A Review of Two Component Water Borne Polyurethane

A Review of
Two-Component
Water-Borne Polyurethane
Coatings for
Industrial Applications
by S.L. Bassner and C.R. Hegedus
Air Products and Chemicals, Inc.
ndustrial maintenance coatings systems

have evolved through a number of
stages over the last several decades. For
many years, many standard systems utilized
solvent-borne vinyl wash primers and coatings based on chlorinated rubbers.1 Until
the 1970s, alkyd resin systems, filled with
red lead and iron oxide, had been perhaps
the most popular choice for conventional,
high solvent content, heavy-duty maintenance applications. As volatile organic
compound (VOC) content has been restricted and the use of lead-containing pigments
has been eliminated, epoxy-based primers
and urethane topcoats have become widely
used for heavy-duty applications. The
epoxy primers, filled with zinc or utilizing
various barrier pigments, have inherently
good chemical resistance. The exceptional
durability of the urethane topcoat provides
long-term gloss and color retention while
protecting the integrity of the corrosion-resistant primer.
Pushed by environmental concerns,
development has continued today toward
52 /
Journal of Protective Coatings & Linings
high performance, water-borne coatings

for heavy-duty maintenance applications.
This review article addresses the development of two-component, water-borne
polyurethane coating systems. These coatings consist of an isocyanate, often modified to improve its water dispersibility,
mixed with a dispersion of a hydroxyl
functional polymer (Fig. 1).
This article first describes the basics
of urethane chemistry and the types of urethane systems used in industrial maintenance applications. After a discussion of
the solvent-borne, two-component urethane benchmark, this article describes formulation, application, and performance of
two-component water-borne systems developed thus far. Once these systems have
been described, formulation and application difficulties associated with two-component water-borne polyurethanes are addressed. The article ends with comments
on the state of the art in reactive waterborne urethanes and areas of current and
future development.
Copyright 1996, Technology Publishing Company
Developments in Water-Borne Urethanes
Urethane Chemistry
The isocyanate functionality, -N=C=O, can
react with a number of different functional
groups at ambient temperature, as shown
in Fig. 2. The reaction of isocyanate with
hydroxyl functionality forms a urethane
group, while reaction with amine functionality forms a urea group. One of the most
usefuland troublesomereactions of isocyanates is with water. The reaction of isocyanate with water first forms an unstable
carbamic acid. This intermediate slowly decomposes to amine, releasing carbon dioxide. The amine that forms reacts rapidly
with additional isocyanate to form a urea
group. At higher temperatures or with appropriate catalysis, isocyanate groups also
will react with urethane and urea groups to
form allophanate and biuret structures, respectively. Isocyanates also undergo trimerization, forming an isocyanurate ring structure (Fig. 3).
One of the most useful aspects of urethane chemistry, which encompasses all of
these reactions, is the breadth of the structural variations that can be used. A variety
of different polymeric backbones can be
functionalized with the isocyanate group,
while a large number of NCO-reactive materials (mainly hydroxyl and amine groups)
are available for use.
For example, isocyanate groups can
be attached to aromatic rings, cycloaliphatic
rings, or linear aliphatic structures. Hydroxyl groups can be used to functionalize
acrylic, polyester, or poly-ether polymers
(Fig. 4). Because of this wide variety, urethane coatings can be formulated to be
elastomeric or rigid, ultraviolet light stable,
highly chemical resistant, hard but tough,
all within a wide range of formulated
cost/performance specifications.
Fig. 1 - Isocyanate
dispersed in a polyol
dispersion yields a
two-component waterborne polyurethane.
Figures courtesy of the
authors
The Solvent-borne,
Two-Component Benchmark
The sections above have presented a
general introduction to polyurethane chemSEPTEMBER 1996
/ 53
Fig. 2 - Typical reactions of isocyanates: with hydroxyl

to form urethane groups; with amine to form urea groups; with
water to form an unstable carbamic acid, which dissociates
to form amine and carbon dioxide (this amine then reacts
with more isocyanate to form urea groups).
Figures courtesy of the authors
Fig. 3 - Generalized polyisocyanate structures
istry. Before discussing the development

of two-component water-borne technology for weatherable topcoats, it is first
necessary to describe the related solventborne benchmark.
For industrial maintenance applica-
54 /
tions, urethanes are most often used as solvent-borne, single-component, moisturecuring primers or two-component (2K) topcoats. The moisture-curing primers utilize
polyurethane prepolymers that are formed
by reacting an excess of a diisocyanate
such as toluene diisocyanate (TDI) or
methylene diphenylisocyanate (MDI) with a
polyether polyol.
These prepolymers, which have reactive isocyanate groups, are then formulated
with sacrificial pigments such as zinc dust,
or barrier pigments such as aluminum or
micaceous iron oxide. Upon application,
the isocyanate groups react with ambient
moisture, as shown in Fig. 2, ultimately
forming urea groups. These single-component primers are known for their fast curing
characteristics and flexibility.2,3
Two-component, solvent-borne topcoats are based on either a polyisocyanate,
such as an isocyanate trimer4 (Fig. 3), or an
isocyanate-terminated prepolymer.5 Both of
these materials are derived from aliphatic
diisocyanates, such as isophorone diisocyanate (IPDI) or hexamethylene diisocyanate (HDI).
The co-reactant with these isocyanates, when used in weatherable topcoat applications, is usually an acrylic polyol or a polyester polyol.
These high-performance, two-component systems are also known for rapid cure
and flexibility, as well as exceptional gloss
and long-term gloss and color retention.
This type of coating is also used indoors in
concrete floor applications, often with a
chemical-resistant polyester polyol co-reactant, to give durable, high gloss, wear-resistant coatings.
With this wide range of available reactants, polyurethane topcoats can be formulated within a full spectrum range of
performance characteristics. There are,
however, some general performance characteristics common to these systems. These
are described below.
Formulation and Application of 2K

