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Introduction/definition
Polyurethane coatings were originally defined as products made from polyisocyanates and polyols,
but today one defines it more broadly and includes all systems based on a polyisocyanate whether the
reaction is with a polyol, a polyamine or with water. This means that a PU paint may contain urethane,
urea, allophanate and biuret linkages. Polyurethane coatings have grown rapidly since they were first
introduced fifty years ago because of their highly versatile chemistry and superior properties particularly
as to toughness, resistance to abrasion and chemicals whilst also being flexible and adhering well to all
sorts of substrates.
There are four broad categories of PU technology used in the paint industry, the first three being reactive
systems and the fourth covering all systems with no isocyanate reaction during final application :
two-component systems consisting of a polyisocyanate and a polyol or polyamine that are mixed
just prior to application and curing at room temperature. In volume terms, this family accounts for
over half of all urethane coatings sold in the world.
oven-curing PUs are similar materials to the previous one, except that a blocked isocyanate is
used to provide a storage stable one-pack mix with the polyol or polyamine. The isocyanate is
then de-blocked when stoved and hence reacts. This includes powder coats, which consume now
over 10% of all urethane in paints.
moisture-cure PUs are one-component, high molecular weight and low free isocyanate containing
prepolymers that cure by reacting with moisture from the air to form urea linkages. This family of
coats represent roughly 5% of all urethane in paints.
The reactive polyurethane paints are generally crosslinked, due either to branched polyols and/or
isocyanates, or through formation of allophanate and biuret. Crosslinking - whilst increasing hardness and
abrasion resistance - improves the resistance to water, solvents, weathering and temperature. However,
they lead to poorer flexibility if too high a level is being used.
non-isocyanate reactive formulations encompass TPU-based lacquers, aqueous PU dispersions,
urethane oils and alkyds, and also radiation-cured polyurethanes. The latter contain urethane
or urea linkages. All just mentioned non-reactive systems have in common that isocyanates do
not react during application. This family of PU paints consume about 35% of all PU for paints.
How you choose raw materials for your Coatings Formulation?
The push for low VOC coatings led to the successfull launch of water-borne PU coatings, which
are today matching closely solvent-borne sytems both in terms of performance and overall
appearance. Those water-based recipes are now commonly used in transportation, machinery,
furniture and protective metal coating applications, whilst their high flexibility also makes them
applicable on polymeric and wooden substrates.
These 2K paints contain dispersable isocyanates and polyols, such as polyacrylates or polyesters
that are emulsifiable or soluble in water. The principal isocyanate is an HDI trimer but IPDI trimers
are also being used as is allophanate modified HDI. Aromatic grades are avoided because they
react too vividly with water. The hydrophobic isocyanate grades can be used as such or can
be emulsified by partial reaction with a hydrophylic polyol. Most water-based paint formulations
still need up to 10% solvent to make the polymer form a homogeneous film. The coat is cured
at temperatures ranging from 20°C to 80°C. To ensure adequate polymer network formation an
excess of isocyanate is added so as to compensate for the isocyanate consumed during the urea
reaction.
Formulations are presently available containing no solvent at all and they are predominantly
used in the building sector, where they are applied as sealants or coats for roofing and flooring
of car parks and also to protect against corrosion. Most of these systems are based on MDI and
polyether or oil-modified polyester polyols, chain extenders and catalysts. There is a very high
variety of recipes, with potlife ranging from a few minutes to more than an hour, and applicable at
temperatures as low as 5°C. Highly filled 2K systems are used as synthetic mortars for concrete
repair and as foundation material for heavy equipment. Spray elastomers were also developed for
use in belting and mining, for pipe linings and as protective membranes in construction.
Polyurea 2K polyurethane paints are an area of hectic development, and normally contain MDI
or IPDI or occasionally also TMXDI with a polyol being a polyoxyalkyleneamine or an amine-
teminated chain extender. The latter may be diethylene diamine (DETDA) or isophorone diamine
(IPDA). The polyurea reaction is particularly rapid hence no catalyst is needed. The outlets for
polyureas are more diverse than for conventional PU spray coats because of their fast cure
and specific characteristics. Polyureas end up in paints for pipes, freight ships, industrial floors,
transportation liners and roofs. They are attractive in products needing to be put back rapidly in
service after painting or where post cure is impossible or too costly.
Oven-curing or stoving systems
Stoving curing paints are obtained by blending a blocked isocyanate with a polyol to form a pseudo one-
component mix that it stable at ambient temperature. When heated to to its activation temperature (100-
200°C) the isocyanate unblocks and reacts with the polyol thereby forming the coat. Isocyanates - may
be aromatic or aliphatic - all contain one active hydrogen and contain a blocking agent most of the time
a caprolactam. Another method of blocking is to form uretidinedione or dimer links. As these coatings
are all baked at relatively high temperatures, their use is restricted to applications withstanding heating/
cooling cycles. In practice, their main use is for coating metals.
