MNL17-EB/Jun.

1995

Amino Resins (Reaction

Products of Melamine, Urea,
etc. with Formaldehyde and
Alcohols)
by J. O w e n Santer 1

INTRODUCTION

Definition and Description /

AMINO, OR AMINOPLAST,RESINS for coatings are the p r o d u c t s of
the r e a c t i o n of either urea (Fig. 1) o r m e l a m i n e (Fig. 2) with
f o r m a l d e h y d e a n d an alcohol. Besides u r e a a n d melamine,
o t h e r c o m p o u n d s with s i m i l a r f u n c t i o n a l i t y - - s u c h as
b e n z o g u a n a m i n e , glycoluril, e t c . - - a r e also used in specific
a p p l i c a t i o n s where certain p r o p e r t y advantages are required.
However, use of these m a t e r i a l s is quite limited, a n d sales of
a m i n o resins are d o m i n a t e d b y those b a s e d on u r e a a n d mela-
mine, with U.S. c o n s u m p t i o n of a b o u t 100 million lb (45 •
106 kg) p e r year.
As p r e p a r e d , a m i n o resins are usually water-white, viscous
m a t e r i a l s which m a y c o n t a i n a d d e d solvent to reduce viscos-
ity for ease of handling. W h e r e a solvent is used, it is m o s t
often an alcohol such as n-butanol, iso-butanol, o r iso-propa-
nol, all of w h i c h are excellent solvents for a m i n o resins.
Mixed solvents, such as n- o r iso-butanol with xylene are also
used, especially for the h i g h e r - m o l e c u l a r - w e i g h t resins m a d e
with b u t a n o l as a co-reactant. S o m e a m i n o resins are w a t e r
soluble or w a t e r reducible with co-solvent.
Amino resins for coatings are g r o u p e d s o m e w h a t a r b i t r a r -
ily into two classes: (1) high solids resins, i.e., resin solutions
at ---80% solids (weight/weight), including resins which con-
tain no solvent, a n d (2) conventional resins, i.e., resin solu-
tions at < 8 0 % solids (weight/weight).
History
Historically, the first a m i n o resins used in coatings were
the r e a c t i o n p r o d u c t s of u r e a o r m e l a m i n e with formalde-
hyde a n d b u t a n o l (either n- or iso-). They were substantially
p o l y m e r i c a n d were f o r m u l a t e d at a b o u t 50 to 60% solids in
butanol/xylene mixtures. They have been c o m m e r c i a l l y avail-
able for a b o u t 60 years. Parenthetically, it should be noted
that resins m a d e by reacting u r e a o r m e l a m i n e with formal-
d e h y d e w i t h o u t subsequent r e a c t i o n with an alcohol have
b e e n available for 70 years o r more. These resins are used as
m o l d i n g p o w d e r s a n d adhesives a n d are generally unsuitable
for coatings applications.
High-solids coating resins, usually m a d e with higher ratios
of r e a c t e d f o r m a l d e h y d e t h a n the older, conventional resins,
have been available for a b o u t 35 years. They are a l m o s t al-
1Principal technologist, Monsanto Chemical Co., 730 Worcester
Street, Springfield, MA 01151.
60
9
Copyright 1995 by ASTM lntcrnational www.astm.org
C=O
FIG. 1-Urea.
NH 2
FIG. 2-Melamine.
ways m a d e with m e t h a n o l or c o m b i n a t i o n s of m e t h a n o l a n d
butanol, a l t h o u g h a small n u m b e r of high-solids resins are
available which are m a d e exclusively with butanol.
Where Used
Amino resins are used in coatings to cross-link the p r i m a r y
film-former, usually a n acrylic, polyester, o r alkyd resin
carrying p r i m a r y o r s e c o n d a r y hydroxyl groups. The cross-
linking r e a c t i o n ("cure") is p r i n c i p a l l y one of trans-etherifica-
tion between hydroxyl groups on the p r i m a r y film-former
a n d alkoxymethyl groups on the a m i n o resin. In a d d i t i o n to
the trans-etherification reaction, the a m i n o resin a l m o s t al-
ways u n d e r g o e s self-condensation reactions.
The m a j o r b y - p r o d u c t s of the cure r e a c t i o n include m e t h a -
nol a n d / o r butanol, formaldehyde, a n d water. Cure t e m p e r a -
tures are in the range of 180 to 400~ (82 to 204~ for t i m e s
w h i c h vary from 20 to 30 m i n at the lower end of the t e m p e r a -
ture range to p e r h a p s only 30 s at the u p p e r end. An a c i d
catalyst m a y be used to accelerate cure, d e p e n d i n g on the
cure t e m p e r a t u r e a n d the p a r t i c u l a r a m i n o used. Claims have
been m a d e for a m i n o resin f o r m u l a t i o n s w h i c h cure at r o o m
t e m p e r a t u r e , but as far as is known, no such f o r m u l a t i o n s are
presently c o m m e r c i a l l y available.
Urea resins are less expensive t h a n m e l a m i n e resins, w h i c h
is u n d e r s t a n d a b l e given that m e l a m i n e is m a d e f r o m urea.
Urea resins are also faster curing t h a n m e l a m i n e resins, b u t
are m o i s t u r e sensitive a n d therefore not suitable for use out-
doors. They are used widely for w o o d finishing, e.g., furni-
ture, kitchen cabinets, a n d in paper, film, a n d foil applica-