Solvent-borne Polyurethane Coatings
In 2K, solvent-borne polyurethane coatings,
all pigments, fillers, additives, and solvents
are added to the co-reactant side, because
of the sensitivity of isocyanates to water.
These coatings are most often formulated
with a slight excess of isocyanate (NCO/
OH = 1.05-1.2) to ensure that all the polyol
is reacted. The remaining isocyanate groups
react with ambient moisture over time to ultimately form urea groups, which tend to
incrementally improve film properties such
as hardness and chemical resistance.
In polyisocyanate-cured formulations
(Fig. 3), volume mix ratios typically vary
from around 3:1 (co-reactant to isocyanate)
to around 6:1. In prepolymer cured formulations, the mix ratios are more often 1:1 or
2:1 because of the higher equivalent weight
of the prepolymer. Usable pot lives for
these formulations range from over 8 hours
for the older, high VOC formulations (>360
g/L [3.0 lbs/gal.) to around 2-4 hours for
low VOC formulations ( 360 g/L [3.0
lbs/gal.]). While applicators must contend
with a defined pot life, urethane coatings
are known for their ease of application and
relatively rapid cure under a wide range of
conditions. Most solvent-borne industrial
maintenance topcoats applied today range
from 420 g/L (3.5 lbs/gal.) VOC down to a
low of 335 g/L (2.8 lbs/gal.) VOC. The
practical limit of solvent-borne urethane
coatings for these applications appears to
be around 240 g/L (2.0 lbs/gal.) VOC.
Coating Properties of 2K
Solvent-borne Polyurethanes
Table 1 lists a set of typical properties for a
weatherable topcoat. Note that these are
only typical ranges and do not represent
the limits obtainable of these properties. Of
importance are the rapid cure times, high
gloss, excellent chemical and solvent resistance, good hardness with good flexibility,
and long-term gloss and color retention.
Fig. 4 - Structures of common isocyanates (top) and

generic polyols (bottom) used in industrial maintenance
coatings
Current 2K Water-borne
Polyurethane Systems
Water-borne polyurethanes have been
available for some time as single component, fully reacted polymers, modified
with carboxylic acid functionality to make
them water dispersible. These single-component polyurethane dispersions, or PUDs,
have found use in applications where
toughness combined with flexibility is important, such as in synthetic leather coatings and in coatings for plastics. While
PUDs offer many of the performance advantages of reactive urethane coatings, they
do not provide the high level of performance required in most heavy-duty industrial maintenance applications.
SEPTEMBER 1996
/ 55
Table 1
Properties of a Typical Two-Component,

Solvent-Borne Urethane
Property
Typical Value (Test Method)
Tack Free Time
2-4 hours (ASTM D 1640)
Pencil Hardness
HB-2H (ASTM D 3363)
Persoz Pendulum Hardness
150-300 seconds (ASTM D 4366)
Adhesion to Treated Steel
5B (ASTM D 3359)
Impact Resistance
80-160 inch-lb (ASTM D 2794)
MEK Double Rubs
200+ (ASTM D 4752)
Resistance to Common Solvents

and Dilute Acids and Bases
Excellent (Spot Test)
60 Degree Gloss
95+ (ASTM D 523)
Gloss Retention (2,000 hrs, UV-B)
70-90 percent (ASTM G 53)
Two-component, water-borne
polyurethane systems are a relatively recent
development. The remainder of this review
will discuss the various types of systems
that have been developed as well as areas
for improvement in application and performance. Note that a number of these systems have been developed for applications
other than industrial maintenance (e.g.,
wood coatings, aerospace), but their relevance to the development of systems suitable for industrial maintenance applications
is apparent.
After an introduction, this section will
be broken down into materials and formulation, application characteristics, and properties and property development.
Introduction2K Water-borne
Polyurethanes
As with the solvent-borne versions, twocomponent water-borne polyurethane coatings consist of a polyol and a multi-functional isocyanate. (Further detail is
provided below.) These materials have
been used in a number of high performance coating applications, including industrial maintenance, automotive,
aerospace, plastic, and wood coatings.6-11
56 /
The popularity and importance of these

