Heat curable coating compositions and their use as top coats

The present invention relates to heat curable coating compositions containing a binder consisting essentially of PA1 A) prepolymers which have butanone oxime-blocked isocyanate groups and are prepared from PA2 A1) (cyclo)aliphatic polyisocyanates and PA2 A2) an organic polyhydroxyl component in which PA3 A2.1 ) 50 to 90% of the hydroxyl equivalents of component A2) are from polyester polyols, PA3 A2.2) 10 to 50% of the hydroxyl equivalents of component A2) are from polyacrylate polyols and/or alkoxylation products of bisphenol A and PA3 A2.3) 0 to 30 of the hydroxyl equivalents of component A2) are from other organic polyhydroxyl compounds, and PA1 B) cycloaliphatic polyamines having at least two primary amino groups, wherein components A) and B) are present in an equivalent ratio of blocked isocyanate groups to amino groups of 1:0.8 to 1:1.2. The invention also relates to the use of these coating compositions for producing decorative, flying-stone-resistant, thick topcoats on metallic substrates.

BACKGROUND OF THE INVENTION 
1. Field of the Invention 
The present invention relates to new heat curable coating compositions 
containing butanone oxime-blocked isocyanate prepolymers and 
cycloaliphatic polyamines and to their use for producing decorative 
coatings that are resistant to flying stones on a metal substrate, e.g., 
in the door sill area of a motor car. 
2. Description of the Prior Art 
Heat curable, one-component primers, which are resistant to flying stones 
and prepared from blocked NCO prepolymers and diamines, are known. This 
type of coating composition, described for example in DE-PS 2,131,299, 
contains aromatic diisocyanates and polyether polyols. In view of these 
structural components it is obvious that these coatings can really only be 
used beneath a top coat. If they were used as a top coat, they would turn 
yellow and chalky in the light. 
The same is true of the coating compositions according to EP-A-0,536,614, 
which are only used as undercoating lacquers or as underbody sealants. It 
is a common feature of both systems that they use .epsilon.-caprolactam as 
a blocking agent, which requires stoving temperatures of about 160.degree. 
C. In practice there is an increasing demand for coatings which are based 
on blocked polyisocyanates which can be cured at about 140.degree. C. 
Coating compositions are known from EP-A-0,059,962, which are based on 
ketoxime-blocked NCO prepolymers prepared from aliphatic diisocyanates. In 
the working examples, only NCO prepolymers prepared from polyether polyols 
are described. The presence of polyether polyols and the disclosed use of 
the systems for producing undercoats, which are resistant to flying 
stones, leads to the conclusion that the coating compositions are not 
intended for use as decorative light-resistant topcoats. 
Although in the general description of the publication, polyesterpolyols 
are also disclosed as suitable polyhydroxyl compounds for producing the 
NCO prepolymers, they were not considered to be preferred polyols as can 
be seen from their absence in the working examples. 
An object of the present invention is to provide heat curable coating 
compositions containing blocked NCO prepolymers and cycloaliphatic 
diamines which combine the following properties: 
light resistance for use to produce light-resistant topcoats; 
stoving temperatures of ca. 140.degree. C.; 
storage stability at 25.degree. C. for a period of at least 6 months. In 
this case, "storage stability" is understood to be the ability to be 
applied without any problems, i.e., with at most a negligible increase in 
viscosity; 
suitability for the production of decorative outer coatings and 
hard and tough consistency, thereby ensuring suitability for protection 
against flying stones. 
This object may be achieved with the binders according to the invention 
which are described below and based on NCO prepolymers prepared from 
selected starting materials. 