tions. Wood and paper applications capitalize on the
relatively rapid cure of the urea resin since lower tempera-
tures must be used to avoid damage to the substrate. In some
wood applications, cure temperature is at or near ambient.
Melamine resins, on the other hand, find much b r o a d e r
application since they are not nearly as water sensitive as the
ureas. Perhaps the largest single use for melamine resins is in
automotive OEM (original equipment manufacture), where
the finished paint must stand up to extremes of temperature,
humidity, and the degradative effects of sunlight, etc, Mela-
mine resins are used also in coil coatings, metal containers,
etc. (see E n d U s e s o f A m i n o R e s i n s ) .
SYNTHESIS OF AMINO RESINS
Reactions of Synthesis
The synthesis of amino resins for coatings is a two-step
process. In the first step, the parent compound is reacted with
formaldehyde (methylolation reaction); in the second, the
methylolated intermediate is reacted with an alcohol (etheri-
fication reaction). Equations 1 through 4 exemplify the pro-
cess, with urea as the parent compound. Reactions with mel-
amine are analogous.
H2NCONH2 + CH2O ) H2NCONHCH2OH (1)
monomethylolurea
HaNCONHCH20H + CH20 ) content as it does a distinction between resin structures. The
HOCH2NHCONHCH20H (2)
dimethylolurea
HOCH2NHCONHCH20H + ROH )
HOCH2NHCONHCH2OR + H20 (3)
HOCH2NHCONHCH20R + ROH ) densation takes place during the synthesis, leading in the case
ROCH2NHCONHCH2OR + H20 (4)
bis(alkoxymethyl)urea
Reactions shown in Eqs 1 and 2 proceed quite rapidly when
catalyzed by either acid or base. Reactions shown in Eqs 3
a n d 4 take place only under acid conditions, with the rate of
reaction strongly pH dependent; the lower the pH, the faster
the reaction. All four reactions are equilibrium reactions.
Hence, the extent of the reaction is dependent on the charge
ratios of the various reactants and on whether or n o t the
reactions are driven by removal of by-products in order to
shift the equilibrium.
The reactions of melamine are similar to those of urea with
one exception. With urea, two of the four available hydrogens
are readily reacted with formaldehyde (Eqs 1 and 2), while
the remaining two hydrogens react more slowly and require
an excess of formaldehyde to force the reaction. With mela-
mine, on the other hand, all six hydrogen atoms may be
reacted with relative ease to give hexa(methylol)melamine.
The kinetics of the methylolation reactions of urea and
melamine have been studied extensively [1-7], but there is
nothing in the literature on the kinetics of the etherification
reaction. Although both of these reactions are superficially
straightforward, a number of other reactions may take place
which complicate the kinetics. These reactions are all self-
condensation reactions in which two or more molecules of
the parent species are joined together through either a
CHAPTER 8 - - A M I N O R E S I N S 61
>NCH2N< (methylene) or >NCH2OCH2N< (methylene
ether) bridge. The reactions leading to self-condensation may
be written as follows:
>NCH2OR + HN< ~ >NCH2N< + ROH (5)
R = H, alkyl
>NCH2OH + HOCH2N< ~ >NCH2OCH2N< + H20 (6)
The bridging groups in amino resins manufactured for
coatings applications are predominantly methylene ether
bridges. When formulated and cured, additional bridges of
both types may be formed; how many of each will depend on
factors such as the composition of the amino resin, cure
temperature, and catalyst level.
It can be seen, then, that a variety of amino resins may be
prepared, with properties which depend on such factors as
the choice of starting material, i.e., urea, melamine, etc., the
combining ratios of the various reactants, the choice of alco-
hol (or alcohols, if more than one is used), and the degree of
polymerization of the resin. The principal manufacturers of
amino resins for coatings typically offer a product line of 25
or more resins. A generalized composition of a typical mela-
mine resin is shown in Fig. 3.
Structure/Property Variations
The difference between conventional solids and high-solids
a m i n o resins represents not so much a difference in solids
conventional solids (<80%) resins are made from melamine
or urea reacted with relatively low levels of formaldehyde,
typically 1.5 to 2.0 tool for urea resins and 2.5 to 3.5 tool for
melamine resins, and etherified with either n- or iso-butanol.
Because of these low reaction ratios, considerable self-con-
of melamine resins to products with degrees of polymeriza-
tion (DP) ->3 and perhaps somewhat higher for the ureas.
Because of the relatively high polymer content, these resins
are viscous and must be reduced with solvent to less than 80%
to obtain a manageable viscosity.
Another, possibly the major, contributor to high viscosity is
the residual imino (>NH) and methylo] (>NCH2OH) groups
on the amino resin, which can form strong hydrogen bonds
with unshared electrons on nitrogen and oxygen.
The high-solids amino resins have much higher levels of
combined formaldehyde than the conventional solids resins.
Typical values for combined formaldehyde are in the range
2.0 to 2.7 for urea resins and 3.5 to 6.0 for melamine resins.
The etherifying alcohol is most often methanol, although res-
ROCH2\ /CH2OH
ROCH2./N"'~NI~N'H
N. N
N
ROCH2/ "CH 2 0 ' ' 9
FIG, 3-Representative structure of a mela-
mine resin,
62 PAINT AND COATING TESTING MANUAL
ins made with both methanol and butanol or even butanol
alone are also widely used. These resins are less polymeric,
with DP <3, and usually more fully etherified and so less
polar than the conventional resins. In some cases, these res-
ins are sufficiently low in viscosity that no solvent is needed.
Where solvent is required, it is usually either isopropanol or
butanol (n- or iso-). Resins are also made which can be
reduced with water.
Analysis/Analytical Methods
Structural analysis of amino resins has been reviewed by