coatings are growing significantly because
of their potential for providing excellent
performance properties, equivalent to those
of their solvent-borne counterparts, combined with a low VOC content. Most current water-borne formulations have a VOC
content of less than 250 g/L (2.1 lbs/gal.);
the leading technologies have been used to
develop zero-VOC coatings. (See State of
the Art section.)
Materials and Formulations2K
Water-borne Polyurethanes
The polyol dispersion in these coatings can
be from the acrylic, polyester,
polyurethane, or alkyd families. In all of
these cases, hydroxyl functionality is required in the polymer for reaction with the
isocyanate. For example, the hydroxyl
functional polyurethane dispersion is made
by reacting a difunctional isocyanate with a
low molecular weight diol and a bishydroxyfunctional carboxylic acid. Hydroxy functional acrylic dispersions are obtained by
including both acrylic acid and hydroxy
acrylates in the polymerization reaction.
Isocyanate cross-linkers for these
systems are typically based on conventional aliphatic isocyanate hardeners, primarily HDI with a biuret, isocyanurate,
or uretdione structure (Fig. 3). Cycloaliphatic (i.e., IPDI) versions also have
been used but they tend to be less compatible with water-borne polyols and have
higher glass transition temperatures (Tg)
than linear isocyanates, making film formation more difficult. In the most common
cases, these isocyanates have been modified with ethylene oxide and propylene
oxide to render them hydrophilic and thus
water dispersible.
However, the more traditional isocyanates, which generally are hydrophobic,
have been used more recently in specially
designed systems. The hydrophilically-modified versions generally have both lower
functionality and glass transition temperature than their unmodified counterparts.

This is because the hydrophilically-modified versions have increased molecular
weight without increased reactive groups.
Use of these modified polyisocyanates results in applied coatings with increased
free volume and molecular mobility, and
with lower Tg and cross-link density. Consequently, these films can be more susceptible to organic solvents and other chemicals, decreasing their swell, stain, and
etch resistance.
Although these are water-borne materials, both the polyol dispersion and the
isocyanate components often contain organic solvents to improve compatibility,
viscosity, manufacturing and application
properties, or film formation. Using the
latest technology, coatings that display
excellent properties have been formulated and applied with no added solvent
for thinning.12
In the formulation of 2K reactive coatings, stoichiometry of the admixed coating
(i.e., NCO/OH ratio) plays an important
role in the properties of the cured coating.
Two-component, solvent-borne polyurethanes are typically formulated at stoichiometries ranging from 1.05 to 1.2. In this
case, a slight excess of NCO ensures complete reaction of the polyol and the desired
high level of properties. In contrast, 2K
water-borne polyurethanes are formulated
at NCO/OH stoichiometries ranging from
1.5 to 3.0. Due to the substantial amount of
water in these systems, some of the isocyanate will inevitably react with water. A
large excess of isocyanate is needed to ensure that all of the polyol will react into the
cross-linked polyurethane system. If this reaction did not occur, coating properties
would be diminished because of unreacted,
low molecular weight, thermoplastic polyol
in the applied coating. Poor mechanical
and chemical resistance properties would
be the result.
Two critical issues with these 2K

water-borne polyurethanes are the viscosity
relationship between the polyol dispersion
and the isocyanate, and the compatibility
between these 2 components. Mixing liquids with similar viscosities is much easier
and more efficient than mixing liquids with
substantially different viscosities. In most
cases, the polyol dispersions have viscosities in the range of 100-400 cps. As a result,
isocyanates with a viscosity within or close
to this range are preferred.
The second issue concerns compatibility between the isocyanate and polyol
particles. Upon mixing, both the isocyanate
and polyol are in a dispersed state. For
the required reaction to occur, isocyanate
and polyol particles must mutually coalesce
by the diffusion of 1 particle into another.
For this to occur, the 2 different components must be compatible and have molecular mobility. Coalescence, then, becomes
more difficult with higher Tg or less compatible materials.
Organic solvents have been used to
address both of the above issues. Solvents
can be mixed with the isocyanate to form a
solution that reduces viscosity and increases molecular mobility and isocyanate-polyol compatibility. For example, IPDI trimer
is generally less compatible with the typical
polyols used in these applications and
therefore generally requires the use of additional co-solvent.
Of course, this has the undesired side
effect of increasing VOC. Commonly used
solvents are acetates (e.g., methoxy propyl
acetate, butyl acetate) and ethers (e.g.,
propylene glycol ethers). Taking this
approach, coatings can be formulated
with organic solvent content of 8 percent
to 12 percent by weight and VOC of less
than 300 g/L (2.5 lbs/gal.). Solvent levels
of 150 to 200 g/L (1.25 to 1.67 lbs/gal.)
are common.
In addition to improving reactant
compatibility, co-solvents help film formaSEPTEMBER 1996
/ 57
Table 2
Comparison of Water-Borne vs
Solvent-Borne Polyurethane Coatings
for Industrial Applications8
Water-Borne
Solvent-Borne
Solvent content (percent by weight)
5-12
40-60
VOC (g/L)*
300
500
Gloss 60 degrees/20 degrees
92/80
95/85
Appearance
very good
very good
Cross cut test on steel or electro

deposition primer (GT)
0-1
Erichsen (proprietary) indentation

tester (mm)**
8-10
8-10
Tack free dry time (hrs)
3-5
2-4
ASTM D 4366, Method A, Knig

pendulum hardness (sec)
130-160
170-200
Solvent resistance
good
good
* grams/liter=pounds/gallon of VOC x 119.8

