV) stabilizers, 
flow-control agents, thickeners, antifoaming agents and/or wetting agents, 
reactive thinners, fillers (talc, mica, kaolin, chalk, quartz powder, 
asbestos powder, slate powder, various silicas, silicates, etc.), 
additional curing agents and additional curable compounds, catalysts and 
the like. These additives cannot be added to the mixture, where 
appropriate, until just before processing. 
Suitable catalysts for accelerating the curing are, for example, salts or 
complexes of metals, such as, for example, lead, zinc, iron, tin, 
manganese and bismuth. Preferred metal catalysts here are lead compounds, 
such as lead carboxylates having 1 to 10 carbon atoms, for example lead 
formate, lead acetate, lead propionate, lead lactate, lead octoate, lead 
acetylacetonate, etc., or tin compounds. For the tin catalysis, dibutyltin 
dilaurate and dibutyltin oxide or tin(IV) compounds of the formula (IX) 
EQU [((R.sup.20).sub.1 Sn).sub.m (X).sub.n ].sub.p (IX) 
in which 
R.sup.20 denotes an alkyl radical having 1 to 10 carbon atoms, preferably 2 
to 4 or 8 carbon atoms, 
X denotes a monovalent or divalent carboxyl radical having 1 to 12, 
preferably 1 to 8 or 12, carbon atoms, or a monovalent or divalent alcohol 
or (poly)amine radical having 1 to 10 carbon atoms, or a mononuclear or 
polynuclear phenolic radical (substituted or unsubstituted), for example 
p-tertbutylphenol, p-nonylphenol, etc., or radicals of monovalent or 
divalent thiols, or denotes 0; 
l=2 or 3; 
m=1 or 2; 
n=1 or 2; and 
p.gtoreq.1, 
are preferably suitable. 
Examples of representatives of this formula are tin(IV) compounds which 
hydrolyze relatively quickly in water, such as dialkyl(butyl)tin 
diacetate. 
The catalysts are usually employed in amounts from 0.1 to 6% by weight, 
preferably 0.2 to 3% by weight (calculated on the metal), relative to the 
curable compound (solid). 
When dibutyltin dilaurate is used as the curing catalyst, it is expediently 
initially homogenized with the binder, and this homogeneous mixture is 
then subsequently added to the surface-coating preparation. 
In the case of dibutyltin oxide, this is preferably initially mixed with 
the pigment and, if appropriate, an admixing resin and then passed to 
grinding. A pigment: binder ratio (PBR) of about 0.2:1 to 1:1 is desired, 
it being possible for the pigmentation to take place in, in principle, two 
ways: 
1) the pigments are added to the neutralized binder, and the mixture is 
ground by means of a bead mill or another suitable grinding machine; 
2) the neutralized binder(s) (dispersion) is pigmented by means of a 
highly-pigmented (PBR=6:1 to 20:1) pigment paste. 
The pigment paste generally contains a paste resin, pigments, fillers, 
other auxiliaries which are customary in surface coatings and, if 
appropriate, the abovementioned catalysts. 
In all cases, grinding of the binder/pigment mixture or of the pigment 
paste should be carried out to adequately small grain sizes (for example 
Hegman 7), preferably in the presence of Al.sub.2 O.sub.3 (corundum) beads 
or ceramic or ZrO.sub.2 beads (diameter 0.5-3 mm). 
In the case of tin compounds of the above formula (IX), such as the 
relatively readily hydrolyzable dibutyltin diacetate, it is expedient to 
initially incorporate this into the pigment paste containing water and 
also, if appropriate, an admixing resin and to carry out appropriate 
comminution (for example Hegmann 7) at the same time. This pigment paste 
is then added to the binder-containing surface-coating material. 
Alternatively, these tin compounds can be metered, if appropriate in 
portions, directly into the surface-coating material already containing 
pigment, with vigorous mechanical mixing, such as, for example, in a bead 
mill using corundum (ceramic) beads. In a modification, only a (small) 
part of the total amount of water is initially present in the 
surface-coating material, while the other (larger) part is not added to 
the surface-coating material until after this tin compound has been 
metered in. In this case, it is also possible to add the tin compound 
mixed with an admixing resin and/or with part of the pigment. 
This above-described way of metering in the tin curing catalyst is also 
suitable for surface-coating preparations which contain binders other than 
the curable compounds according to the invention. 