Christensen [8 ]. Methods discussed include 1H NMR and 13C
NMR for determining levels of combined formaldehyde and
alcohol, analysis of alkoxy groups by Zeisel cleavage, and by
trans-etherification followed by gas chromatography. Chris-
tensen [8] and Kambanis and Rybicky [9] also describe non-
destructive methods for removing solvent from amino resin
solutions in order to determine nonvolatile content.
Classically, amino resins for coatings have been character-
ized by three test procedures. These procedures, which tell
the coating formulator most of what he needs to know with
regard to formulation and cure conditions, are measurement
of (1) solids content, (2) viscosity, and (3) solvent tolerance.
These are discussed below.
Solids Content
The most common methods used to determine solids con-
tent are gravimetric. Solvent is allowed to evaporate from a
weighed sample under carefully controlled conditions of time
and temperature. The sample is then reweighed. The loss in
weight gives a measure of solvent content, and the solids
content is obtained by difference. One difficulty with this test
is the tendency of amino resins to deformylate and/or self-
condense when heated, with evolution of formaldehyde, alco-
hol, and water. To the extent that this occurs, the measured
solids content will be lower than the "true" value. Frequently,
however, the paint formulator is interested in the "contrib-
uted solids," i.e., what fraction of the amino resin solution
remains in the cured film. In that case, a solids test method
which approximates the time and temperature of cure might
be more appropriate.
For these reasons, solids test methods fall into two groups:
(1) methods which reflect the solids content in the absence of
self-condensation, etc., and (2) other methods, which reflect
varying degrees of self-condensation in addition to loss of
formaldehyde and solvent(s).
The most common of the first methods is the so-called foil
solids test, which is used almost universally for high-solids
amino resins. Essentially, a 1-g sample of resin solution is
weighed onto a piece of preweighed aluminum foil. The foil is
folded over on itself and the sample compressed between the
two foil surfaces to provide a thin film about 3 to 4 in. (7 to 10
cm) in diameter. The foil is then opened up to give a thin film
on each foil surface. The foil is placed in a 45~ oven for 45
min, at the end of which time it is removed, reweighed, and
the solids content calculated. These conditions are known to
be sufficiently mild that no resin condensation occurs; nor
does the resin lose formaldehyde via demethylolation. Sur-
prisingly, the foil solids test may on occasion overestimate
the solids content, particularly when (1) the resin is relatively
polar, i.e., carries appreciable > N H and >NCH2OH groups,
and (2) the solvent is not low boiling. Apparently, the increase
in viscosity as solvent evaporates slows the diffusion rate and
effectively prevents complete removal of solvent within the
time frame of the test. There may also be a hydrogen-bonding
effect between solvent and resin which contributes to the
retention of solvent.
Other test methods involve much higher temperatures,
where resin condensation/degradation does occur. One stan-
dard method is the ASTM Test Methods for Volatile Content
of Coatings (ASTM D 2369), where a small resin sample (0.3
to 0.5 g) is diluted with xylene and placed in a 110~ oven for
1 h. There are a number of other, similar tests.
Viscosity Measurement
Amino resin viscosities are most commonly measured by
the Gardner bubble viscometer method. This method is simi-
lar to the Test Method for Viscosity of Transparent Liquids by
Bubble Time Method (ASTM D 1545). A tube containing the
resin under test is placed in a rack containing reference tubes
of known viscosity. The tubes are equilibrated to 25~ in a
constant temperature bath. The rack is quickly inverted, and
the rate of rise of an air bubble in the sample tube is com-
pared against similar bubbles in the reference tubes. The
reference tubes are letter graded A through Z and Z1 through
Z6.
Solvent Tolerance
There are a number of different solvent tolerance tests. All
involve titrating a weighed sample of the amino resin with a
standard reagent (solvent). The object of the test is to mea-
sure how much of the reagent the amino resin can accept
before the solution turns cloudy/milky. Results are typically
reported in milliliters of reagent per gram of sample. Typical
reagents used include xylene, iso-octane, and the iso-octane/
decahydronaphthalene/toluene mixture described in ASTM
Test Method for Solvent Tolerance of Amine Resins (D 1198).
While the immediate objective of the solvent tolerance test
is to determine the amount of reagent which the amino resin
can accept before solution clouding occurs, the real purpose
of the test is to gain insight into the structure and composi-
tion of the resin and hence have a better understanding of
how it will perform in a given coating application. In general,
amino resins of high molecular weight, or having high levels
of polar functional groups, i.e., >NH, >NCH2OH, will have
limited compatibility with the typical hydrocarbons used and
hence will give low tolerance test results. Experience shows
that a low tolerance value means a faster curing resin and vice
versa, especially in the absence of acid catalyst. However,
although the tolerance test represents a quick and easy way to
measure potential cure response, it does not uniquely define
the resin structure. Thus, a low tolerance reading can be
caused by either high polarity or high molecular weight or
both.
Size Exclusion and High-Performance Liquid
Chromatography
To obtain more detailed knowledge of resin structure,
amino chemists now rely very heavily on gel permeation or
size exclusion chromatography (SEC) and on high-perform-
ance liquid chromatography (HPLC). The size exclusion
 CHAPTER 8--AMINO RESINS 63