** 1 mm=40 mils
Editors Note: Not all test methods are reported
tion, addressed in more detail later. They

also can have an effect on optical properties (gloss and haze) and property development. For example, less compatible co-solvents can decrease gloss and increase haze.
We have also found that compatible, low
vapor pressure co-solvents decrease hardness. This is probably caused by the solvents extremely low vapor pressure and
slow release from the film, causing them to
be a fugitive plasticizer. This plasticization
can also have a negative effect on chemical
and solvent resistance.
The effects of other additive formulating aids (wetting agents, flow and leveling
aids, defoamers, rheology modifiers, light
stabilizers, and catalysts) depend on the
specific systems, desired properties, and
application scenario. Selection of additives
is much more critical than in solvent-borne
systems, and it seems that additives play a
much larger role in attaining acceptable
coatings. Catalysts can be used but are generally not required. Traditional tin catalysts
are common.
58 /
As with solvent-borne polyurethanes,

pigmentation is included in the polyol
component. Most available publications
describing 2K water-borne polyurethane
coatings provide high gloss white formulations with titanium dioxide pigment. Jacobs
and McClurg7 provided a low gloss gray
formulation designed for aircraft applications. The literature has proclaimed (and
we have seen in our laboratory) that
with the use of appropriate dispersants
and dispersion procedures, pigment compatibility and stability in these systems
are excellent.
Application Characteristics
2K Water-borne Polyurethanes
Since these are 2K reactive coatings with a
defined pot life (up to several hours), the 2
components must be mixed just before application. The mixing process is made more
difficult by the fact that the applicator is
not simply mixing 2 solutions, but dispersing 1 component (the isocyanate) in the
continuous phase of a second component,
the polyol dispersion.
Most of the available literature describes manual mixing; however, twocomponent (in-line) mixing also has been
reported. At this stage of coating preparation, similarity in the viscosities of the reactive components is critical. As stated previously, liquids of dissimilar viscosity are
difficult to mix, while those of similar viscosity will mix much more readily. Therefore, the formulator must adjust the composition of the 2 components to increase
mixing efficiency.
Kahl and Bock6 reported that the
compatibility of the polyol and isocyanate
also has a dramatic effect on mixing of
these co-dispersed systems. They found the
best results in mixing, application, and performance with hydrophilically-modified,
linear isocyanates. Hydrophobic isocyanates could also be used but required
additional amounts of co-solvents to imCopyright 1996, Technology Publishing Company
Table 3
Evaluation Test Results of the Two-Component

Water-Borne vs Solvent-Borne Topcoats13
Property
Water-Borne
prove compatibility. Consequently, a decreasing amount
Wet Paint
of solvent was required to obVOC at application viscosity (g/L)*
148
tain acceptable polyol-isoCo-solvent at application viscosity
7
cyanate compatibility.
(percentage by weight)
The preferred method
NCO to OH ratio (percent)
150
with manual mixing is to slowSolid content (percentage by weight)
60
ly add the isocyanate compoApplication viscosity (sec DIN Cup r)
30
nent into the polyol compoDust-dry time (hrs:min)
4:15
nent. This causes a noticeable
Tack-free time (hrs:min)
7:30
viscosity rise due to emulsificaTNO drying
phase 1 (hrs:min)
0:15
tion of the isocyanate. Water is
phase 2 (hrs:min)
1:30
phase 3 (hrs:min)
2:00
then added slowly to reduce
phase 4 (hrs:min)
6:30
the viscosity to suit the desired
application scenario. Bock
Dry Paint
and Petzoldt11 reported that
Film thickness (m)
42
improvements in gloss, hardHardness Persoz/Knig, ASTM D 4366,
281/142
after 7 days at room temperature
ness, and chemical resistance
Haze (Haze Units), ASTM D 4039
19
were obtained by increasing
the shear used in the disperGloss 20 degrees (Gloss Units)
81
sion process.
Gloss 60 degrees (Gloss Units)
85
Theoretically, this should
Appearance
OK
decrease the particle size of
Adhesion
Gt 2
the dispersed isocyanate. It is
Erichsen indentation (mm)**
9
suspected that as with latex
Conical mandrel (diameter in mm),
0
dispersions, smaller particle
ASTM D 522
size results in improved film
Impact face/reverse (kgcm)
>105
formation because of enXylene resistance 5 min after
OK
7 days at room temperature
hanced diffusion of polymers
across particle boundaries. In
Yi (yellowing index)
-0.1
the case of the 2K system, this
Wi (whiteness)
93
will enhance coalescence and
* grams/liter=pounds/gallon of VOC x 119.8
further promote the iso** 1 mm=40 mils
cyanate-polyol reaction.
Note that in newer, high
solids systems described later
in this article, the polyol itself
emulsifies the isocyanate.
This eliminates the need for
evaluated for a number of high performodified isocyanates as well as the
mance applications. Each of these applicaneed for co-solvents. (See State of the Art
tions has unique performance requiresection below.)
ments, and formulation of 2K water-borne
urethanes can be tailored to meet specific
Properties and Property
needs. Certain properties of the waterDevelopment2K Water-bornes
borne polyurethanes are consistent across
As previously mentioned, 2K water-borne
these application scenarios. The pot life of
polyurethanes have been developed and
Solvent-Borne
501
43
150
56.7
20
4:00
7:30
35
322/196
6
91
93
OK
Gt 0
>9
0
>105
OK
-1.2
91
SEPTEMBER 1996
/ 59
Table 4
Property Comparison of Solvent-Borne vs

