Acid etch resistant automotive topcoat

The present invention relates to improved acid etch resistant polymers and coatings, and their method of preparation whereby polyurethane polyols, which because of long alkyl side chains that include a single ether group in the chain, when reacted with a melamine compound, such as, hexakismethoxymethylmelamine, form coatings that have excellent solubility in hydrophobic solvents and provide films with excellent acid etch resistance. The polymers, because of their excellent acid etch resistance and exterior durability can be used for automotive clear coats or single coats.

FIELD OF THE INVENTION 
This present invention relates to chemically resistant polymers that have 
excellent acid etch resistance and exterior durability and can be used for 
automotive clear coats or single coats. Specifically, the present 
invention relates to polyurethanes that are melamine cross-linked to 
provide polymer coatings with improved acid etch resistance. 
BACKGROUND OF THE INVENTION 
Polymeric materials have been used for coating substrates in many 
industries. For example, in the automotive industry, these polymeric 
coatings, e.g., single coats or clear coats, are used to provide 
resistance to environmental acids for automotive products. Automotive 
topcoats represent one of the most demanding coating applications. These 
have to provide an aesthetic, long lasting appearance, and retain their 
gloss under the influence of moisture, UV radiation and temperature. 
Further, due to the acidity of rain, these automotive coatings must also 
be acid etch resistant. 
To avoid environmental pollution and improve safety, reduced volatile 
organic solvent content (VOC), high solids content (HSC) automotive clear 
coats have been developed. The HSC coatings are predominantly based upon 
acrylic polymers. Over the past 10 years, the average molecular weights of 
the acrylic polymers have been lowered to achieve higher solids content 
and lower VOC, and the low molecular weight acrylic resins are 
cross-linked with an amino formaldehyde resin. As the molecular weight of 
the acrylic polymers is lowered, a higher level of the melamine 
cross-linker is required to achieve acceptable properties. 
For example, the lower solids acrylic polymers which were previously used 
in automotive coatings contained about 20-25% melamine resin. At this 
level of melamine resin the acid etch resistance of the coating was 
acceptable. However, for high solids coatings, a melamine resin level of 
30-45% was required to achieve sufficient crosslinking in a lower 
molecular weight resin, to provide solvent resistance and exterior 
durability. For a high molecular weight acrylic polymer with a molecular 
weight ("MW") of 100,000, a film with excellent mechanical properties will 
form without the need of a crosslinker. Thus, if the MW of a polymer is 
low, the polymer chain will need to be extended by adding a chain 
extension agent, i.e. a crosslinker. A further complication arises when 
the MW of a polymer is decreased. For example, acrylic polymer prepared by 
free radical polymerization have a random MW distribution. For a polymer 
with an average MW of 2000, there are high and low MW fractions. The low 
MW fractions are of concern. It is known that only a fraction of the 
monomer units contain functional groups such as hydroxyl groups, for chain 
extension. If 20% of the monomer units are functional and reactive with 
the melamine resins and a polymer chain contains only 5 monomer units, 
there will be on the average only one functional group per chain. Also, a 
certain proportion of the polymer chains will contain no functional 
groups. It has been found by experience that polymer chains without 
functional groups plasticize with a resultant decrease in exterior 
durability. Therefore, to assure the presence of sufficient functional 
groups on the low molecular weight polymer chains in a high solids acrylic 
polymer, the content of functional monomer has to be increased. As a 
result of this increase in the content of functional monomers, the content 
of the crosslinker must also be increased. 
It has been found, however, that at higher levels of the melamine 
crosslinker the acid etch resistance of the polymer is reduced. Acid etch 
testing conducted on melamine resins crosslinked coatings show a clear 
relationship between acid etch resistance and melamine resin content. It 
is known that the ether linkage between the melamine resins and the 
acrylic polymer is acid catalyzed and, therefore, will hydrolyze under 
acid conditions. In contrast, the acrylic backbone itself consisting of 
carbon--carbon bonds is more resistant to acid attack. 
The presently used HSC automotive coatings utilize hydroxyl function 
acrylic polymers having molecular weights of about 2000-5000 and a 
hydroxyl number of 150 to 200. Such high solid content acrylic polymers 
are commercially available, e.g., Acryloid QR-1120 available from Rohmand 
Haas or, Elveron 100 from Dupont. The melamine cross-linker is usually a 
fully alkylated hexamethylol melamine resin, such as, 
hexakismethoxymethylmelamine (HMMM), the oligomers thereof or a mixed 
ether melamine resin such as a methylated/butylated resin. 
The composition of a typical mixed ether melamine resin is described in 
U.S. Pat. No. 4,374,164. The chemistry and reactivity of melamine resin is 
described in W. J. Blank, "Reaction Mechanism of Amino Resins," J. Coat. 
Techn., Vol. 51, No. 6567, pg. 61-70 September 1979; N. Albrecht and W. J. 
Blank, "The Use of Triazine Resins in High Solids Coatings", Proceedings 
of the Sixth International Conference in Organic Coatings and Technology, 
Athens, Greece, 1980; W. J. Blank, "Amino Resins in High Solids Coatings," 
J. Coat. Techn. Vol. 54; Nu 687; pg 26-41. The attack by acids on 
automotive coating is described in Alrich Schulz & Peter Trubiroha, 
"Simulated acid precipitations, Advances in the weathering of automotive 
finishes", Europcoat 9/1993, Pg 600-602. Formulations prepared from 
hydroxyl function acrylic polymers and HMMM are catalyzed with a strong 
sulfonic acid catalyst such as p-toluenesulfonic acid or dodecylbenzene 
sulfonic acid, dinonylnaphthalene disulfonic acid or the amine salts of 
these acids. 
It has now been found that the low molecular weight acrylic/cross-linked 
melamine coatings of the prior art are sensitive to acid rain. As a 
result, when these HSC coatings are applied to surfaces that are exposed 
to typical industrial conditions, such as acid rain found in an industrial 
environment, the acid attacks the surface of the HSC coating. The acid 
rain causes leaching of the slightly basic melamine resins leading to a 
dull surface with the loss of gloss and eventually, pitting. 
Two component acrylic/isocyanate coatings have been developed in an attempt 
to avoid this problem. However, because of the toxicity of the isocyanates 
and the short pot life of these coatings, they have not been accepted 
widely by the coating industry. 
Thus, the objective of the present invention is to provide a polymeric 
coating that avoids the above mentioned problems. This objective have been 
achieved by polyurethane-polyol-melamine cross-linked polymers and 
coatings according to the present invention that have improved acid etch 
resistance. 
THE PRIOR ART 
The instant applicants are aware of the following references: John L. 