chromatograph provides an excellent measure of number
and weight-average molecular weight and molecular weight
distribution (polydispersity), while HPLC, which fractionates
the resin components primarily by functional groups, pro-
vides information on resin composition. The more polar spe-
cies are eluted first, followed by the less polar fractions. Thus,
taken together, SEC and HPLC provide detailed information
on molecular weight and functionality which cannot be di-
rectly obtained or inferred from any of the various solvent
tolerance tests. Size exclusion and liquid chromatograms for
a representative commercial high-solids methylated mela-
mine resin are shown in Figs. 4 and 5.
Combining Ratios
Amino resins may also be characterized by measurement
of the amounts of formaldehyde and alcohol which have re-
acted. For example, see hexa(methoxymethyl)melamine
(HMMM) (Fig. 6), which has exactly 6 mol each of combined
formaldehyde and methanol per mole of melamine. Unlike
HMMM, most resins are, of course, mixtures of products
which are best described by an average composition. One of
the most widely sold commercial high-solids methylated mel-
amine resins has an average combining ratio melamine/form-
aldehyde/methanol of about 1/5.6/5.1. Because methanol re-
acts with an already-reacted formaldehyde molecule, a resin
can never have combined methanol greater than the com-
bined formaldehyde. The excess formaldehyde, 0.5 tool in
the commercial example, represents formaldehyde which
has not reacted with methanol and which must therefore
be present as methylol (>NCH2OH), bridging groups
(>NCHzOCH2N<), and acetals (>NCH2OCH2OCH3). Acetals
are formed when an excess of formaldehyde is used in the