Solvent-based oven-curing coats
Typically used for high-speed paint processes as is the case for continuous coils of steel and
aluminium that are further processed by profilers making panels for construction, appliance and
transport industries. Coatings in this category require high flexibility and are typically applied in
a one-machine operation, with TDI commonly used for the base coat whilst the topcoat contains
an IPDI trimer. With HDI-based formulations both base and topcoat have the same isocyanate.
Polyols are predominantly polyester grades, acrylics and phenolics, as long as they resist
yellowing.
Water-based oven-curing coats
Water-borne systems are mainly used for coating of appliance and vehicles as primer or base
layer, to provide protection against corrosion and where needed against stone chips. These
recipes have dispersions of blocked aromatic isocyanates, usually modified with hydrohylic
components for emulsification and also polyester polyols or modified epoxies. The paint is
frequently applied through cathodic electrodeposition, sometimes referred to as EPD or e-coat,
and after drying the isocyanate is activated on stoving.
Powder coatings
High molecular weight linear polyurethanes are formed or dissolved in solvents. These PUs are
obtained through reacting aromatic or aliphatic isocyanates (mainly MDI and IPDI) with polyester
or polyether polyols and chain extenders. The PU polymer has molecular weight of up to 100,000
and has thus a fairly low solids content of no more than ten percent. The lacquers are brushed or
sprayed and their film is formed by evaporating the solvent. These films are reportedly extremely
flexible and elastic on top of being remarkably resistant to mild solvents. Their major outlets are
for topcoating of flexible substrates such as leather, fabrics, shoe soles and integral skin foam.
Another important application is for electronics, where they are used to coat magnetic tapes when
polyester polyol-based TPUs modified with sulphonate or phosphate groups are used to bind and
hold magnetic particles in the film.
Polyurethane dispersions
This will be the subject of a next coming article, because this family of products grows in
significance year after year. Let is just mention here that PUDs are fully reacted polyurethane
systems under the form of small discrete particles of maximum one tenthn of a micrometer.
These particles are dispersed in water to provide a material that is both chemically and colloidally
stable.
Urethane oils and alkyds
Natural oils such as linseed or soybean can be heated with polyols such as glycerol and
pentaerythritol. In that case, the reaction converts them to diglycerides and monoglyderides.
These hydroxyl-containing oils can then be reacted with isocyanates (TDI or IPDI) and thereby
form long chain hydroxyl-terminated polymers that can be dissolved in solvents. They are applied
by brush or spray and after solvent evaporation one obtains a film that crosslinks by air oxidation
of the unsaturated oils with the help of catalysts.
Urethane alkyds consist of an alkyd resin in which a portion of the dibasic acid (usually
phthalic acid) is replaced by a diisocyanate. Ester links are synthesised during the reaction by
polycondensation, and the isocyanate is added for reaction with the remaining hydroxyl groups
to form urethane linkages. Urethane alkyds are similar to traditional alklyds and may be drying
or non-drying. Above described urethane alkyds should be labelled "urethane-modified alkyds"
as urethane oils are often described as "urethane alkyds" or "urethane oil" and even "uralkyds".
They all exhibit better mechanical and weathering properties than unmodified alkyds, but are not
nearly as good as the other reactive PU paints. Main uses are in varnishes for flooring and boats,
undercoats and for industrial maintenance finishes.
Radiation curing
This family consists mainly of urethane acrylate coatings that are one-component, low viscosity
and hundred percent solids products. They normally are easy to apply and can be rapidly cured
by ultraviolet or ellectron beam energy sources at room temperature. Aromatic grades are used
in wood, paper, plastic and ink coats while aliphatic systems are utilised where non-yellowing is a
must, which is the case among other for PVC floor tiles and continuous flooring. The UV curable
urethane acrylates are also ending up in adhesives, sealants and potting or encapsulation
compounds.
The oligomer is obtained by reacting a prepolymer, obtained from diisocyanate and a polyether
or polyester polyol, with a stoichiometric amount of a hydroxyl-containing acrylate such as
hydroxypropyl acrylate. Urethane acrylate oligomers are usually blended with some acrylate
monomer such as tripropylene glycol diacrylate or trimethylolpropane ethoxylate acrylate as a
reactive diluent and a photoinitiator, for UV curing. Benzophenone is a typical photoinitiator which
produces free radicals when absorbing UV and then initiates the crosllinking through the acrylate
groups. EB is powerfull enough to eliminate the need for photoinitiators. The main difference
between UV and EB curing is that the electron beams penetrate thick and opaque film layers
whilst UV curing is restricted to clear or thin films.