Gordon, "Polyurethane Polyols: Ester-Bond Free Resins For High Solids 
Coatings," J. of Coating Technology, Vol. 65, No. 819, April 1993, Pages 
25-33; Werner J. Blank, "Non-Isocyanate Routes To Polyurethanes," 
Water-Borne and Higher Solids Coatings Symposium, Feb. 21-23, 1990, New 
Orleans, La. and U.S. Pat. Nos. 5,134,205 and 4,820,830. 
SUMMARY OF THE INVENTION 
The present invention provides improved acid etch resistant coatings that 
are prepared from polyurethane polyols, which are soluble in conventional 
solvents such as aromatic hydrocarbons, ketones, esters, glycolethers, 
glycolether acetates and alcohols. Examples for such solvents are xylene, 
toluene, methylethylketone, acetone, methylisobutylketone, ethylacetate, 
butylacetate, 2-methoxypropanol, 2-methoxypropylacetate. 
The polyurethane polyols of this invention do not require exotic and 
expensive solvents such as methypyrrolidinone, dimethylformamide, 
dimethylacetamide or dimethylsulfoxide. In addition the polyurethane 
polyol of this invention is broadly compatible with a wide range of 
melamine formaldehyde resins, including hexakis (methoxymethyl) melamine, 
partially alkylated melamine formaldehyde resins, butylated melamine 
formaldehyde resins, alkylated glycoluril formaldehyde resins and with 
most amino formaldehyde resins. Melamine formaldehyde resins are preferred 
because of their excellent combination of properties and cost. 
It is an object of the present invention to provide a polyurethane polymer 
having an average molecular weight of from about 500 to about 5000 and 
prepared from at least one monomer having at least one hydrophobic side 
chain per molecule that contains one ether group per chain. 
It is a further object of the subject invention to provide a process of 
preparing polyurethane polyol polymers by reacting a diol or at least one 
polyol with a poly(hydroxyalkyl carbamate) of an aliphatic or 
cycloaliphatic amine and a monohydroxyalkyl carbamate of an 
alkoxypropylamine or an alkoxypropylamine to form a polyurethane polyol 
and reacting the polyurethane polyol and a melamine cross-linker with a 
catalyst to form the improved acid etch resistant coating. 
It is still another object of the present invention to improve the acid 
etch resistance of polyurethane polymers by using a polyol having an ether 
group in the hydrophobic side chain. 
It is a further objective of this invention to render these polyurethane 
polyols water-dispersible by reacting these polyols with an anhydride, to 
form a half ester of said anhydride, and dispersing this half ester in 
water in the presence of a volatile base, such as an amine. 
In order that the concepts of the present invention may be more fully 
understood, the following drawings and examples are set forth in which all 
parts are by weight unless otherwise indicated. These examples are set 
forth primarily for illustration and any specific enumeration of detail 
set forth therein should not be interpreted as a limitation on the case 
except as is indicated in the appended claims.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS 
The present invention involves coatings prepared from polyurethane polyols, 
which are soluble in conventional solvents such as xylene, and have 
substantially improved acid etch resistance. The improved acid etch 
resistant polymers can be applied as a coating to metallic or primed 
substrates, such as steel or electrocoated steel, to provide a bright 
surface with high gloss that resists dulling and pitting from acid rain 
and/or harsh environments. 
Conventional urethane polymers known in the art are polyester or polyether 
urethanes. The polymers are normally obtained by reacting a polyester or 
polyether polyol with a diisocyanate or by nonisocyanate routes such as a 
condensation reaction of a carbonate and a diamine, followed by condensing 
the dicarbamate with a diol. See W. J. Blank, Preprint, Water-Borne and 
Higher Solids Coatings Non-Isocyanate Routes to Polyurethanes. Symposium 
at University of Southern Mississippi (February 1990). 
Although these urethane coatings have excellent flexibility and abrasion 
resistance, they do not provide any improvement in acid etch resistance 
despite the replacement of the ester groups with urethane groups which are 
more resistant to acid hydrolysis. Moreover, it has been found that 
polymers containing only urethane groups have poor solubility in 
conventional, low polar solvents such as, xylene and toluene. This poor 
solubility renders the urethane polymers unacceptable in automotive 
coating. 
It is also known from alkyd resin synthesis that long oil alkyds have 
improved solubility versus short oil alkyds or polyester resins. Long oil 
alkyds or short oil alkyds refer to the amount (weight) of fatty acid in 
the polymer. The fatty acids used in alkyds have normally a chain length 
of 12 to 18. A short oil alkyd has a fatty acid content of approximately 
30-50% and a long oil alkyd of 60-75%. There have been attempts to improve 
the solubility of polyurethane resins in solvents typically used in the 
automotive industry. However, though the solubility in xylene at higher 
temperature was improved, the resulting solutions turn hazy, gel and 
eventually crystallize at room temperature. Therefore, introducing long 
alkyl side chains results in an unacceptable source material for 
automotive coatings. Accordingly, their commercial use of such 
polyurethane resins is quite limited. 
It has been found unexpectedly that the presence of an ether group in the 
long alkyl side chain introduced to a polyurethane polyol overcomes these 
disadvantages, such as hazing, gelling and crystallizing. It further 
provides polyurethane polyols with excellent solubility in hydrophobic 
solvents. Further, films formed from such polyurethane polyol resins have 
excellent acid etch resistance. 
The polymer according to the present invention is defined by the formula 
EQU D.sub.n {[P(B).sub.x ].sub.y A.sub.z } 
wherein D is OH group, a carboxyalkylester or a carboxyarylester obtained 
by the reaction of an OH group with a C.sub.4 to C.sub.20 acyclic 
aliphatic, a C.sub.4 to C.sub.20 cycloaliphatic or a C.sub.8 aromatic 
anhydride group, or a combination of an OH group and the above 
carboxyalkyester or carboxyarylester groups; 
n is at least 2, preferably 3 or higher, with a maximum average of about 
10; 
P is a C.sub.2 -C.sub.10 aliphatic or C.sub.3 -C.sub.10 cycloaliphatic 
moiety and is derived from a diol or polyol; 
B is a di or tri functional aliphatic or cycloaliphatic urethane and or 
urea moiety with the structure 
##STR1## 
wherein R.sub.1 is C.sub.2 to C.sub.18, or 
##STR2## 
wherein R.sub.1 is C.sub.2 to C.sub.18, or 
##STR3## 
wherein R.sub.1 is C.sub.2 to C.sub.18 ; and derived from the reaction 
with a polyhydroxyalkyl carbamate 
A is defined as, 
##STR4## 
wherein R.sub.2 is a C.sub.6 to C.sub.18 aliphatic linear or branched 
alkyl group derived from the reaction product of an amine with a cyclic 
carbonate, or 
EQU --(CH.sub.2).sub.3 O--R.sub.2 
wherein R.sub.2 is a C.sub.6 to C.sub.18 aliphatic linear or branched alkyl 
group derived from an etheramine, and optionally at least a portion of the 
above etheramine can be replaced with A' defined as 
##STR5## 
with R.sub.2 being a C.sub.6 to C.sub.18 aliphatic linear or branched 
alkyl group derived from the reaction product of an amine and a cyclic 
carbonate, or a C.sub.6 to C.sub.18 aliphatic linear or branched alkyl 
group derived from an amine; and z is on the average at least one. 