400 -
mV Monomer
350 -
300 -
I
250"~

200 - Dimer
150 ~

100-

50 -

20 25 30 35 40 45

Minutes
FIG. 4-Size exclusion chromatogram of a typical high-solids methylated mela-
mine resin.

600"-
mV
500- Hexamethoxy

400 - Penta-
methoxy
350-

200 -
Tetra-
I A I
100-

0 -
20 25 30 35 40 45 50

Minutes
FIG. 5-High-performance liquid chromatogram of a typical high-solids methylated
melamine resin.
64 PAINT AND COATING TESTING MANUAL
(C H 30C H2)2N...h/N__,h/N(CH 20C H 3)2
II I
N.~N
N(CH2OCH3)2
FIG. 6-Hexa(methoxymethyl)melamine.
synthesis. They are therefore present in many high-solids
amino resins.
Determination of combining ratios may be done most eas-
ily by either IH or 13C NMR techniques [8]. Older methods
involve complete hydrolysis of the resin to the starting mate-
rials, followed by wet-chemical analysis for formaldehyde
and gas chromatographic determination of alcohol (metha-
nol or butanol).
Free Formaldehyde
Amino resins always contain some unreacted formalde-
hyde, usually referred to in product specifications as "free"
formaldehyde. Free formaldehyde may be analyzed quantita-
tively by a number of methods. One of the most commonly
used is the sodium sutfite method [10]. Formaldehyde reacts
rapidly and completely with aqueous sodium sulfite to form a
bisulfite addition complex. Sodium hydroxide is liberated
quantitatively on a mole-for-mole basis
CH20 + Na2SO3 + HaO ~NaOH + CHa(OH)NaSO3 (7)
The NaOH is either titrated directly with a standard HC1
solution, or neutralized with a known excess of standard HC1,
which is then back-titrated with NaOH. Care must be taken to
ensure that reacted formaldehyde, particularly methylol
groups, is not analyzed as free formaldehyde. This can occur
because of the following reaction, which can be minimized by
performing the titration as rapidly as possible at cool temper-
atures, e.g., room temperature or lower.
>NCH2OH ) >NH + CHaO (8)
PHYSICAL PROPERTIES
General
Amino resins are typically viscous liquids, with an amine-
like odor. Depending on composition, they may also smell of
formaldehyde and/or solvent. They are readily soluble in alco-
hols, ketones, hydroxy-functional glycol ethers, esters, etc.,
but have limited solubility in hydrocarbons. Some resins,
especially methylol-rich resins with low levels of both com-
bined formaldehyde and combined methanol, are water solu-
ble. Many more are water reducible in the presence of other
solvents, e.g., alcohols and glycol ethers.
Because of their resinous nature, aminos have neither a
well-defined freezing point nor boiling point. Uncured resins
typically have glass transition temperatures around -40~
When heated, they undergo decomposition, with release of
formaldehyde and alcohol, at temperatures above about
140~ This tendency to decompose causes difficulties in de-
termining the solids content of resin solutions, as described
in Analysis/Analytical Methods. The problem is particularly
acute with resins having high methylol functionality.
Viscosity
The viscosity of an amino resin is a function of (1) polymer
content (degree of polymerization) and (2) the nature of its
functional groups. The latter may be a more important con-
tributor to viscosity than the former.
Amino resins are not generally very polymeric, especially in
comparison with other coating resins, e.g., polyesters, alkyds,
and acrylics. Typically, average degrees of polymerization are
in the range of I to 5. High-molecular-weight "tails" increase
viscosity significantly.
Because of strong hydrogen bonding, resins carrying sig-
nificant amounts of >NH and >NCH2OH functionality are
quite viscous, even though they may not be highly polymer-
ized. There is a marked drop in viscosity when amino resins
are diluted with solvent, largely due to breaking of hydrogen
bonds. Good solvents (e.g., alcohols) are more effective at
reducing viscosity than poor ones [11 ]. Methanol is probably
the best, although it is not widely used because of its low
boiling point. Isopropanol is almost as effective, and because
it is somewhat higher boiling, represents a good compromise.
Surface Tension
The surface tension of amino resins is quite strongly re-
lated to the nature of the etherifying alcohol and is much less
affected by the level of combined formaldehyde and alcohol.
In the author's laboratory, surface tension measurements on
high-solids, solvent-free resins using a DeNouy tensiometer
have given values ranging from about 45 dynes/cm for meth-
ylated resins to about 28 dynes/cm for butylated resins. Mixed
methyl/butyl resins give intermediate values, depending on
the methyl and butyl content. The reduction in surface ten-
sion vghen butanol is the etherifying alcohol may be one rea-
son that high-solids butyl and methyl/butyl resins provide
improved flow and leveling in high-solids formulations com-
pared to their fully methylated counterparts.
REACTIONS OF AMINOS IN COATINGS
Cure Reactions
Amino resins in coating formulations cure by reactions
which are chemically and mechanistically similar to those
which take place during synthesis of the resin. The principal
reaction of cure is one of trans-etherification, wherein a hy-
droxyl group on the primary film-former (acrylic, polyester,
or alkyd) reacts with an alkoxymethyl group on the amino
resin
>NCH2OR + HO--A ~ >NCH20--A + ROH (9)
where
R = alkyl, and
A = primary film-former.
Additionally, direct etherification may take place, the end
result being the same
 CHAPTER 8 - - A M I N O R E S I N S 65