The electrodeposition of the surface-coating particles takes place by known 
methods, to which reference is made here. The deposition can take place on 
any electroconducting substrates, for example metal, such as steel, 
copper, aluminum and the like. 
After deposition, the coating is cured at elevated temperatures, which are 
generally dependent on the nature of the curing component, temperatures 
from 100.degree. to 220.degree. C., preferably 130.degree. to 180.degree. 
C., being used. The use of customary lead catalysts in the curing of the 
surface-coating resins according to the invention is particularly 
effective only when these surface-coating resins contain polyisocyanate 
radicals which are blocked, for example, by .beta.-alkoxy- or 
.beta.-dialkylamino alcohols and/or by ketone oximes, and can result in 
shorter curing times or lower baking temperatures. 
In the examples below, P denotes parts by weight and % denotes percentages 
by weight. The amine numbers always relate to solid resin. 
EXAMPLES 
I. Preparation of the precursors 
I.1. Preparation of 1,3-bis(methyl-5-aminopentylamino)-2-propanol 
(.fwdarw.component (B)) 
463 g (5 mol) of epichlorohydrin were added dropwise at 27.degree. to 
42.degree. C. under nitrogen to a well-stirred mixture of 2325 g (20 mol) 
of 2-methylpentamethylenediamine .RTM.Dytek A from Du Pont) in 1.6 liters 
of toluene and sodium hydroxide solution prepared from 205 g (5.1 mol) of 
sodium hydroxide in 210 ml of demineralized water, in a 6 liter 
four-necked flask equipped with dropping funnel, stirrer, thermocouple, 
reflux condenser with Dean-Stark water separator. After the first 50 to 60 
ml (in about 5 minutes), about 10 minutes were waited until a reaction 
(somewhat exothermic, salt-forming) was detected. About 2 hours were 
required for the further addition with ice cooling. The reaction was 
allowed to proceed to completion at a maximum of 45.degree. C. for a 
further 1.5 hours with occasional cooling and stirring until the batch no 
longer produced any inherent heat. After a further 20 minutes for 
completion at about 55.degree. C., the water (300 g in theory) was 
expelled azeotropically, and the mixture was then cooled to 95.degree. C. 
and finally, after addition of 5 g of .RTM.Corolite or .RTM.Celite, 
filtered under suction while hot through the filter into the distillation 
flask (rinsed with 200 ml of toluene). Firstly the toluene (slight 
vacuum), then the excess of amine (boiling point=82.degree. C./20 torr) 
were removed by distillation, finally at a flask bottom temperature of 
150.degree. C./20 torr. A yellowish oil was obtained having an amine 
number of 779. The yield was 1440 g (100% of theory). 
I.2. Preparation of 
1,7-di(2-ethylhexylamino)-2,6-dihydroxy-4-isononyloxypropyl-4-iminoheptane 
(.fwdarw.component (B)) 
a) Using the same apparatus as in I.1., epichlorohydrin (186 P, 2 mol) was 
added dropwise at 30.degree. C. to 35.degree. C. to a well-stirred mixture 
of 202 P (1 mol) of isononyloxypropylamine in 250 P of n-butanol. After 
about 20 to 50 ml, a measurable evolution of heat began, and the remaining 
amount of epichlorohydrin was subsequently metered in over the course of 3 
hours with cooling. The reaction was then allowed to continue at 
35.degree. C. to 50.degree. C. (for about 1 hour). 
b) 774 P (6 mol) of 2-ethylhexylamine were run into 80 P (2 mol) of NaOH in 
90 P of demineralized H.sub.2 O. 
The reaction product from step a) was added to the amine from step b) at 
40.degree. C.-50.degree. C. Salt formation was subsequently observed, and 
the reaction was allowed to continue at 50.degree. C. for 1 hour. The 
water was then expelled azeotropically (about 110 P), and the mixture was 
then cooled to 95.degree. C. and, after addition of 5 g of Corolite, 
filtered with suction while hot through the filter into the distillation 
flask (rinsed with 200 ml of n-butanol). Firstly the n-butanol (60.degree. 
C., 50-100 torr) and then the excess of amine (20 torr, 130.degree. C.) 
were removed by distillation. 
Yield: 575 g (100% of theory), amine number: 296 (theory 293) (only 
secondary amino groups). 