According to the present invention, polyurethane polyols are prepared by 
reacting a diol or polyol or a combination of polyols with (1) a 
poly(hydroxyalkyl carbamate) of an aliphatic or cycloaliphatic amine 
and/or (2) a monohydroxyalkyl carbamate of an alkoxyalkylamine. Optionally 
some of the alkoxyalkyl amine can be replaced by an alkylamine. 
The polyol contains, on the average, at least one hydrophobic side chain 
per molecule. At least a part of the side chain contains one ether group 
per chain. The average hydroxyl functionality of these polyurethanes is at 
least 2, preferably 2.5 or higher. The average molecular weight of above 
polymer is between 500 and 5000, preferably between 800 and 3000, and most 
preferably between 1000 and 2000. If the polymer is to be 
water-dispersible, the carboxyl content should be between 0.5 to 
approximately 1.5 MEQ/g of polymer, preferably between 0.8 to 1.2 COOH 
MEQ/g (milliequivalent per gram). Preferably, the polymer should have on 
the average of one carboxyl group per chain. 
The polyurethane according to the present invention are soluble in aromatic 
hydrocarbons, ketones, esters or alcohols. The polyurethane polyols of the 
present invention are essentially devoid of ester groups, but can contain, 
besides the urethane groups, urea groups. 
The preferred method of preparing the polyurethane polyol is by condensing 
a bis(.beta.-hydroxyalkyl carbamate) of a linear aliphatic or 
cycloaliphatic diamine with a polyol or a .beta.-hydroxyalkyl carbamate of 
a C.sub.6 -C.sub.30 monoamine containing one ether group per chain with a 
polyol. Optionally, if urea groups are desired, parts of the 
.beta.-hydroxyalkyl carbamate monomers can be replaced with a free diamine 
or monoamine. The .beta.-hydroxalkyl carbamates used in the present 
invention can be prepared by the reaction of a cyclic carbonate with a 
primary diamine or mono amine as shown below: 
##STR6## 
and disclosed in U.S. Pat. Nos. 4,820,830 and 5,134,205 the subject matter 
of which is incorporated herein by references. The cyclic carbonates used 
in the present invention are defined in the above referenced patents. 
The diamines that can be used in the present invention include (1) C.sub.2 
-C.sub.12 linear alkyl diamines, (2) C.sub.5 -C.sub.15 cycloaliphatic 
amines and combination of linear amines, as well as the diamines disclosed 
in U.S. Pat. Nos. 4,820,830 and 5,134,205. Amines other than those 
identified above can also be used. The preferred amines used are the 
branched chain amines disclosed in U.S. Pat. No. 4,820,830. 
Examples of other amines which are useful in the present invention includes 
alkyl diamines such as: ethylenediamine, 1,3-propane diamine, 1,4-butane 
diamine, 1,5-pentane diamine, 1,6-hexane-diamine, 1,7-heptane diamine, 
1,8-octane diamine, 1,9-nonane diamine, 1,10-decane diamine, 1-12-dodecane 
diamine and the branched chain analogs of said amines, such as 
2,2,4-trimethyl hexamethylene diamine, 2,4,4-trimethyl hexamethylene 
diamine; cycloaliphatic amines such as 1,2-cyclohexane diamine, 
1,4-cyclohexane diamine, 1,3-cyclohexane diamine, 
3-aminomethyl-3,5,5-trimethyl-cyclohexylamine, 4,4-diaminodicyclo 
hexylmethane, 3,3-dimethyl-4,4-diaminodicyclohexylmethane; 
isodecyloxypropyldiaminopropane; alkoxyproplyamines such as: 
isohexyloxypropylamine, isodecyloxypropylamine, isotridecyloxypropylamine, 
hexyloxypropylamine, decyloxypropylamine, tridecyloxypropylamine. Typical 
anhydrides which can be used to render the polyurethanes water-soluble or 
dispersible are: succinic anhydride; glutaric anhydride; phthalic 
anhydride; hexahydrophthalic anhydride; tetra hydrophthalic anhydride; 
methylhexahydrophthalic anhydride; substituted succinic anhydrides such as 
alkylenesuccinic anhydrides: octenylsuccinic anhydride, 
tetradecenylsuccinic anhydride, octadecenylsuccinic anhydride, 
5-norbornene-2,3-dicarboxylic anhydride, and maleic anhydride. 
The monoamines used in this invention are the linear or branched aliphatic 
alkoxypropylamines or alkoxyethylamines with a total carbon content per 
chain of between 6 to 30 carbon atoms. Preferred are the monoamines with a 
chain length of between 9 to 20 carbon atoms. 
Typical polyols that are used in the present invention include for example, 
trimethylolpropane, trimethylolethane, pentaerythritol, glycerine, but are 
not limited thereto. 
An exemplary condensation reaction between a .beta.-hydroxalkyl carbamate 
and trimethylolpropane is shown below: 
##STR7## 
The condensation reaction is conducted at a temperature of between about 
120.degree. C. and about 200.degree. C., preferably between about 
150.degree. C. and about 180.degree. C. The reaction is conducted under 
nitrogen or under a vacuum to facilitate the removal of glycol from the 
reaction of the .beta.-hydroxyalkyl carbamate with the polyol or from 
self-condensation. 
The self-condensation of a .beta.-hydroxyalkylcarbamate or the reaction 
with a hydroxyl group require the presence of a catalyst. Examples of 
suitable catalysts are strong bases such as the hydroxide of the alkali 
and earth alkali metals, transesterification catalysts such as the 
dialkyltin oxides, acetates, or laurates, zinc and lead salts. This is an 
illustrative list of the suitable catalysts and is by no means 
comprehensive. The catalyst is usually present in a concentration of 
approximately 100 ppm to 10000 ppm. For the condensation reaction to 
proceed it is essential that glycol such as the propylene glycol formed 
from the reaction of .beta.-hydroxypropyl carbamate with a hydroxyl group 
is removed by distillation, either by vacuum or by using an azeotropic 
solvent. A suitable vacuum is between 0-400 mmHg. Azeotropic solvents 
suitable for the removal of 1,2-propylene glycol are aliphatic and 
aromatic hydrocarbons. The endpoint of the reaction can be measured by 
determining the molecular weight by gel phase chromatography, viscosity, 
hydroxyl number or by a combination of these methods. 