>NCH2OH + HO--A ) >NCH20--A + H20 (10) enced by heat. The trans-etherification reaction takes place
very rapidly under strong acid catalysis, even at low tempera-
where
tures. This is especially true for aminos with a high level of
A = primary film-former. alkoyxmethyl substitution, i.e., a very low NH content, which
tends to inhibit catalysis. Thus, most formulations involving
These two reactions both result in chemical bond forma-
tion between the amino and the primary film-former (co- resins with high alkoxymethyl ether content and designed for
condensation). Two other reactions may also take place, both low-temperature cure (250~ or lower) will call for a sulfonic
acid catalyst, either blocked or free.
of which involve reaction of the amino resin with itself (self-
condensation). These are Although the individual reactions of cure are reasonably
well understood and have been described in numerous pa-
>NH + ROCHzN< ) >NCH2N< + ROH (11) pers [13-18], there is still much to be learned about the overall
where behavior of amino resins during cure, in particular the rela-
tive contributions of each of the various reactions. One of the
R = H, alkyl. difficulties is, of course, that the coating becomes intractable
>NCH2OH + HOCH2N< ) >NCH2OCHzN< + H20 (12) as cure progresses. Hence, a majority of studies involve analy-
sis of the by-products of cure [13,17,30]. Other methods, such
Besides the co-condensation and self-condensation reac- as dynamic mechanical analysis [19], nuclear magnetic reso-
tions, hydrolysis and deformylation reactions may also occur nance [20,21], FTIR [17], ESCA, etc. investigate the structure
>NCH2OR + H20 ) >NCHzOH + ROH (13) of the cured film.
These techniques are useful not only for analyzing the
>NCH2OCH2OR + H20 ) >NCH20H + CH20 + ROH (14) freshly cured coating, but also as a means of following the
>NCHzOH ~ >NH + CH20 (15) coating through its lifetime, either natural or accelerated.