Water-Borne Clearcoats and Topcoat9
was observed to be softer
with a lower Tg (30 C versus
MEK 2X Rubs
200+
200+
200+
100+
49 C) than the solvent-borne
Pendulum Hardness (sec)
170
23
134
120
analog. Of course, the hardness and Tg of the waterReverse Impact (in. lbs)
160
160
160
160
borne could be increased
Tensile Strength (psi)*
4900
6200
5755
by altering the polyol, isoElongation (percent)

<5
150
10
cyanate, or the NCO/ OH ratio

60 Degree Gloss
>90
>90
>90
85
of the formulation.
Increasing isocyanate conA = Solvent-borne HDI polyisocyanate and highly functional polyester (clear)
B = Solvent-borne HDI polyisocyanate and tri-functional polyester (clear)
centrations from 1.5 up to 3
C = Reactive 2K water-borne system (clear)
does affect coating properties.
D = Reactive 2K water-borne topcoat (pigmented)
Wingerde and Brinkman13
* 1000 psi=6.895 MPa
found that increasing
NCO/OH from 1.0 to 2.0 increases hardness and water
resistance. (They recommend
NCO/OH of 1.5 or higher.)
Our
work
indicated
similar relationships:
these admixed coatings typically ranges
from 1 to 4 hours. Pot life is affected by the increasing the NCO/OH ratio led to increased hardness and chemical resistance
surfactant/emulsifier, compatibility between
with decreased flexibility and toughness.
the isocyanate-polyol, and catalyst. GenerAn NCO/OH of 1.5 was optimal for indusally, pot life is longer with improved emultrial maintenance applications.
sification and compatibility. As expected,
In developing coatings for aircraft
formulations without catalyst tend to have
topcoats, Jacobs and McClurg7 found once
longer pot life and shorter dry time.
again chemical resistance increased and
Bittner and Ziegler8 investigated
flexibility decreased with increasing
water-borne versus solvent-borne 2K
NCO/OH ratios ranging from 1.5 to 3.5.
polyurethane coatings for industrial mainteThey found that an NCO/OH of 3.0 was
nance applications. They formulated an
optimal for this application. Additionally, as
acrylic polyol dispersion with an HDIthe NCO/OH ratio increases, formulation
based polyisocyanate. VOC was 300 g/L
cost typically increases due to higher cost
(2.67 lbs/gal.) for their water-borne materiof the isocyanate component relative to the
als versus more than 500 g/L (4.2 lbs/gal.)
for the solvent-borne analog. They reported polyol component.
Wingerde and Brinkman13 also utiexcellent overall properties for both syslized an acrylic polyol dispersion with an
tems (Table 2) and concluded that both
HDI-based polyisocyanate to formulate
coatings displayed acceptable gloss, apclear and pigmented industrial coatings.
pearance, hardness, adhesion, and flexibiliOnce again, the coatings were comparable
ty for these applications. Using hardness
(Table 3) except that the water-borne coattesting, solvent resistance testing, and difings (clear and pigmented) were slightly
ferential scanning calorimetry, they found
softer than their solvent-borne counterparts.
that the water-borne coating reached ultiThe pigmented water-borne coating had
mate properties within 1 day (at ambient
slightly lower gloss than the pigmented solconditions) while the solvent-borne coating
vent-borne coatings. Lower gloss with pigtook up to 14 days.
mented water-borne coatings is relatively
However, the water-borne coating
Formulation
60 /
Table 5
common due to film formation issues (discussed below) and pigment dispersion effects, though again, the newer higher solids
systems are an exception.
Jacobs and Yu9 formulated industrial
coatings using a hydroxy-functional
polyurethane dispersion with a hydrophilic
(water-dispersible) HDI trimer. Once again,
properties of both clear and pigmented formulations were comparable with control
solvent-borne formulations (Table 4) when
applied and cured at typical laboratory conditions (e.g., 23 C [73F], 55 percent RH).
They also found property development of
the water-borne version to be relatively
fast. Solvent resistance, impact resistance,
and hardness reached ultimate levels in 2
days. Tg reached its ultimate level in 3
days, and tensile strength was reached in
4-5 days.
Jacobs and Yu did report that extremes in temperature and humidity during
curing had substantial effects on properties.
At higher humidity (e.g., 90 percent RH),
properties were reduced. This reduction is
caused by water remaining in the film
longer, favoring the isocyanate-water reaction. Increasing temperature up to 31-38 C
(88-100 F) can help overcome this effect
by helping to drive the water from the system and promote coalescence of the polyol
and isocyanate.
Other Applications of 2K Water-borne
Polyurethane Coatings
Two-component, water-borne polyurethanes have been investigated for use in
other coatings applications, such as automotive6,11, aircraft7, and wood finishing.10
Bock, et al.11, have evaluated these systems for automotive coatingsexterior
clearcoats, primer surfacers, base coatings,
single layer topcoats, and soft feel coatings.
For exterior clear coats, they evaluated
acrylic and polyurethane polyols and mixtures of both, cross-linked with hydrophilically-modified HDI trimer. They found that
Properties of High Solids Pigmented