SUMMARY OF THE INVENTION 
The present invention relates to heat curable coating compositions 
containing a binder consisting essentially of 
A) prepolymers which have butanone oxime-blocked isocyanate groups and an 
average molecular weight, calculated from the NCO content and NCO 
functionality, of 1000 to 10,000, and are prepared from 
A1) (cyclo)aliphatic polyisocyanates and 
A2) an organic polyhydroxyl component in which 
A2.1) 50 to 90%, preferably 60 to 80% of the hydroxyl equivalents of 
component A2) are from polyester polyols, 
A2.2) 10 to 50%, preferably 20 to 40% of the hydroxyl equivalents of 
component A2) are from polyacrylate polyols and/or alkoxylation products 
of bisphenol A that contain 2 to 4 alkylene oxide units per molecule and 
A2.3) 0 to 30 of the hydroxyl equivalents of component A2) are from organic 
polyhydroxyl compounds other than those set forth in A2.1) and A2.2), and 
B) cycloaliphatic polyamines having at least two primary amino groups, 
wherein components A) and B) are present in an equivalent ratio of blocked 
isocyanate groups to amino groups of 1:0.8 to 1:1.2. 
The invention also relates to the use of these coating compositions for 
producing decorative, flying-stone-resistant, thick topcoats on metallic 
substrates. 
DETAILED DESCRIPTION OF THE INVENTION 
Polyisocyanates A1) are preferably selected from (cyclo)aliphatic 
diisocyanates having a molecular weight of 140 to 300, more preferably 168 
to 300, such as 1,6-diisocyanatohexane, 
1-isocyanato-3,5,5-trimethyl-5-isocyanatomethyl-cyclohexane (isophorone 
diisocyanate or IPDI), 4,4'-diisocyanatodicyclohexylmethane, 
1,4-diisocyanatobutane, 2,4 and/or 2,6-diisocyanato-1-methyl-cyclohexane 
("hydrogenated TDI") and 1,3-bis-(1-isocyanato-1-methylethyl)-benzene 
(tetramethyl-xylylene diisocyanate or TMXDI). 
Polyhydroxyl component A2) is selected from mixtures of the individual 
components A2.1), A2.2) and optionally A2.3), in which the percentages 
preferably add up to 100. Component A2.3) is preferably not used. 
Component A2.1) has a hydroxyl value of 28 to 280 and a number average 
molecular weight (M.sub.n of 400 to 4000, preferably 500 to 2000, and 
preferably is selected from polyhydroxyl compounds which contain ester 
groups, but do not ether groups. 
Suitable polyhydroxyl compounds containing ester groups include the known 
condensation products of polybasic acids or their anhydrides with excess 
amounts of polyhydric alcohols. Suitable polybasic acids or acid 
anhydrides include adipic acid, maleic acid, maleic anhydride, phthalic 
acid, phthalic anhydride, tetrahydrophthalic acid, tetrahydrophthalic 
anhydride, hexahydrophthalic acid, hexahydrophthalic anhydride and 
mixtures of these or other polybasic acids or acid anhydrides. Suitable 
polyhydric alcohols are those having a molecular weight of 62 to 200, such 
as ethylene glycol, propylene glycol, the isomeric butanediols, 
pentanediols, hexanediols and octanediols, glycerine, trimethylolpropane 
and mixtures thereof. Polyester polyols prepared from adipic acid and 
neopentyl glycol and/or 1,6-dihydroxyhexane and having a molecular weight 
of 500 to 2000 are particularly preferred. 
Also suitable as polyhydroxyl compounds containing ester groups are 1) 
polylactonediols, for example, the reaction product of hexanediol-1,6 and 
.epsilon.-caprolactone having molecular weights of 500 to 1500 and 2) 
polycarbonate diols, in particular hexanediol-1,6-polycarbonate diols 
having a molecular weight of 500 to 2000, which may be prepared by 
condensing the diol with diphenyl carbonate or dimethyl carbonate in known 
manner. 
Component A2.1) may also be selected from oligoesters of long-chain 
carboxylic acids which contain hydroxyl groups and are difficult to 
saponify, such as castor oil, in amounts of up to 50 wt. %, based on the 
total weight of component A2.1). 
Component A2.2), which is used to regulate the hardness of the coating, is 
preferably selected from either polyacrylate polyols or alkoxylated 
bisphenol A. 