The relative contributions to cure of the co-condensation and

self-condensation reactions will depend on a variety of fac- Degradation and Weathering
tors. These include:
Amino-based cross-linked coatings exposed to the atmo-
1. The functionality of the amino resin, i.e., the relative pro-
sphere are subject to both hydrolysis and UV-degradation.
portions of >NCH2OR, >NCH2OH, and >NH groups pres-
The mechanisms by which melamine resins hydrolyze have
ent initially, as well as those generated during formulation
and/or cure. been described in detail by Berge [22-24], who was the frst to
2. The functionality (hydroxyl number) of the primary film- distinguish between mono- and di-substituted nitrogen with
former (coreactant). respect to their behavior towards acid or base hydrolysis.
3. The amino/coreactant ratio. Thus, in an alkaline medium, hydrolysis of an alkoxymethyl
4. The level and type of catalyst (weak acid/strong acid). group on a singly substituted nitrogen is initiated by removal
5. Cure time and temperature. by the base of the proton attached to nitrogen
A coreactant resin with a low hydroxyl number is best if --NHCH2OR + B ) --I~ICH2OR + BH § (16)
formulated with a "polar" amino (i.e., one rich in >NH and/or
--NCH2OR ) - - N = CH2 + OR- (17)
>NCH2OH) since these groups help build molecular weight
during cure via self-condensation, particularly if little or no - - N = CH2 + H20 ) --NHCH2OH (18)
catalyst is present. Conversely, a high hydroxyl resin is best if
OR- + BH + ) ROH + B (19)
matched with an alkoxymethyl-rich amino and cured with a
strong acid catalyst. Where high cure temperatures are em- This mechanism is clearly not applicable to di-substituted
ployed (e.g., can or coil coating operations), the choice of nitrogen (N(CH2OR)2), and these groups are in fact extremely
amino resin is less obvious, and, in practice, both polar and resistant to alkaline hydrolysis.
nonpolar aminos are used. On the other hand, acid hydrolysis takes place readily for
Acid catalysts are usually used as an aid in curing amino- both mono- and di-substituted nitrogen. Berge proposed two
based formulations. These catalysts include very strong mechanisms (a) specific acid catalysis
acids such as p-toluenesulfonic acid (PTSA), dodecyl-
>NCH2--OR + H + :, >NCH2OHR + (20)
benzenesulfonic acid (DDBSA), dinonylnaphthalenedi-
sulfonic acid (DNNDSA), etc., and weaker acids such as phe- >NCH2OHR + ) >NCH~- + ROH (21)
nyl acid phosphate (PAP), butyl acid phosphate (BAP), etc.
> N C H f + H20 ) >NCH2OH + H + (22)
Amine blocking agents are sometimes used to help minimize
resin advancement prior to cure. Some coatings, particularly and (b) general acid catalysis
those designed for high-bake temperatures, need no catalyst,
>NHCHzOR + HA ) >NCH2OHR + + A- (23)
relying instead on the combination of high temperature and
perhaps carboxylic acid functionality on the primary film- >NHCH2OHR + + A- ) >N = CH 2 + ROH + HA (24)
former to bring about cure [12]. While all of the various
- - N = CH 2 + H20 ) --NHCHEOH (25)
reactions which take place during cure are accelerated by
either acid or heat, it is fair to say that reactions of Berge's work with melamine resins is undoubtedly relevant
transetherification are most influenced by catalyst level and to acid hydrolysis of paint films, which has been studied by a
type, while reactions of self-condensation are most influ- number of workers.
66 PAINT AND COATING TESTING MANUAL
English et al. [25,26] found that coatings prepared from
highly alkylated melamines underwent extensive hydrolysis
of residual methoxy groups during two years exposure in
Florida, but there was no evidence of hydrolysis of bonds
between melamine and the primary film-former. Bauer [27-
28] used IR to analyze acrylic-melamine coatings exposed to
both UV and moisture and found evidence of hydrolysis of
both residual methoxy groups and acrylic-melamine bonds,
with the rate of hydrolysis being faster in the presence of UV
light. The rate of hydrolysis was slowed considerably when a
hindered amine light stabilizer was used.
In recent years, degradation of melamine-containing auto-
motive coatings has been particularly severe because of etch-
ing and spotting due to "acid rain." The problem is com-
pounded because modern high-solids automotive coatings
use very high levels of melamine resins (35 to 45% of total
binder weight), giving rise to correspondingly high levels of
acrylic-melamine bonds and residual alkoxymethyl groups in
the cured film, all of which are susceptible to hydrolysis
under acid conditions. Suppliers of high-solids coatings for
automobiles are presently evaluating and using alternative
cross-linkers, such as isocyanates and epoxies, which are
more stable under acid rain conditions and which can serve
as either a partial or complete replacement for melamines. An
interesting aspect of the acid etch problem is that the damage
always occurs to relatively new coatings. If a newly painted
automobile is protected from the acid environment for the
first six to twelve weeks, damage thereafter is much less
severe. An obvious conclusion is that the paint is undergoing
additional cure (probably melamine self-condensation) as it
ages.
Automotive paint manufacturers are also actively pursuing
waterborne systems, which use higher molecular weight, less
functional coreactant resins, and lower levels of melamine
cross-linker and which are therefore less severely degraded
by acid rain. At the present time, however, these waterborne
systems are only used in the base coat, where acid attack is in
any case minimized by the protective clear top coat. It is the
top coat, with its high melamine content, which is the princi-
pal site for acid attack. But it is also the high level of mela-
mine resin which provides the excellent gloss and "distinct-
ness of image" (DOI), characteristic of basecoat/clearcoat
technology. The melamine resin also minimizes the amount
of solvent required because of its low viscosity at high-for-
mulated solids, behaving in some ways as a reactive diluent
and plasticizer.
E n d Uses o f A m i n o R e s i n s
Amino-based surface coatings protect and decorate the
substrate to which they are applied. Their technology and use
has developed over many years. As already mentioned, resins
based on urea and melamine dominate the field. Urea resins
are traditionally used in clear coatings for wood, e.g., furni-
ture, kitchen cabinets, in paper, film, and foil applications,
and in some appliance and general industrial coatings. They
are also used to some extent in automotive primers. They
cannot be used in automotive topcoats because of their sensi-
tivity to hydrolysis.
Melamine resins are much more widely used. They give
better chemical resistance, as well as resistance to weathering
in exterior applications, despite some of the recent difficulties
described earlier in connection with water spotting and acid
etch of automobiles. Besides automobiles, they are used in
appliance formulations (both coil appliance and conven-
tional post-sprayed), general metal applications, container
coatings (beer and beverage cans), etc.
In choosing an amino resin for a particular application,
consideration must be given not only to interior versus exte-
rior use, but also to possible restrictions on cure conditions
and compatibility of the amino resin with its co-reactant
resin, both when formulated and as the paint film is formed
during solvent flash-off and cure, etc. Compatibility of the
amino is especially important in water-borne coatings, which
are becoming more widely used. Another factor is the stabil-
ity of the amino towards advancement (molecular weight
buildup) during storage of the formulated paint.
Benzoguanamine-based (Fig. 7) amino resins are used
where film flexibility and hardness are required, as in some
appliance applications (e.g., refrigerator doors made from
coil stock, etc.). They also have good corrosion and humidity
and detergent resistance. Their use is limited by cost and poor
exterior durability due to the pendant phenyl group on the
benzoguanamine molecule.
Glycoluril (Fig. 8) resins have been available for about a
dozen years. They may require a higher cure temperature or a
higher catalyst level than melamine-based resins, but show
excellent corrosion and humidity resistance and release
lower amounts of formaldehyde during cure [29].
ENVIRONMENTAL/TOXICITY
The past 20 years have seen increased emphasis on the
quality of the environment both in the workplace and beyond.
In the coatings industry, this has meant strict controls on
exposure of workers to hazardous ingredients in the coating
formulation when applied, as well as on the nature and
.2.yN.yN.2
FIG. 7-Benzoguanamine.
H H
"N~ ~'N ~
H H
FIG. 8-Glycoluril.