In addition, solubility tests with hydrophobic solvents can be used to 
determine the extent of the reaction. To achieve water-dispersibility, a 
portion of the hydroxyl groups of the polyurethane polyol is reacted with 
an anhydride usually in the melt or in the presence of an aprotic solvent. 
To achieve the formation of the half ester of the anhydride and the 
urethane polyol a reaction temperature of 50.degree.-150.degree. C. is 
used, preferably between 80.degree.-130.degree. C. The reaction time is 30 
to 180 minutes, preferably between 60-120 minutes. The course of the 
reaction can by followed by acid number titration. This reaction is 
preferably base catalyzed with a t-alkylamine or an inorganic base, 
although it will also proceed in the absence of a catalyst. The resulting 
carboxyl and hydroxyl functional polymer is partially or completely 
neutralized with an amine and dispersed in water. To achieve 
water-dispersibility a carboxyl content of about 0.5 to 1.5 MEQ/g is 
required. It is generally desirable to keep the carboxyl content as low as 
possible to assure optimum in acid resistance properties. A higher acid 
number means an increase in the ionic charge on the polymer and shows 
improved solubility of the polymer. It is possible to replace 90-95% of 
the hydroxyl groups of the polymer with anhydride and achieve an 
essentially all carboxyl functional polymer. Such a polymer can be 
crosslinked with both melamine resins and also with epoxy resins. To 
disperse polyurethane in water, a base such as ammonia or a simple organic 
amine can be used. Examples for such amines are t-alkylamines and 
alkanolamines such as triethylamine, trimethylamine, dimethylethanolamine, 
dimethylpropanolamine, methyldiethanolamine; diisopropanolamine or primary 
alkyl amines such as ethylamine, propylamine, ethanolamine or 
propanolamine. These amines may be gaseous at room temperature such as 
ammonia or they can have a boiling point as high as 250.degree. C. Many of 
these amines will partially or completely evaporate during cure, some 
amines such as diisopropanolamine will co-react with the melamine resins 
and be incorporated into the polymer film. In addition, the reaction of 
the melamine resin with the carboxyl and hydroxyl groups of the polymer 
can be catalyzed with a strong acid catalyst such as a sulfonic acid. The 
carboxyl groups will catalyze the reaction of a polyol with a melamine 
resin. Temperatures of 150.degree. C. or higher are required for carboxyl 
groups to catalyze the reaction of a full aklylated melamine resins such 
as hexamethoxymethylmelamine (HMMM) with a polyol. 
Sulfonic acid catalyst can reduce the cure temperature to as low as 
80.degree. C. Typical acid catalysts used are well known in the art. These 
include p-toluene sulfonic acid, xylene sulfonic acids, dodecylbenzene 
sulfonic acid, dinonylaphthalene di and mono sulfonic acid and the amine 
and Lewis acid metal salts of these acids. The level of acid catalyst is 
about 0.2 to 3% on the solids of the coating. A high level of the acid 
catalyst may impair water resistance and corrosion resistance and are to 
be avoided. 
The coatings an be applied directly onto a metal substrate or onto a primed 
substrate. In automotive coatings, the metal is usually first alkali 
cleaned and then pretreated with iron phosphate or zinc phosphate and then 
electrocoated with a water-borne primer. The coating is baked at high 
temperatures and then the primer is sprayed with a filler to cover all 
metal imperfections. Then a base coat which determines the color and 
appearance of the car is applied. As a final coating, a clear coat is 
applied. The clear coat is also formulated with additives to improve the 
UV resistance of the coating, such as a UV absorber or a free radical 
scavenger such as hindered amine light stabilizer. This coating protects 
the car from UV radiation, acid rain and the environment. In less 
demanding applications the coating can be directly applied on the metal. 
Acid etch resistance is a critical problem for automotive coatings, because 
of the high performance requirements of these coatings. Rain in industrial 
areas may have a pH as low as 4. This low pH is predominantly a result of 
sulfuric acid and sulfurous acid formed by burning of sulfur containing 
fuel. Although it is highly diluted the acid becomes concentrated on the 
surface of the coating in areas may reach a pH as low as 1. This acid 
attack is especially a problem in area of high sun shine and UV radiation, 
when the surface of a car can reach temperatures as high as 65.degree. C. 
To simulate acid attack on exposure many complicated laboratory tests have 
been developed. Most of these complicated accelerated tests do not 
completely agree with results shown on actual exposure. 
It has been found that a simple spot test with 20% sulfuric acid at 
different temperatures gives an indication if a polymer coating is 
resistant to acid rain. This acid spot test is conducted in the laboratory 
by placing one drop of 20% sulfuric acid on a panel and heating the panel 
for 15 minutes to a temperature of 50.degree. or 60.degree. or 75.degree. 
C. For each acid spot test a panel is required. The test procedure can be 
simplified using a gradient oven. This oven is similar to a hot plate 
where the temperature is controlled. The different zones of the gradient 
oven are adjusted to 50.degree., 60.degree. and 75.degree. C. Three 
sulfuric acid spots are placed at appropriate positions on the panel. The 
panels are kept 15 minutes on the gradient oven. The temperatures of the 
panels are monitored with thermocouples. After exposure, the panels are 
washed with water and the surfaces are immediately examined. The rating 
scale is as follows: 
0--no visible attack; 
1--spot barely visible only in presence of moisture; 
2--slight surface haze visible in the absence of solvent, no discoloration; 
3--surface hazy, no discoloration; 
4--discoloration, surface swollen; 
5--Film attacked, partially dissolved. 
Besides automotive applications, there are other end uses where coatings 
with high chemical resistance are desired. These include aerospace 
coatings, coatings for laboratory instruments. 
The invention will now be described with reference to the followings 
non-limiting, examples. 
EXAMPLE 1 
Preparation of a Mono .beta.-hydroxyalkyl Carbamate from an 
Alkoxyalkylamine 
216 part by weight (1 mole) of a blend of C.sub.6 -C.sub.10 
n-alkoxypropylamine with an amine equivalent weight of 216 was charged 
into a suitable reactor equipped with stirrer, temperature control and 
nitrogen inlet. The reactor was flushed with nitrogen and 112 parts by 
weight (1.1 mole) of propylene carbonate was slowly added to the reactor. 