Suitable polyacrylate resins are copolymers which are soluble in lacquer 
solvents and formed from monomers which contain hydroxyl groups and other 
olefinically unsaturated monomers such as butyl acrylate, methyl 
methacrylate, styrene, acrylic acid, acrylonitrile and/or 
methacrylonitrile. Suitable monomers which contain hydroxyl groups 
include, in particular, 2-hydroxyethyl (meth)acrylate and the isomeric 
mixture of hydroxypropyl (meth)acrylates obtained by the addition of 
propylene oxide to acrylic acid or methacrylic acid. The hydroxyl group 
content of suitable polyacrylate polyols is generally 1 to 10 wt. %. 
Particularly preferred are polyacrylate polyols prepared from a mixture of 
hydroxypropyl methacrylate isomers, n-butyl acrylate, styrene and acrylic 
acid, and having an OH group content of 4 to 7 wt. %, based on solids, and 
a maximum acid value of 15 mg KOH/g. 
Suitable alkoxylation products are preferably the ethoxylation or 
propoxylation products of bisphenol A, which contain a statistical average 
of 2 to 4 alkylene oxide units per molecule. These alkoxylation products 
have hydroxyl values of 243 to 354, preferably 300 to 340. The 
propoxylation products of bisphenol A are particularly preferred. The 
alkoxylation products may be used instead of the polyacrylate polyols and 
less preferably in admixture with the polyacrylate polyols. 
Suitable polyhydroxyl compounds A2.3) include polyhydric alcohols having a 
molecular weight of 62 to 200, which have previously been described for 
the production of the polyester polyols. 
The blocked NCO prepolymers are produced in known manner, for example, in a 
two-stage reaction by reacting polyhydroxyl compounds A2) with excess 
amounts of polyisocyanates A1) while maintaining an NCO/OH equivalent 
ratio of 2:1 to 2.5:1. The type and proportions of the starting components 
A1) and A2) are generally selected so that the resulting NCO prepolymer 
has an NCO content of 3.0 to 8.0 wt. %, preferably 4.5 to 7.0 wt. %, and 
has an average molecular weight in blocked form of 1000 to 10,000. 
The blocking reaction with preferably stoichiometric amounts of butanone 
oxime follows production of the NCO prepolymer, optionally with the aid of 
solvents. Both reactions are generally performed at temperatures of about 
50.degree. to 120.degree. C., preferably 60.degree. to 80.degree. C. 
The blocked NCO prepolymers A) can also be produced in a one-step reaction, 
by reacting polyhydroxyl compounds A2), butanone oxime and polyisocyanate 
A1) within the previously disclosed temperature range until the NCO bands 
(IR spectrum) vanish. The proportions of the reaction components are 
selected such that there are approximately 1 hydroxyl equivalent and 1 
oxime equivalent to 2 NCO equivalents. 
The blocked NCO prepolymers A) may be diluted with organic solvents or 
plasticizers to form a solution having a solids content of 25 to 50 wt. % 
to obtain the optimum spray viscosity of the coating composition. Suitable 
solvents are known and include Solvesso 100 solvent, solvent naphtha, 
isobutanol, butyl acetate and/or methoxypropyl acetate. Suitable 
plasticizers are known and include plasticizers based on adipates, 
phthalates or alkylsulphonates. 
Curing component B) is a cycloaliphatic polyamine having at least two 
primary amino groups. Examples include 4,4'-diaminodicyclohexylmethane, 
1,4-diaminocyclohexane, 3,3,5-trimethyl-5-aminomethylcyclohexylamine 
(IPDA) and perhydrogenated triamino-diphenylmethanes, such as those used 
in accordance with DE-OS 3,417,683 to produce the corresponding 
cycloaliphatic triisocyanates. Mixtures of polyamines may also be used. 
3,3'-dimethyl-4,4'-diamino-dicyclohexylmethane and 
4,4'-diamino-dicyclohexylmethane are preferred. 
The binder is produced by mixing components A) and B) in proportions 
selected such that there is an equivalent ratio of blocked NCO groups to 
primary amino groups of 1:0.8 to 1:1.2, preferably 1:1 to 1:1.2, and more 
preferably 1:1.05 to 1:1.1. 
