9 AMINO RESINS

The term amino resin is used to describe the range of amine condensation products such as urea-
formaldehyde, melamine-formaldehyde and others that are used in, among others, the surface coatings
industry. More correctly described, amino resins are products resulting from the reaction of
formaldehyde (HCHO) with an amino (-NH 2 ) containing compound and which undergoes later
reaction with an alcohol (R -OH).
Formaldehyde is a pungent gas under normal conditions, but it is handled as a solution in water
(Formalin) or in a suitable alcohol. Available as asolid, paraformaldehyde, which is a
polymerized form.
H
"C==ü Formaldehyde
H/

Urea is a white crystaHine solid ofmelting point 133 0 C. H is soluble in water, and made by the
high pressure reaction of carbon dioxide and ammonia.
H 2N
"C==ü Urea
/
H 2N
Melamine is 1,3,5, triamino 2, 4, 6, triazine, a white crystalline solid with a melting point of350° C.
It is insoluble in water. Made from nitrogen and calcium carbide via and intermediate,
cyanamide, N=C-NH 2

Melamine

The range of end uses for amino resins covers the fields of plastics and moulding compounds,
adhesives and surface coatings as weH as paper and textile treatments.
87

Oil and Colour Chemists’ Association, Australia, Surface Coatings

© Springer Science+Business Media Dordrecht 1983
88 SURFACE COATINGS

In surface coatings, the amino resins used are generally water white syrups used in baking or
thermosetting finishes. When used as a sole film former, they form a hard britde solid when baked.
When combined with other film formers, such as acrylic, alkyd or polyester resins, they produce
coatings with superior hardness, chemical resistance, baking speed and colour retention.
The introduction of amino resins allowed baking type drying-oil alkyd finishes, which
previously possessed a cure time of about I hour, to permit the present-day 20 minute bake and
allowed specialized high speed processes, such as coil coatings, to be produced with cure speeds of
30 seconds. An important area of development of amino resins at present is that of curing agents
for water based coatings. In surface coatings amino resins are classified as cross-linking or curing
agents.

9.1 FORMATION OF AMINO RESlNS

The reactions involved in the production of amino resins involve

(a) methylol formation; and
(b) alkylation
as weIl as some degree of polymerization.
9.1.1 Methylol FonnatioD
Amino containing materials such as urea and melamine will react with aldehydes (especially
formaldehyde) to produce a product termed a methylol:
-NHII + HCHO - -NH-CHlIOH
amme formaldehyde methylol amine
These products, usually water soluble, can be polymerized by heating. Urea and melamine
methylols differ in their behaviour and should not be considered together.

9.1.2 A1kylatioD
The methylol product is then modified to make it less polar and more organic-solvent soluble by
etherifying the compound with an alcohol to obtain an alkylated methyol product. Under the
conditions of alkylation (agitation and heating) a competing polymerization reaction also occurs.
The presentation of simple chemical formulae to illustrate the reactions involved are an aid to
understanding, and these are shown later. It must be stressed, however, that competing reactions
of condensation, polymerization and etherification can occur simultaneously. Control of the
reactions is obtained only by careful adjustment ofreaction conditions and ratio ofreactants.

9.2 UREA FORMALDEHYDE RESlNS

9.2.1 Methylol ConnatioD

Urea will react with up to three, but more usually with one or two, moles offormaldehyde, and,
depending on the choice of acid or basic conditions, different products are formed. Those formed
under acid conditions are insoluble products of no use in the coatings area. Methylol urea
formation is as shown on the following page.
Under slighdy basic conditions, at pH 7 to 8, the product formed, dimethylol urea, is a white solid
which is water soluble. This product may be polymerized by heating and concentrating under
vacuum and is the route taken for the production of moulding powders and adhesives. They are
unsuitable for coatings, for even though they form hard, britde films, they have poor solubility in
conventional paint solvents and are generally incompatible with potential plasticizing resins.