Two-Component Water-Borne
Polyurethane Topcoat12
Dry Times at 72F (22 C)/50 percent RH
Set to Touch
Tack-Free
2.5 hrs
4.0 hrs
Appearance
20 Degree Gloss
60 Degree Gloss
89
94
Adhesion
Dry Tape (ASTM D 3359)
Dry Scrape (ASTM D 2197)
Wet Tape (24 hr/70 F [21 C])
Wet Tape (4 days/70 F [21 C])
5A
6 KG
5A
5A
Chemical Resistance
Acid. 10 percent HCl Spot. (7 days)
Base. 10 percent NaOH Spot. (7 days)
Acid. 5 percent Nitric Spot (7 days)
No Effect
No Effect
Very Slight
Solvent Resistance (ASTM D 4752)

MEK
Toluene
Isopropanol
>200 Double Rubs

>200 Double Rubs
>200 Double Rubs
Impact Resistance (ASTM D 2794)

Direct
Indirect
>160 in. lbs

>160 in. lbs
Flexibility (ASTM D 4145)

0-T BEND
PASS
Hardness
Pencil (ASTM D 3363)
Pendulum (ASTM D 4366)
2H
190
All coatings were applied over zinc-phosphated cold- rolled steel to a dry
film of 2.5 mils (63 micrometers) by conventional air spray application.
Results obtained after 7 days room temperature cure.
Fifty percent RH although most properties reached full development
within 24 hrs.
a balance of properties can be obtained

with a mixture of the 2, resulting in excellent overall properties.
Bock and Petzoldt11 found that 2K
water-borne primer surfacers have greater
flexibility and impact properties than their
solvent-borne counterparts, especially at
low temperatures. This improves performance in applications over plastic components by providing a barrier to the notching
effect of a brittle topcoat, which can catastrophically crack the plastic substrate.
These mechanical characteristics also favor
application as pigmented topcoat systems
by providing a resistance to cracking and
chipping, while providing the chemical reSEPTEMBER 1996
/ 61
tant to point out the difficulties that the

resin chemist, formulator, and paint applicator face in converting to a water-borne
analog. These difficulties are related mostly
to film formation issues. Related to film formation, but especially troublesome in its
own right, is carbon dioxide generation
and entrainment. Finally, limitations on vehicle solids affect a number of processing,
handling, and application issues.
Fig. 5 - Latex film formation mechanism
sistance of 2K solvent-borne polyurethanes.

The authors conclude that further development can overcome existing limitations in
terms of application conditions such as atmospheric moisture, temperature, and
flash-off times.
Jacobs and McClurg7 used a
polyurethane polyol and a water-reducible
alkyd cross-linked with a water-dispersible
(hydrophilic) isocyanate to formulate clear
and pigmented coatings for aircraft topcoats. They concluded that the performance properties of these 2K water-borne
systems were comparable to the traditional
aircraft topcoats while reducing VOC by
greater than 50 percent. Coatings formulated with the hydroxy functional alkyd displayed high gloss and excellent chemical
resistance as required for commercial aircraft applications. The polyurethane polyolbased coating had excellent flexibility and
toughness, as well as the chemical resistance needed for military aircraft.
Development Challenges with

2K Water-borne Polyurethanes
Now that the characteristics of the 2K solvent-borne and water-borne polyurethane
coatings have been identified, it is impor-
62 /
Film Formation
Film formation is not a significant issue in
solvent-borne coatings, since all reacting
components are fully dissolved in the
solvent carrier and intimately mixed. Upon
application of the coating, a continuous
thin film forms, solvent evaporates, and
the well-mixed components react to
form the final film. In single component
dispersions, such as PUDs and acrylic latexes, the polymer is not dissolved in the
water, but dispersed as very small particles
or drops.
Upon application of the coating
and evaporation of the water, good film
formation is contingent on effective coalescence of these particlesor their ability
to flow into one another to form a continuous polymer film. This process is often
assisted by a small amount of solvent in
the coating formulation that softens the
particles and allows them to coalesce.
The solvent then evaporates to allow the
coating to achieve its ultimate film properties (Fig. 5).
A reactive, 2K water-borne coating
formulation has to overcome not only the
coalescence issue described above, but also
the difficulties of getting good mixing of
the reactants so that once the film has been
applied and water evaporates, complete reaction can occur. Two-component waterborne polyurethane formulations also must
contend with the competing reactions of
isocyanate with polyol (desired) and with
water (not desired).
Fig. 6 - Time line of events in film formation mechanism of two-component polyurethane coatings
There has been a full treatment of issues surrounding film formation of 2K

water-borne polyurethane coatings in
which the polyol and a hydrophilically
modified isocyanate are co-dispersed in an
aqueous matrix.14 The specific events and
their timeframes are shown schematically in
Fig. 6.
The dispersion of isocyanate in the
aqueous system appears to occur immediately upon addition and mixing. Particle coalescence during the admixed state was
found to be minimal by particle size experiments. Isocyanate reaction with hydroxyl
groups occurs within 2 to 5 hours, as evidenced by the maximum exotherm from
calorimetry data.
Reaction with water occurs at a much
slower rate, as shown in calorimetry work
on a water/isocyanate system. These results
correlate well with pot life studies and carbon dioxide generation from the isocyanate/water reaction.
After application, evaporation of most
volatiles (including water) occurs within 30
minutes. During this time, a critical