a m o u n t s of volatile organics (the so-called VOCs) released to
the e n v i r o n m e n t w h e n the f o r m u l a t i o n is cured.
Amino resin suppliers have r e s p o n d e d to these environ-
m e n t a l challenges in a n u m b e r of ways. Chief a m o n g these
has been a progressive shift t o w a r d s higher-solids, lower-
molecular-weight aminos, w h i c h are n o w the resins of choice
of coatings formulators. M a n y a m i n o resins are supplied at
100% nonvolatiles, especially for the a u t o m o t i v e industry.
W h e r e solvents are needed, those presenting the least h a z a r d
to w o r k e r a n d e n v i r o n m e n t are selected. F o r their part, p a i n t
p r o d u c e r s have i n c r e a s e d the functionality of the c o r e a c t a n t
resin while lowering its m o l e c u l a r weight to m i n i m i z e solvent
use with the object of b u i l d i n g m o l e c u l a r weight to the maxi-
m u m possible extent d u r i n g cure. This has m e a n t using
h i g h e r levels of a m i n o resin, as m u c h as 40 to 50% of total
b i n d e r weight in s o m e cases.
Perhaps the m o s t i n t r a c t a b l e e n v i r o n m e n t a l p r o b l e m with
a m i n o resins is the use of f o r m a l d e h y d e in t h e i r m a n u f a c t u r e .
F o r m a l d e h y d e is r e c o g n i z e d b y the I n t e r n a t i o n a l Agency for
R e s e a r c h on Cancer (IARC) as a carcinogen. The A m e r i c a n
Conference of G o v e r n m e n t a l I n d u s t r i a l Hygienists (ACGIH)
lists f o r m a l d e h y d e as an "A2" substance, i.e., one suspected of
carcinogenic potential for m a n , a n d the O c c u p a t i o n a l Safety
a n d Health A d m i n i s t r a t i o n (OSHA) has set w o r k p l a c e expo-
sure limits of 0.75 p p m (8-h t i m e w e i g h t e d average) a n d 2
p p m (15-min s h o r t - t e r m exposure limit).
The f o r m a l d e h y d e content of a m i n o resins is p r e d o m i -
n a n t l y "combined," i.e., chemically reacted, a n d r e p r e s e n t s
a b o u t 30 to 50% by weight of the resin. A small a m o u n t ,
ranging from a b o u t 0.1 to a b o u t 3% is present free, o r un-
r e a c t e d (see the section entitled A n a l y s i s / A n a l y t i c a l Meth-
ods). Amino resin suppliers have m a d e c o n s i d e r a b l e progress
over the p a s t several years in lowering the level of free formal-
d e h y d e in their products, w h i c h is i m p o r t a n t b e c a u s e of
OSHA labelling requirements.
In an ideal situation, all of the c o m b i n e d f o r m a l d e h y d e
w o u l d r e m a i n in the coating after cure as p a r t of the p o l y m e r
network, In practice, however, some of the c o m b i n e d formal-
dehyde a n d all of the free f o r m a l d e h y d e is released d u r i n g
cure a n d m a y r e a c h the environment, d e p e n d i n g on the me-
chanics of the coating a n d curing operation. It is the p a r t i a l
release of c o m b i n e d f o r m a l d e h y d e d u r i n g cure w h i c h is of
m o s t concern, since the a m o u n t released c a n easily be several
times t h a t of the free formaldehyde. I n c i n e r a t i o n of off gases,
w h e r e possible, is the best solution.
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CHAPTER 8 - - A M I N O R E S I N S 67
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