The reaction was exothermic and the temperature was controlled to below 
120.degree. C. The mixture is held at 120.degree. C. for 3 to 5 hours or 
until the amine content drops to below 0.15 MEQ/g. The resulting 
monocarbamate material was an amber viscous liquid and had a viscosity of 
142 cps at 25.degree. C. 
EXAMPLE 2 
Preparation of a Polyurethane Polyol 
1272 parts by weight (4 moles approximately) of the mono carbamate of 
Example 1 and 1072 parts by weight (8 moles) of trimethylolpropane were 
charged into a suitable reactor and heated under nitrogen to 160.degree. 
C. The solution cleared at about 70.degree. C. At this time 0.1 part by 
weight of KOH catalyst dissolved in 5 parts of methanol were added. Vacuum 
was applied and distillation started at about 28.5" of Hg. The temperature 
was slowly raised to 170.degree. C. and about 317 parts by weight of 
distillate, 1,2-propylene glycol, were collected. The reaction mixture was 
cooled to 150.degree. C. and 2550 parts by weight of a bis-hydroxypropyl 
carbamate of 2-methyl-1,5-pentanediamine were added. The reaction mixture 
was slowly heated to 175.degree. C. and vacuum was applied. About 460 
parts by weight of distillate were collected. The resin produced had an 
ICI melt viscosity of 4.9 Poise at 75.degree. C. The reaction was 
continued and an additional 538 parts by weight of distillate were 
collected. The ICI viscosity of the melt was 5.1 Poise at 100.degree. C. 
The mixture was cooled to 140.degree. C. and diluted with xylene to a 
nonvolatile content of 75.5% (60 minutes at 110.degree. C.) and a 
Brookfield viscosity of 16900 cps at 25.degree. C. The resin had a Gardner 
color of about 3-4. IR analysis of the distillate shows it to be 
predominantly 1,2-propylene glycol. 
EXAMPLE 3 
Preparation of a Polyurethane Polyol 
318 parts by weight (1.0 mole) of the monocarbamate of Example 1 was 
charged to a suitable reactor with 201 parts by weight (1.5 moles) of 
trimethylol propane. The mixture was heated under a nitrogen blanket to 
170.degree. C. Approximately 0.1 part by weight of potassium hydroxide 
dissolved in 1 part of methanol was added as a catalyst. Vacuum was slowly 
applied and approximately 110 parts of distillate were collected. In a 
second reaction step the thus formed alkyl urethane substituted 
trimethylolpropane was then reacted with 348 parts by weight (1.05 moles) 
of a bishydroxy-propylcarbamate of 2-methyl-1,5-pentanediamine. The 
reaction was continued at 160.degree.-170.degree. C. FIG. 1 schematically 
shows this reaction. Full vacuum was applied and about 179 parts of 
distillate were collected, which corresponds approximately to a complete 
reaction of the bishydroxyalkyl carbamate with the remaining hydroxyl 
groups of the trimethylolpropane. The reaction mixture was cooled to 
140.degree. C. and 150 parts by weight of xylene were charged. The 
resulting resin had a solids content of 78.6% and was completely soluble 
in xylene. Viscosity of this resin was about 50600 cps at 25.degree. C. 
EXAMPLE 4 
Comparative Example of Preparing a .beta.-hydroxypropyl Carbamate (Lacking 
an Ether Substituted Alkyl Side Chain) 
A primary alkyl amine was reacted with propylene carbonate to form the 
.beta.-hydroxypropyl carbamate. 185 parts by weight (1.0 mole) of 
dodecylamine was reacted with 112 parts of propylene carbonate following 
the instruction of Example 1. The resulting mono .beta.-hydroxypropyl 
carbamate had a residual amine content of 0.15 MEQ/g and was solid at room 
temperature. The melting point was approximately 40.degree.-50.degree. C. 
and the nonvolatile about 96.6%. 
EXAMPLE 5 
Comparative Example of Preparing a Polyurethane Polyol 
143 parts by weight (0.49 mole) of the .beta.-hydroxypropyl carbamate of 
Example 4 in molten form was charged into a suitable reactor. To the 
reactor, 134 parts (1 mole) of trimethylolpropane and 486 parts by weight 
(0.152 mole) of a bishydroxypropyl carbamate of 
2-methyl-1,5-pentanediamine were charged. In addition, 0.1 parts by weight 
of KOH catalyst dissolved in methanol were added. The reaction mixture was 
heated to 165.degree. C. and vacuum was applied. Reaction products were 
distilled over. The reaction temperature was slowly raised to 170.degree. 
C. A total of 215 parts by weight of distillate was collected. The resin 
melt was cooled to 140.degree. C. and 150 parts of xylene were added. 
Initially, on dilution with xylene, the resin was soluble in xylene. 
However, with further addition of xylene and cooling, the resin became 
insoluble. 
EXAMPLE 6 
Comparative Example of Preparing a Polyurethane Polyol 
Example 2 was repeated in all essential details but the 
.beta.-hydroxypropyl carbamate of Example 1 was replaced with an equal 
molar amount of the .beta.-hydroxypropyl carbamate of Example 4. The 
resulting resin was on completion diluted with xylene. This resin was 
soluble in hot xylene but started to crystallize on cooling to room 
temperature. 
EXAMPLE 7 
Coating formulation Nos. 1 and 2 were prepared with the polyurethane polyol 
of Example 3 and evaluated in Table 1. As cross-linker, a commercial grade 
of hexamethoxymethylmelamine (HMMM) (Resimine 747 of Monsanto) was used. 
The formulation was catalyzed with a commercially available dodecylbenzene 
sulfonic acid catalyst (NACURE 5076 from King Industries). 
TABLE 1 
__________________________________________________________________________ 
FORMULATION # 
1 2 
WEIGHT % WEIGHT % 
SOLIDS CHARGE SOLIDS CHARGE 
__________________________________________________________________________ 
Polyurethane Example 3 
79.0 122.1 84.0 122.1 
RESIMINE 747 20.0 25.8 15.0 18.2 
(HMMM) 
NACURE 5076 catalyst 
1.0 1.8 1.0 1.7 
2-Methoxypropylacetate 50.0 50.0 
TOTAL 100.0 199.7 100.0 192.0 
RESULTS 
SOLIDS % CALC 63.4 62.0 
VISCOSITY, CPS, 25.degree. C. 
357 349 
BONDERITE 1E 1000, iron 
phosphated cold rolled 
steel 
CURE SCHED 20 MIN 
100.0 110 120 150 100 100 120 150 
.degree.C. 