solids content of the coating is reached,
so that particle-to-particle contact is completed throughout the film. When this occurs, diffusion of polymer molecules
across particle boundaries leads to particle coalescence.
This also favors the isocyanate/hydroxyl reaction. Isocyanate reactions after
application are 80 percent complete
within 3 days, suggesting substantial crosslinking by this time. To account for the
isocyanate/water reaction and ensure
complete hydroxyl reaction, NCO/OH
ratios are typically 2.0.
Studies on film property development illustrate that barrier properties
began to be established within 3 hours,
and chemical resistance develops within
3 days.
As noted earlier, solvent-borne
polyurethanes normally reach ultimate
properties at a slower rate. Chemical
resistance is usually reached within
7 days.
SEPTEMBER 1996
/ 63
Dr. Sherri L. Bassner

received a BA in
chemistry from Goucher
College in 1984 and
a PhD in inorganic
chemistry from
Penn State
Univeristy in 1988.
In the fall of 1988, she
began working at
Air Products and
Chemicals, Inc. in
the Professional
Development Program.
After spending 1 year
in the Electronics
Division developing
new compounds
for metal vapor
deposition, she joined
the Polyurethane
Chemicals Division,
where her charge
was developing new
polyurethane
prepolymers for
high solids coatings
applications. In the
following 6 years, she
was involved in
the development,
applications,
scale-up, and
commercialization
of many new products
for the industrial
maintenance market.
She is now a Senior
Principal Applications
Chemist in the
Polymer Chemical
Division.
64 /
Carbon Dioxide Generation

and Entrainment
With 2K solvent-borne polyurethanes, the
end of pot life is defined by a rise in viscosity and gelation of the admixed coating.
In contrast, the viscosity of most waterborne versions is relatively constant
throughout the pot life. As the induction
time of these coatings increases, the potential for the isocyanate-water reaction greatly
increases. (A number of researchers have
reported that in these systems, the isocyanate-water reaction is delayed by up to
2 hours after mixing.) As the isocyanatewater reaction occurs, carbon dioxide is
produced within the coating.
This has several consequences. First,
it increases the potential for defects from
foam and bubbling within the cured coating. Second, as the reaction of isocyanate
with water increases, the amount of isocyanate available for reaction with polyol
decreases. This can result in unreacted
polyol in the applied coating, which will
plasticize the film and reduce hardness,
toughness, and chemical resistance. Finally,
as isocyanate begins to react with water,
urea particles form that inhibit good coalescence. Therefore, the pot life of these 2K
water-borne coatings is often controlled by
this isocyanate-water reaction, which can
be difficult to assess in an industrial application scenario. Newer, high solids waterborne systems, however, tend to exhibit a
viscosity increase similar to their solventborne counterparts.
The isocyanate-water reaction also
has consequences on limiting coating thickness. This reaction will inevitably produce
carbon dioxide in the applied coating, especially if formulated at higher NCO/OH
ratios. This carbon dioxide must then diffuse out of the film in such a manner as to
avoid film defects. As film thickness increases, release of this carbon dioxide becomes more difficult, and bubbles will form
within the cured coating.
This effect is even more prominent

later in pot life. Most reports limit the potential dry film thickness obtained in 1 application of these coatings to 2 to 3 mils (50
to 75 micrometers). Thicker films may be
obtained by multiple applications, but this
is usually not preferred from a logistics and
scheduling standpoint. Ideally, the formulator would like to be able to produce waterborne systems that mimic their high solids
counterparts in application characteristics as
well as properties. Recent developments in
2K water-borne polyurethane coatings12
have resulted in systems applied at higher
solids (65 percent to 75 percent) that handle
very similarly to the solvent-borne analog.
State of the Art

and Future Work
Research and development in both resin
and formulation work for 2K water-borne
polyurethanes is continuing at a rapid pace.
This article captures works published
through April 1996. At the time of this writing, a very interesting development in this
area has been that of an extremely high
solids, water-dispersed polyol that allows
formulation of coatings quite similar in
handling and performance to high solids
solvent-borne coatings.12 This polyol, supplied at 70 percent non-volatiles, is capable
of dispersing standard isocyanates, alleviating the need to use modified isocyanates
and the problems associated with them, as
noted above.
Possibly because of the high solids
level of the formulated coating, these materials exhibit a definitive end of pot life
through viscosity build and gelation, without loss of properties before that point. Additionally, since the polyol itself disperses
the isocyanate, film formation issues
surrounding particle coalescence are
dramatically lessened, leading to exceptional film properties (Table 5). As a result,
coatings based on this polyol can be formulated with no co-solvent addedessentially zero VOC.
While the performance of 2K waterborne polyurethane coatings has risen to
approach that of their solvent-borne counterparts, work continues on the development of improved resins and formulations.
Areas of focus include enhancing the ability
to mimic the handling characteristics of solvent-borne coatings, increasing the range
of properties available by extending the
family of products, and reducing raw material costs. JPCL
Notes
1. C. H. Hare, Protective Coatings: Fundamentals of Chemistry and Composition,
SSPC 94-17 (Pittsburgh, PA: Technology
Publishing Co., 1994).
2. G. Gardner, Moisture Curing Polyurethanes, JPCL (February 1996), 81-100.
3. J. Kramer and S. L Bassner, Polyurethane Prepolymers for Moisture Cure
Primers, Modern Paint and Coatings (June
1994), 20-23.
4. R. R. Roesler and P.R. Hergenrother,
Two Component Polyurethane Coatings,
JPCL (January 1996), 83-94.
5. J. Kramer and S.L. Bassner, Using Novel
Polyurethane Prepolymers in VOC-Compliant, Two Component Weatherable Topcoats, Paint and Coatings Industry (August 1994), 42-44.
6. L. Kahl and M. Bock, Water-borne 2Component PU Clear Coats for Automotive
Coatings: Development of Raw Materials
and Mixing Technology, in Proceedings of
the 3rd Nurnburg Congress, Nurnburg, Germany, March 13-15, 1995 (Middlesex, England: Paint Research Association, 1995).
7. P.B. Jacobs and D.C. McClurg, Water-Reducible Polyurethane Coatings for
Aerospace Applications, in Proceedings of
the Low and No VOC Coatings EPA ConferCopyright 1996, Technology Publishing Company
ence, San Diego, CA, May 25-27, 1993