If desired, the coating compositions according to the invention may also 
contain known additives from lacquer technology, such as pigments, flow 
controllers, UV stabilizers, antioxidants, fillers and thixotropic agents. 
The binder components may be mixed with these additives before, during or 
after mixing components A) and B). 
The coating compositions according to the invention are especially suited 
for producing stoved coatings on optionally pretreated metal substrates, 
in particular those which are used in the automobile industry. The 
coatings are generally stoved at a temperature of 120.degree. to 
160.degree. C., preferably 120.degree. to 140.degree. C.

In the following examples, all percentages are by weight, except for 
relative changes in properties, which are given in %. 
EXAMPLES 
Example 1 
This example describes the production of a coating composition according to 
the invention and the properties of a coating prepared therefrom. The 
polyol component contained 70 equivalent-% of polyester A2.1) and 30 
equivalent-% of polyacrylate A2.2). 
1.1. Preparation of the binder 
Mixture: 
______________________________________ 
595.0 g (0.7 equiv.) 
of an adipic acid/hexanediol/neopentyl 
glycol polyester (wt. ratio of hexanediol: 
neopentyl glycol = 77:33) having an OH 
number of 66 
108.6 g (0.3 equiv.) 
of a commercial hydroxypolyacrylate hav- 
ing an acid number of 10 and prepared 
from hydroxypropyl methacrylate, butyl 
acrylate, styrene and acrylic acid. The 
OH group content, based on the 75% so- 
lution in xylene, is 4.7% and the OH equi- 
valent weight is 362 g (Desmophen A 
Experimental Product LS 2051 of Bayer 
AG, Germany) 
2.4 g (1.1. equiv.) 
of 1,6-diisocyanatohexane 
144.1 g (1.1 equiv.) 
of 4,4'-diisocyanatodicyclohexylmethane 
104.4 g (1.2 equiv.) 
of butanone oxime 
409.0 g of solvent naphtha 100 
1453.5 g (1.2 equiv of blocked NCO groups) 
______________________________________ 
Experimental 
The polyester, polyacrylate and two diisocyanates were initially introduced 
into a container and heated to 100.degree. C. with stirring. After a 
reaction time of 1 hour, an NCO content of 5.3% was measured (calculated 
5.36%). The mixture was diluted with the solvent and allowed to cool to 
about 60.degree. C., and then butanone oxime was added incrementally such 
that the temperature did not rise above 70.degree. C. Stirring was 
continued for 40 minutes at 70.degree. C., until the NCO content could no 
longer be detected (IR spectrum). The blocked NCO prepolymer solution had 
a viscosity of about 2800 mPa.s at 23.degree. C. and a blocked NCO 
equivalent weight of 1211 g (blocked NCO content: 3.46%). 
1.2. Preparation of the coating composition 
______________________________________ 
470.0 pts by wt. 
blocked NCO prepolymer according to 1.1 
48.5 pts by wt. 
3,3'-dimethyl-4,4'-diaminodicyclohexyl- 
methane 
47.0 pts by wt. 
titanium dioxide (rutile form) 
211.5 pts by wt. 
barium sulphate 
3.0 pts by wt. 
carbon black FW 200 
95.0 pts by wt. 
magnesium silicate hydrate (Norwegian talc) 
12.0 pts by wt. 
highly dispersed silica 
45.0 pts by wt. 
3-methoxy-n-butyl acetate 
56.0 pts by wt. 
pine oil 
12.0 pts by wt. 
butyl acetate 
1000.0 pts by wt. 
______________________________________ 
The components, with the exception of the diamine cross-linker, were 
dispersed in a dissolver (8000 rpm) for about 30 minutes. Care was taken 
that the temperature of the material being dispersed did not exceed 
50.degree. C. The 48.5 pts by wt. of 
3,3'-dimethyl-4,4'-diaminodicyclohexylmethane were then vigorously stirred 
into the dispersed mixture. 
A heat curable, one-component coating composition was obtained, which can 
be used in this form in a compressed air process or an airless spraying 
process. The binder of the coating composition contained 470 g (0.388 
equiv.) of the blocked NCO prepolymer and 48.5 g (0.407 equiv NH.sub.2) of 
3,3'-dimethyl-4,4'-diamino-dicyclohexylmethane. 