I.3. Preparation of the diketimine of 
1,3-bis(methyl-5-aminopentylamino)-2-propanol (.fwdarw.component (B)) 
290 P (1 mol, 2 equivalents of primary amine) of the amine of Example I.1 
were dissolved in 313.5 P (3.135 mol) of methyl isobutyl ketone, and the 
water produced was expelled azeotropically at 115.degree. C. to 
140.degree. C. (about 36 to 30 ml). This ketimine solution (about 80% 
strength) was then concentrated under reduced pressure at 60.degree. C. to 
100.degree. C. until about 113 g of methyl isobutyl ketone (corresponding 
to a solid content of the product of about 100%) had been stripped off. 
Yield: 452 g (100% of theory), amine number: 478 (theoretically 498), 
yellowish oil. 
I.4. Preparation of a semi-blocked diisocyanate 
124 P (105 mol) of butyl glycol were run into 174 P (1 mol) of 
.RTM.Desmodur T 80 (80% of 2,4-, and 20% of 2,6-toluylene diisocyanate) at 
30.degree. C. to 70.degree. C. in the presence of 0.9% by weight of 
benzyltrimethylammonium hydroxide as catalyst, and the reaction was 
carried out to a NCO content of about 13.0 to 14.1%. 
I.5. Preparation of a flexibilizing compound 
415 P (1 equivalent of OH) of .RTM.Capa 205 (polycaprolactonediol, MW about 
840, supplied by Interos, England) and 300 P (1 equivalent of OH) of 
commercially available polyethylene glycol 600 (supplied by Hoechst AG, MW 
about 600) were mixed with 152 P (1 mol) of tetrahydrophthalic anhydride 
and 266 P (1 mol) of dodecenylsuccinic anhydride (Shell), and reacted in 
the presence of 0.3% of triethylamine at 80.degree. C.-120.degree. C. 
until an acid number of about 98 to 102 mg of KOH/g of solids had been 
reached. 
II. Preparation of the curable compound (binder) 
II.1. 832 PW of a monoepoxy-monocyclocarbonate (=2 equivalents of epoxide) 
based on commercially available .RTM.Epicote 828 (=diglycidyl ether of 
bisphenol A) were warmed to about 60.degree. C. to 80.degree. C. and, in 
the presence of 0.2 to 0.4% by weight of commercially available chromium 
catalyst .RTM.AMC-2 (100% purity by weight, product of Cordova Chemicals, 
U.S.A.), run into a mixture of 1133 PW of flexibilized dicarboxylic acid 
(=2 equivalents of HOOC groups), prepared in accordance with Example I.5, 
and PW of dimethyl diglycol. The reaction mixture was allowed to react at 
80.degree. C. to 120.degree. C. until an acid number of &lt;5 and an epoxide 
number of &lt;0.1 had been reached. The resultant reaction product was 
obtained as an approximately 90% strength by weight solution in DMDG and 
subsequently diluted to a content of 80% by weight of reaction product by 
adding about 273 PW of DMDG. The yield of the flexibilized 
bis-cyclocarbonate desired was virtually 100%. 
2620 P (4 equivalents of cyclic carbonate) of a bis-cyclocarbonate (80% 
strength in DMDG) based on commercially available Epicote 1001 and 608 P 
of a monocyclocarbonate (2 equivalents of cyclic carbonate) based on the 
glycidyl ester of versatic acid were introduced into this mixture, and the 
mixture was reacted at 30.degree. C. to 80.degree. C. with 2384 P (about 
7.6 equivalents of NCO) of semi-blocked diisocyanate prepared in 
accordance with Example I.4. until a NCO content of about 0% was obtained. 
A mixture of 452 P (2 equivalents of NH) of the diketimine of I.3., 645 P 
(6 equivalents of NH.sub.2) of bishexamethylenetriamine, 627 P of butyl 
diglycol and 2746 P of methoxypropanol was reacted with this carbonate 
solution at 60.degree. C. to 100.degree. C. in the presence of 0.1% 
strength DABCO to an amine number of 34.5 mg of KOH/g of solids. The 
resultant reaction product was obtained as a 65% strength by weight highly 
viscous binder resin solution. 