FILM TH. MIL 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 
APPEARANCE GLOSSY GLOSSY 
GLOSSY 
GLOSSY 
GLO GLOSSY 
GLOSSY 
GLOSSY 
KNOOP HARDNESS 
4.2 9.5 11.9 15.8 1.3 2.5 3.9 6.6 
PENCIL HARDNESS 
B-HB HB-F HB-F HB-F 3B-2B 3B-2B 2B-B 2B-B 
IMT DIR IN. LB 
160 60-80 
20-40 
20-40 
0-20 0-20 0-20 80-100 
REV IN. LB 160 140-160 
160 160 160 40-60 
80-100 
60-80 
MEK 2X RUBS 75 200 200 200 30 35 60 180 
CONICAL MANDREL 
ELONGATION, % 
31 31 2 2 31 31 31 31 
ACID ETCH TEST 
15' @ 50.degree. C. 1* 1* 
.sup. @ 60.degree. C. 2* 2* 
.sup. @ 75.degree. C. 3* 3* 
__________________________________________________________________________ 
*Acid Etch Rating see page 18 
EXAMPLE 8 
Coating formulation Nos. 3 and 4 were prepared with the polyurethane polyol 
of Example 3 and evaluated in Table 2. As cross-linker, a commercial grade 
of hexamethoxymethylmelamine (HMMM) similar to that used in Example 7 was 
added but at higher levels (Resimine 747 of Monsanto was used). The 
formulation was catalyzed with a commercially available dodecylbenzene 
sulfonic acid catalyst (NACURE 5076 from King Industries). 
TABLE 2 
__________________________________________________________________________ 
FORMULATION # 
3 4 
WEIGHT % WEIGHT % 
SOLIDS CHARGE 
SOLIDS CHARGE 
__________________________________________________________________________ 
Polyurethane Example 3 74.0 122.1 69.0 122.1 
RESIMINE 747 HMMM 25.0 34.5 30.0 44.4 
NACURE 5076 catalyst 1.0 1.9 1.0 2.1 
2-Methoxypropyl acetate 50.0 50.0 
TOTAL 100.0 208.5 100.0 218.5 
RESULTS 
SOLIDS % CALC 63.4 66.3 
VISCOSITY, CPS, 25.degree. C. 382.0 407.0 
BONDERITE 1000, iron phosphated coldold rolled steel 
CURE SCHED 20 MIN .degree. C. 
100 120 150 100 120 150 
FILM TH. MIL 1.0 1.0 1.0 1.0 1.0 1.0 
APPEARANCE EXCEL EXCEL 
EXCEL EXCEL EXCEL EXCEL 
KNOOP HARDNESS 4.2 9.5 11.9 1.3 2.5 3.9 
PEL HARDNESS B-HB HB-F HB-F 3B-2B 3B-2B 2B-B 
IMT DIR IN. LB 160 60-80 
20-40 
0-20 0-20 0-20 
REV IN. LB 160 140-160 
160 160 40-60 
80-MEK 
2X RUBS 75 200 200 30 35 60 
CONICAL MANDREL ELONGATION, % 
31 31 2 31 31 31 
ACID ETCH TEST 15' @ 50.degree. C. 1* 1* 
@ 60.degree. C. 2* 2* 
@ 75.degree. C. 3* 3* 
__________________________________________________________________________ 
*Acid Etch Rating see page 18 
EXAMPLE 9 
Comparative Example Using Acrylic Polymer 
As a comparative example for acid etch resistance, a high solids acrylic 
melamine resin crosslinked coating was prepared. A commercial grade of 
hexamethoxymethylmelamine (HMMM) (Cymel 303, American Cyanamid Co.) as a 
cross-linker was used. The formulation was catalyzed with a commercially 
available dodecylbenzene sulfonic acid catalyst (NACURE 5225 from King 
Industries). The formulation and evaluation results of Example 9 are shown 
in Table 3. The acrylic resin was a commercially available resin available 
from Rohm & Haas with following characteristics: Nonvolatile 84%; solvent 
n-butylacetate; viscosity, 6000-1000 cps Specific gravity 1.08; hydroxyl 
number (solids) 155; Acid number (solids) 5. This resin was designed 
specifically for low VOC high solids chemically resistant coatings. DISLON 
was a commercially available acrylic flow and leveling agent available 
from Kusomoto Chemical (Tokyo, Japan). 
TABLE 3 
__________________________________________________________________________ 
HIGH SOLIDS ACRYLIC/MELAMINE SYSTEM 
WEIGHT 
% RESIN 
CHARGE 
__________________________________________________________________________ 
ACRYLOID QR-1120 70.8 119.0 
CYMEL 303 28.2 39.9 
2-Methoxyproply acetate 20.0 
NACUURE 5225 0.5 2.8 
DISLON 1985-50 0.5 1.4 
(Flow agent) 
TOTAL 100.0 183.1 
RESULTS 
SOLIDS \% CALC 77.1 
VISCOSITY, CPS 220 
BONDERITE 1000, iron phosphate on cold rolled steel 
URE SCHED. 20 MIN .degree.C. 
120 150 
FILM TH. MIL 0.80 0.80 
APPEARANCE GLOSSY 
GLOSSY 
KNOOP HARDNESS 10.30 
13.50 
PENCIL HARDNESS HB-F H-2H 
IMT DIR IN. LB 60-80 
60-80 
REV IN. LB 0-20 0-20 
CROSSHATCH ADH. % 100 100 
MEK 2X RUES 140 200 
CONICAL MANDREL ELONGATION % 
31.3 15.8 
ACID ETCH TEST* 15' @ 50.degree. C. 
2* 2 
@ 60.degree. C. 
4 4 
@ 75.degree. C. 
5 5 
__________________________________________________________________________ 
*See page 18 
EXAMPLE 11 
Comparative Example Using a Polyurethane Polyol Without Hydrophobic Side 
Chains 
A polyurethane polyol was prepared by self-condensing a 
bis(.beta.-hydroxypropyl carbamate) of 2-methyl-1,5-pentanediamine. 2811 
parts by weight of above biscarbamate were charged into a suitable 
reaction vessel and catalyzed with 0.09 parts by weight of potassium 
hydroxide. The reaction mixture was heated to 180.degree. C. Vacuum was 
applied at 145.degree. C. and propylene glycol was distilled off. A sample 
was taken at a conversion corresponding to a dimer or a molecular weight 
of about 564. This material dissolved in 2-methoxypropyl acetate and had 
at a solids content of 85.3% and a viscosity of 14400 cps. The hydroxy 
content of the sample was 3.546 MEQ/g (milliequivalent) or a hydroxyl 
number of 198. This sample was designated A. The reaction was continued 
and a sample was taken at a conversion corresponding to a degree of 
polymerization of 3.07. This corresponds to a molecular weight of 822 and 
a hydroxyl content of 2.430 MEQ/g or a hydroxyl number of 136. This sample 
dissolved in 2-methoxypropyl acetate had a viscosity of 40400 cps at a 
solids of 89.1%. This sample was designated B. 