The blocked NCO/NH.sub.2 equivalent ratio was 1:1.05. 
1.3. Properties of the coating composition 
1.3.1. Viscosity 
Coating composition 1.2 had a calculated solids content of about 75% and a 
viscosity, determined according to DIN 53 214 (with a rate of shearing 
fall D of 39.9 sec.sup.-1), of 3000 to 3500 mPa.s, depending on the 
rotating body used. 
1.3.2. Stoving conditions 
The coating composition was cured without the addition of a catalyst at 
130.degree.-140.degree. C. within 30 minutes to give a tough, elastic film 
having a Shore A hardness of about 65. 
1.3.3. Storage stability 
Since the coating composition represented a potentially reactive system 
containing primary amino groups, blocked NCO groups and also polyester 
groups (which represent the backbone of the polymer structure), storage 
stability was a major test criterion. It was found that after 30 days 
storage at room temperature, the viscosity remained unaltered. After 
storage for 1 year at room temperature, the viscosity rose (DIN 53019/01) 
only slightly, i.e., only by about 30% compared to the starting value. 
Also, storage for 7 days at 50.degree. C. in a drying cabinet resulted in 
a viscosity increase of only about 20%, compared to the starting value. 
1.3.4. Resistance to flying stones 
Coating composition 1.2 was applied to test metal sheets (which had been 
precoated with a cathodic deposition primer) in an amount such that a film 
with a thickness of 200 .mu.m was produced after stoving (30 min at 
140.degree. C.). The coated sheets were subjected to an abrasion test in 
accordance with the Daimler Benz AG company specification. For this, 
morainic stone chippings having a diameter of 5 to 8 mm (supplier: C. F. 
Mayer, Sindelfingen-Dachsklinge) were shot at the coating with a pressure 
of 0.8 bar. The time which was required for clean sheet metal to appear at 
the point of impact of the beam of stone chippings was then measured. When 
the preceding coating was tested, the stone chippings required a time of 
75 sec, which represents good abrasion resistance for a coating prepared 
from the coating composition according to the invention. 
1.3.5. Weathering behavior 
Test metal sheets coated with the coating composition 1.2 were subjected to 
a QUV test according to ASTM G 53-77 in UVB equipment 313. After 2000 
hours of weathering, the coating was inspected and no cracks, chalking or 
decrease in gloss was observed. 
Example 2 
Example 1 was repeated with the exception that 51.9 g (0.3 equiv.) of a 
propoxylated bisphenol A having molecular weight 346 were used instead of 
108.6 g (0.3 equiv.) of the polyacrylate resin. 
The viscosity of the coating composition, determined using the method given 
in example 1, was 3000 to 4000 mPa.s. The storage stability corresponded 
to the storage stability of the coating composition according to example 
1. The coating composition was applied to test panels as described in 
example 1 and cured at 130.degree. to 140.degree. C. to form a tough, 
elastic film having a Shore A hardness of 70. The flying stone test 
produced a time of 75 secs. The weathering behavior corresponded to the 
weathering behavior of the coating from example 1. 
Example 3 (comparison) 
Example 1 was repeated with the exception that the polyacrylate resin was 
omitted and the amount of polyester polyol was increased to 850.0 g (1.0 
equiv.). 
The viscosity of the coating composition, determined by the method given in 
example 1, was 2000 to 3000 mPa.s. The storage stability corresponded to 
the storage stability of the coating composition according to example 1. 
The coating composition was applied to test panels as described in example 
1 and cured at 130.degree. to 140.degree. C. to form a soft, elastic film 
having a Shore A hardness of only 40. Consequently, an abrasion time of 
only 45 sec was produced in the flying stone test, which represents a time 
of resistance which is more than 1/3 shorter than that of the coating 
compositions according to the invention. 