II.2. 3930 P (6 equivalents of cyclic carbonate, 80% strength in DMDG) of a 
biscarbonate based in Epicote 1001, 608 P (2 equivalents of cyclic 
carbonate) of a monocyclocarbonate based on the glycidyl ester of versatic 
acid were mixed with 978 P of DMDG and the mixture was heated to about 
60.degree. C. 2384 P (about 7.6 equivalents of NCO) of semi-blocked 
diisocyanate prepared according to Example I.4. were introduced into this 
mixture and reacted at 60.degree. C. to 80.degree. C. to a NCO content of 
about 0%. 430 P (4 equivalents of primary amine) of 
bishexamethylenetriamine, 452 P (2 equivalents of secondary amine) of the 
diketimine of Example I.3., 575 P (2 equivalents of secondary amine) of 
the amine of Example I.2. in 2017 P of methoxypropanol and 500 P of butyl 
diglycol were run into this solution. The reaction was carried out in the 
presence of 0.1% strength N-pyrrolidinopyridine at 80.degree. C. to 
100.degree. C. to an amine number of about 45.1 mg of KOH/g of solid 
resin. The resultant reaction product was obtained as a 65% strength 
highly viscous binder resin solution. 
III. Use of the binders of Examples II for surface-coating preparations 
Pigmented surface-coating materials were prepared, corresponding to the 
following batches, from the binders of Examples II.1 and II.2: 
III.1. Preparation of a pigment paste (PBR about 12:1) 
70.5 P of 100% SWE 5219 paste resin from Vianova 
6.9 P of lactic acid, 100% 
220.0 P of demineralized water 
51.0 P of lead silicate 
80.0 P of dibutyltin oxide 
9.2 P of carbon black (.RTM.Printex 25) 
370.0 P of titanium dioxide (.RTM.Kronos RN 59) 
13.2 P of butyl glycol 
1500.0 P of zirconium oxide beads 
The batch was ground for 60 minutes with thorough cooling and subsequently 
adjusted to the processing viscosity using 108.0 P of demineralized water 
and sieved. 
III.2. Pigmentation of II.1 
690.0 P of the binder of II.1 (65% strength) and 16.6 P of 50% strength 
aqueous formic acid (=meq =40) were thoroughly homogenized in a dissolver 
and subsequently mixed with 286.0 P of the pigment paste of III.1 (63% 
strength), the mixture was thoroughly homogenized, and 25.07 P of 
demineralized water was subsequently added slowly (bath solids content 
about 18%). 
III.3. Pigmentation of II.2 
690.0 P of the binder of II.2 (65% strength) and 22.5 P of dibutyltin 
dilaurate were thoroughly homogenized and neutralized using 18.6 P of 50% 
strength aqueous formic acid (meq=45). 160.0 P of titanium dioxide (Kronos 
RN 59), 5.0 P of carbon black (Printex 25) and 15.0 P of lead silicate 
were subsequently added, and the total mixture was ground in a triple-roll 
mill, and 2590 P of demineralized water were subsequently added (bath 
solids content about 18%). 
III.4. Use as an electrocoating material 
The surface-coating preparations III.2 and III.3 were subjected to 
cataphoretic deposition in an open glass vessel. The cathode used was 
zinc-phosphated steel sheeting and the anode used was bare steel sheeting 
at a distance of 5 to 10 cm from the cathode. The duration of deposition 
was 2 minutes. 
The voltages applied in each case, the form of thicknesses achieved and the 
properties of the deposited and subsequently cured films (baking 
conditions: 20 minutes at an object temperature of 150.degree. C.) are 
shown in summarized form in the table below): 
TABLE 
______________________________________ 
Resin employed I.1 II.2 
______________________________________ 
Bath pH 6.8 6.5 
Maximum rupture voltage (V).sup.1 
300 250 
Depositon voltage (V).sup.1 
250 200 
Film thickness (.mu.m) 
18-20 16-18 
Throw.sup.2) 1 1-2 
Adhesion.sup.2) 0 0 
Crosslinking.sup.3) &gt;100 &gt;100 
Impact cupping.sup.4) 
&gt;80 &gt;80 
Erichsen cupping (mm) 
5-6 5 
______________________________________ 
.sup.1) at 28.degree. C. 
.sup.2) 0 = best, 5 = worst value 
.sup.3) Double rups with MEK, 1 kg weight addon; baking conditions: 20 mi 
(oven), 150.degree. C. 
.sup.4) Inch pound, in accordance with ASTM