EXAMPLE 11 
A clear coat formulation No. 5 was prepared using the polyurethane polyol A 
according to Example 11 and described and evaluated in Table 4. This 
polyurethane was cross-linked with a commercially available HMMM 
cross-linker, Resimene 747 of Monsanto. The formulation was catalyzed with 
a dodecylbenzene sulfonic acid catalyst from King Industries. 
TABLE 4 
__________________________________________________________________________ 
FORMULATION # 
5 
WEIGHT % 
SOLIDS CHARGE 
__________________________________________________________________________ 
Polyurethane A EXP. 11 73.57 117.23 
Resimine 747 (HMMM) 25.43 35.28 
NACURE 5076 (DDBSA) 1.00 1.94 
2-Methoxypropyl acetate -- 60.00 
Silicone Surfactant (10\%) 3 DROPS 
TOTAL 100.00 214.46 
RESULTS 
SOLIDS \% CALC 63.39 
VISCOSITY, CPS, 25.degree. C. 
-- 192 
SOLIDS 20' 150.degree.C. -- 59.8 
BONDERITE 1000, iron phosphate on cold rolled steel 
CURE SCHED. 20 MIN, .degree.C. 
125 150 
FILM TH. MIL 1.00 1.00 
APPEARANCE GOOD GOOD 
KNOOP HARDNESS 23.0 29.0 
PENCIL HARDNESS 2H-3H &gt;5H 
IMT DIR IN. LB 20-40 20-40 
REV IN. LB 0-200 0-20 
CROSSHATCH ADH. % 0 25 
MEK RUBS 200 200 
ACID ETCH TEST* 15' @ 50.degree. C. 
5 5 
@ 60.degree. C. 
5 5 
@ 75.degree. C. 
5 5 
__________________________________________________________________________ 
*See page 18 
EXAMPLE 12 
A clear coat formulation No. 6 was prepared using the polyurethane polyol B 
according to Example 11. Formulation No. 6 is described and evaluated in 
Table 5. This polyurethane was cross-linked with a commercially available 
HMMM cross-linker, Resimine 747 of Monsanto. The formulation was catalyzed 
with a dodecylbenzene sulfonic acid catalyst from King Industries. The 
cross-linking level in this formulation had been adjusted to account for 
the lower hydroxyl number of the polyol. 
TABLE 5 
__________________________________________________________________________ 
FORMULATION # 
6 
WEIGHT % 
SOLIDS CHARGE 
__________________________________________________________________________ 
Polyurethane B EXP. 11 80.02 112.23 
Resimine 747 (HMMM) 18.98 24.21 
NACURE 5076 (DDBSA) 1.00 1.79 
2-Methoxypropyl acetate -- 60.00 
TOTAL 100.00 198.23 
RESULTS 
SOLIDS \% CALC 63.05 
VISCOSTY, CPS, 25.degree. C. 312 
SOLIDS 20' 150.degree. C. 60.2 
BONDERITE 1000, iron phphate on cold rolled steel 
CURE SCHED MIN, .degree.C. 120 150 
FILM TH. MIL 1.00 1.00 
APPEARANCE GOOD GOOD 
KNOOP HARDNESS 23.0 27.0 
PENCIL HARDNESS 2H-3H 4H-5H 
IMT DIR IN. LB 20-40 20-40 
REV IN. LB 0-20 0-20 
CROSSHATCH ADH. % 100 80 
MEK RUBS 200 200 
ACID ETCH TEST* 15' @ 50.degree. C. 
5 5 
@ 60.degree. C. 
5 5 
@ 75.degree. C. 
5 5 
__________________________________________________________________________ 
See page 18 
EXAMPLE 14 
Clear coat formulation No. 7 was prepared using the polyurethane polyol A 
according to Example 11. This polyurethane was cross-linked with a 
commercially available mixed methylate/butylated melamine cross-linker, 
Resimine 755 of Monsanto. This more hydrophobic cross-linker was reported 
to show improved acid etch resistance. The formulation was catalyzed with 
a dodecylbenzene sulfonic acid catalyst from King Industries. The 
cross-linking level in this formulation had been adjusted to account for 
the lower hydroxyl number of the polyol. 
TABLE 6 
__________________________________________________________________________ 
FORMULATION # 
7 
WEIGHT % 
SOLIDS CHARGE 
__________________________________________________________________________ 
Polyurethane A EXP. 11 68.59 117.23 
Resimine 755 30.41 45.23 
NACURE 5076 (DDESA) 1.0 2.08 
2-Methoxypropyl acetate 60.00 -- 
TOTAL 100.00 224.55 
RESULTS 
SOLIDS 20' 125 C. 54.4 
VISCOSITY, CPS 105 
SOLIDS % CALC 64.92 
BONDERITE 1000, iron phosphate on cold rolled steel 
CURE SCHED. 20 MIN 150.degree. C. 
FILM TH. MIL 1.00 
APPEARANCE GLOSSY 
KNOOP HARDNESS 34.00 
PENCIL HARDNESS 4H-5H 
IMT DIR IN. LB 0-20 
REV IN. LB 0-20 
CROSSHATCH ADH. % 10 
MEK RUBS 200 
ACID ETCH TEST* 15' @ 50.degree. C. 
5 
@ 60.degree. C. 
5 
@ 75.degree. C. 