Example 4 
4.1. Preparing the binder 
Mixture: 
______________________________________ 
425.0 g (0.5 equiv.) 
of the polyester from example 1 
102.0 g (0.3 equiv.) 
of castor oil, OH value 164 
34.6 g (0.2 equiv.) 
of the propoxylated bisphenol A from 
example 2 
131.0 g (1.0 equiv.) 
of 4,4'-diisocyanato-dicyclohexylmethane 
92.4 g (1.1 equiv.) 
of 1,6-diisocyanatohexane 
95.7 g (1.1. mol) 
of butanone oxime 
378.0 g of solvent naphtha 100 
1258.7 g (1.1 equiv. blocked NCO groups) 
______________________________________ 
Experimental 
The two diisocyanates, the polyester and the bisphenol A derivative were 
initially introduced and heated to 100.degree. C. with stirring. After a 
reaction period of about 2 hours at 100.degree. C., an NCO content of 5.9% 
was measured (5.98% calculated). The mixture was diluted with solvent 
naphtha 100, cooled to about 50.degree. C. and butanone oxime was added 
dropwise. Stirring was continued at 70.degree. C. for about 30 minutes 
until no more NCO groups were detectable (IR spectrum). A clear, pale 
yellow solution was obtained (70% solids content) having a viscosity at 
23.degree. C. of ca. 3700 mPa.s and a blocked NCO equivalent weight of 
1144, which corresponds to a blocked NCO content of 3.6%. 
4.6. Preparation of the coating composition 
Mixture: 
______________________________________ 
468.5 parts by wt. 
blocked NCO prepolymer according to 2.1. 
51.1 pts by wt. 
3,3'-dimethyl-4,4'-diaminodicyclohexyl 
methane 
41.4 pts by wt. 
titanium dioxide (rutile form) 
224.1 pts by wt. 
barium sulphate 
94.2 pts by wt. 
magnesium silicate hydrate (Norwegian talc) 
11.3 pts by wt. 
highly disperse silica 
11.0 pts by wt. 
butyl acetate 
43.8 pts by wt. 
3-methyl-n-butyl acetate 
54.6 pts by wt. 
pine oil 
1000.0 pts by wt. 
______________________________________ 
The above components, except for the diamine crosslinker, were dispersed in 
a dissolver (8000 rpm) for about 30 minutes. Care was taken to avoid the 
material being dispersed from exceeding a temperature of 50.degree. C. 
Then the 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane was mixed with the 
dispersed material. A heat curable, one-component coating composition was 
obtained which can be used in a variety of spraying processes. The binder 
of the coating composition contained 8.5 g (0.409 equiv.) of the above 
blocked NCO prepolymer and 51.1 g (0.430 equiv. NH.sub.2) of 
3,3'-dimethyl-4,4'-diaminodicyclohexylmethane. 
The blocked NCO/NH.sub.2 equivalent ratio was 1:1.05. 
4.3. Properties of the coating composition 
4.3.1. Viscosity 
The viscosity at 23.degree. C. of the coating composition, determined by 
the method given in example 1, at a solids content of about 75% was 
3000-4000 mPa.s (DIN 53 214). 
4.3.2. Stoving conditions 
The coating composition was cured at 130.degree.-140.degree. C. without the 
use of a catalyst for 30 minutes to give a tough elastic film having a 
Shore A hardness of about 65. 
4.3.3. Storage stability 
The coating composition was storage stable. After storage for 30 days at 
room temperature, no increase in viscosity was observed. After storage for 
7 days in a drying cabinet at 50.degree. C. an increase in viscosity (DIN 
53019/01) of only 20%, compared to the starting value, was found. 
4.3.4. Resistance to flying stones 
The above coating composition was applied to lacquer test metal sheets from 
Mercedes Benz AG, which had been precoated with a cathodic deposition 
primer, and stoved at 140.degree. C. for 30 min in a drying cabinet. A dry 
film thickness of 150 .mu.m was produced. This coated sheet was subjected 
to the abrasion test in accordance with the Mercedes Benz specification, 
i.e. the sheet was shot at with morainic stone chippings (diameter 5-8 mm) 
under a pressure of 0.8 bar. The time was measured at which the coating 
was rubbed off the sheet and bare metal was exposed at the point of 
impact. Abrasion times of 70 sec were determined, which is an excellent 
value since 60 sec represents a high abrasion resistance. 
4.3.5. Adhesion 
The coating composition according to the invention was intended to be used 
as decorative protection against flying stones, i.e., occasionally as a 
topcoat. To determine if the preceding coating composition was suitable 
for this application, it was applied to a lacquer test metal sheet which 
had been precoated with two-layers (undercoat and clear coat) of a 
two-component polyurethane coating composition, and stoved at 140.degree. 
C. for 30 min. A dry film thickness of 200 .mu.m was produced. A 
cross-hatch adhesion test was then performed (DIN 53 151). The coating had 
a characteristic GT value of 0, i.e., the edges of the cut were completely 
smooth and no sections of the hatched cut coating had flaked away. 
Example 5 
This example describes the production of a binder according to the 
invention in plasticizer instead of solvent. Using these binders, 
bubblefree coatings having a thickness of several millimeters can be 
produced. 
5.1. Preparing the binder 
______________________________________ 
255.0 g (0.3 equiv.) 
of the polyester from example 1 
153.0 g (0.45 equiv.) 
of castor oil, OH value 164 
43.3 g (0.25 equiv.) 
of the propoxylated bisphenol A from 
example 2 
100.8 g (1.2 equiv.) 
of 1,6-diisocyanatohexane 
117.9 g (0.9 equiv.) 
of 4,4'-diisocyanato-dicyclohexylmethane 
95.7 g (1.1 equiv.) 
of butanone oxime 
138.0 g (1.16 equiv.) 
of 3,3'-dimethyl-4,4'-diaminodicyclohexyl 
methane 
430.0 g plasticizer; benzyloctyl adipate 
1333.7 g one-component binder 
______________________________________ 
Experimental 
The two diisocyanates and then the polyester and the bisphenol A derivative 
were initially introduced and heated to 100.degree. C. with stirring. 
After a reaction period of about 2 hours, an NCO content of 6.5% was 
measured (6.9% calculated). While the mixture cooled to about 50.degree. 
C., it was diluted with plasticizer. Butanone oxime was added dropwise, 
which caused the temperature to increase to 70.degree. C. The mixture was 
then stirred at 70.degree. C. for about 30 min until no more NCO groups 
were detectable (IR spectrum). The liquid diamine was then added to from a 
clear, pale yellow, one-component binder having a viscosity at 23.degree. 
C. of ca. 7500 mPa.s. 
5:2. Properties of the binder 
5.2.1. Stoving conditions/hardness of the film 
The composition was poured into an aluminum dish (diameter 6 cm). The 
thickness of the layer was several millimeters. The composition was cured 
in a drying cabinet at 140.degree. C. for 30 minutes. The cured, 
approximately 5 mm thick test specimens were tough and elastic and had a 
Shore A hardness of 45. The specimens were cut up. No evaporation bubbles 
were observed at the cut faces, i.e., the thick layer had cured without 
the production of bubbles. 
5.2.2. Storage stability 
After storage for 30 days at room temperature, no increase in viscosity was 
observed. After storage for 7 days in a drying cabinet at 50.degree. C., 
an increase in viscosity (DIN 53019/01) of about 20%, compared to the 
initial value was found. This finding means that the binder was storage 
stable. 
5.2.3. Resistance to flying stones 
The binder was applied to a test metal sheet to provide a film thickness of 
300 .mu.m and stoved at 140.degree. C. for 30 min. This thickly coated 
sheet was shot at with morainic stone chippings under a pressure of 0.8 
bar, as described in example 1.3.4. An abrasion time of 255 sec was 
determined for the thick coating, which was a very good result. The fact 
that this value was higher than in the preceding examples is attributed to 
the lack of pigment in the formulation. 
Although the invention has been described in detail in the foregoing for 
the purpose of illustration, it is to be understood that such detail is 
solely for that purpose and that variations can be made therein by those 
skilled in the art without departing from the spirit and scope of the 
invention except as it may be limited by the claims.