5 
__________________________________________________________________________ 
See page 18 
EXAMPLE 14 
(Comparative Example) Polyester Urethane 
A polyester urethane polyol was prepared by condensing 
cyclohexanedimethanol (5 mole), a blend of dimethylesters of succinic 
(DMS), glutaric (DMG) and adipic acid (DMA), (DMS 22%, DMG 62% and DMA 
16%) (7 mole) and a bis, --.beta.-hydroxypropyl carbamate of 
2-methyl-1,5-pentane diamine (4.5 mole). The resulting product had a 
solids of 74.0% in xylene and a viscosity of 4000 cps at 25.degree. C. The 
hydroxyl number of the resin solids was 109. This polyurethane was 
cross-linked with a commercially available HMMM cross-linker, Resimine 747 
of Monsanto. The formulation was catalyzed with an amine blocked 
dodecylbenzene sulfonic acid catalyst from King Industries. The 
cross-linking level in this formulation had been adjusted to account for 
the lower hydroxyl number of the polyol. Formulation No. 8 using the 
polyester urethane of Example No. 15 is described and evaluated in Table 
TABLE 7 
__________________________________________________________________________ 
FORMULATION # 
8 
WEIGHT % 
SOLIDS CHARGE 
__________________________________________________________________________ 
Polyurethane polyol (Example 15) 
79.04 134.77 
Resimine 747 19.96 25.77 
2-Methoxypropyl acetate -- 15.00 
NACURE 5225 (DDBSA BL.) 1.00 5.06 
TOTAL 100.00 180.61 
RESULTS 
SOLIDS \% CALC -- 70.06 
VISCOSITY, CPS -- 302 
BONDERITE 1000 iron phosphate on cold rolled steel 
CURE SCHED0 MIN 120.degree. C. 
150.degree. C. 
FILM TH. MEL 0.80 0.80 
APPEARANCE GLOSSY GLOSSY 
KNOOP HARDNESS 1.8 3.5 
PENCIL HARDNESS HB-F HB-F 
IMT DIR IN. LB 160 160 
REV IN. LB 160 160 
CROSSHATCH ADH. % 10 5 
MEK RUBS 50 110 
MANDREL ELONGATION % 31.3 31.3 
ACID ETCH TEST* 15' @ 50.degree. C. 
1 0 
@ 60.degree. C. 
4 3 
@ 75.degree. C. 
5 4 
__________________________________________________________________________ 
*See page 18 
EXAMPLE 16 
(Preparation of an Urea and Urethane Group Containing Polyurethane Polyol) 
403 parts by weight of trimethylolpropane (3 mole) and 432 parts by weight 
of a isodecyloxypropylamine (1.8 mole) were blended with 1440 parts by 
weight of bis(hydroxypropyl) carbamate of 2-methyl-1,5pentanediamine. This 
blend was catalyzed with 0.3 gram of potassium hydroxide. The mixture was 
heated in a suitable reactor equipped with a nitrogen inlet and agitator 
to 150C. The temperature was slowly raised to 165C. The amine content of 
the reaction mix was measured. Initial titration gave a MEQ/g of 0.88, 
after a reaction time of 5 hours at 165.degree. C., the MEQ/g dropped to 
&gt;0.9. Vacuum was slowly applied to the reactor and full vacuum was slowly 
applied. A partial condenser was used to recycle any unreacted amine. 
Propylene glycol was collected as a distillate. 582 grams of distillate 
were collected, predominately propylene glycol. Amine titration of the 
final resin shows the resin to be essentially amine free. The resin was 
cooled to 130.degree. C. and diluted with 520 parts by weight of xylene. 
Example 16 is described, evaluated and used in Formulation Nos. 9 and 10, 
in Table 8. 
TABLE 8 
__________________________________________________________________________ 
FORMULATION 
9 10 
WEIGHT % WEIGHT % 
SOLIDS CHARGE 
SOLIDS CHARGE 
__________________________________________________________________________ 
Resime 747 (HMMM) 20.00 12.92 
15.00 9.11 
DodecylbenzeneSulfonic 1.00 0.90 1.00 0.95 
Acid (70%) 
2-Methoxypropanol 20.00 20.00 
TOTAL 100.00 100.00 
100.00 96.63 
RESULTS 
VISCOSITY, CPS 25.degree. C. 703 
BONDERITE 1000, iron phosphate on cold rolled steel 
CURE SCHEDULE 20 MIN, .degree.C. 
120 150 120 150 
FILM THICKNESS, MIL/MICRON 1/25 1/25 1/25 1/25 
RESIN EXAMPLE 16 79.00 66.67 
7 84.00 66.67 
APPEARANCE GLOSSY GLOSSY 
GLOSSY GLOSSY 
KNOOP HARDNESS 4.0 15.8 1.8 12.5 
PENCIL HARDNESS F-H 2H-3H 3B-2B H-2H 
ADHESION, \% 100 100 100 0 
MEK DRUBS 40 200 15 200 
IMT DIRECT, inch. lbs. 40-60 
100-120 
40-60 
IMT REVERSE, inch. lbs. 160 0-20 40-60 20-40 
HUMIDITY, CLEVAND, 65.degree. C. 9VF* 9VF* 
1000 HRS HARDNESS 2H-3H 2H-3H 
ACID ETCH TEST* 15' @ 50.degree. C. 
2 1 2 
@ 60.degree. C. 
5 2 3 
@ 75.degree. C. 
5 5 5 
__________________________________________________________________________ 
*Blister very few (VF), blister size ASTM ratio small (&lt;0.5 mm) 
**See page 18 
EXAMPLE 16 (water-dispersible) 
403 parts by weight of trimethylolpropane and 862 parts by weight of the 
hydroxypropyl carbamate of isodecyloxypropylamine (2.5 mole) and 800 parts 
by weight of the bis(hydroxypropyl carbamate) of 
2-methyl-1,5-pentanediamine were charged to a suitable reactor and heated 
to 150.degree. C. in the presence of 0.2 gram of potassium hydroxide 
catalyst. Vacuum was slowly applied and propylene glycol was removed as a 
reactant. About 460 parts of distillate was collected as the temperature 
was slowly increased to 170.degree. C. The final resin had a viscosity of 
40 Poise at 100.degree. C. 100 parts by weight of succinic anhydride were 
added to this reaction mixture and the mixture was held at 100.degree. C. 
for about two hours. The resin was then dispersed in water in the presence 
of dimethylaminoethanol. 
The water-dispersed polyurethane resin was formulated with HMMM 
cross-linker as showed in Example 16 and cured at 150.degree. C. The resin 
was 100% neutralized with dimethylethanolamine and dispersed hot in the 
absence of any solvent. The acid etch results were 1, 2 and 5 respectively 
at 50.degree., 60.degree. and 75.degree. C. 
FIG. 2 shows non-limiting examples of polymer chains in schematic with form 
from units such as, etheramine propylene carbonate, trimethylol propane 
urethane diol and, hydroxyl groups. FIG. 3 shows a polymer derived from a 
urethane diol, a polyol and an etheramine propylene carbamate. 
Although the invention has been described in conjunction with the specific 
embodiments, it is evident that many alternatives and variations will be 
apparent to those skilled in the art in light of the foregoing 
description. Accordingly, the invention is intended to embrace all of the 
alternatives and variations that fall within the spirit and scope of the 
appended claims. Further, the subject matter of the above cited United 
States Patents are incorporated herein by reference.