Washington, DC: Environmental Protection
Agency, 1993).
8. A. Bittner and P. Ziegler, Water-borne
Two-Pack Polyurethane Coatings for Industrial Applications, in Proceedings of the 3rd
Nurnburg Congress, Nurnburg, Germany,
March 13-15, 1995 (Middlesex, England:
Paint Research Association, 1995).
9. P.B. Jacobs and P.C. Yu, Two Component
Water-borne Polyurethane Coatings, Journal
of Coatings Technology (July 1993), 45.
10. C.A. Renk and A.J. Swartz, Fast Drying,
Ultra-Low VOC, Two Component Waterborne Polyurethane Coatings for the Wood
Industry, in Proceedings of the Waterborne, Higher Solids, and Powder Coatings
Symposium, New Orleans, LA, February 2224, 1995 (Hattiesburg, MS: Univ. of So.
Miss., 1995), 266-276.
11. M. Bock and J. Petzoldt, Aqueous
Polyurethane Coatings Systems for Plastics,
in Proceedings of the Water-borne, Higher
Solids, and Powder Coatings Symposium,
New Orleans, LA, February 14-16, 1996
(Hattiesburg, MS: Univ. of So. Miss., 1996),
502-513.
12. W.O. Buckley, E.H. Klingenberg, T.L.
Richards, and J.M. Snyder, High Performance Two Component Water-borne
Polyurethane Coating Systems, in Proceedings of the Water-borne, Higher Solids, and
Powder Coatings Symposium, New Orleans,
LA, February 14-16, 1996 (Hattiesburg, MS:
Univ. of So. Miss., 1996), 127-139.
13. M. Wingerde and E. Brinkman, Two
Component Polyurethane Paints: A Comparison Between Solvent and Water-borne,
in Proceedings of the 3rd Nurnburg
Congress, Nurnburg, Germany, March 1315, 1995 (Middlesex, England: Paint Research Association, 1995).
14. C.R. Hegedus, A.G. Gilicinski, and R.J.
Haney, Film Formation Mechanism of Two
Component Water-borne Polyurethane
Coatings, Journal of Coatings Technology
(January 1996), 51-61.
Dr. Charles R.
Hegedus has worked
as a Lead Applications
Chemist in industrial
coatings resins at
Air Products and
Chemicals in
Allentown, PA, since
1993. He is responsible
for research and
development of high
performance coatings
for industrial
applications. Before
joing Air Products,
he was employed for
17 years at the Naval
Air Development
Center, where he was
Technical Leader of
the Protective Coatings
Group.
Dr. Hegedus
received his BS in
chemical engineering
and PhD in materials
engineering from
Drexel University.
He has published more
than 60 technical
papers and reports.
He recently received
the FSCT Roon and
Corrosion Committee
Publication Awards.
He has 18 patents and
6 patents pending.
He is a member of the
Journal of Coatings
Technology editorial
review board, and he
chairs the FSCT
Corrosion Committee.
He is also a member
of SSPC and ACS.
The authors can
be reached at Air
Products and
Chemicals, Inc.,
7201 Hamilton
Boulevard, Allentown,
PA 18195-1501,
610/481-2561; 610/
481-2225; fax: 610/
481-7923.
SEPTEMBER 1996
/ 65

A Review of Two Component Water Borne Polyurethane

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A Review of Two Component Water Borne Polyurethane

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A Review of

ndustrial maintenance coatings systems

Journal of Protective Coatings & Linings

high performance, water-borne coatings

Developments in Water-Borne Urethanes

Developments in Water-Borne Urethanes

Fig. 2 - Typical reactions of isocyanates: with hydroxyl

Fig. 3 - Generalized polyisocyanate structures

istry. Before discussing the development

Journal of Protective Coatings & Linings

Developments in Water-Borne Urethanes

Formulation and Application of 2K

Fig. 4 - Structures of common isocyanates (top) and

Developments in Water-Borne Urethanes

Properties of a Typical Two-Component,

Typical Value (Test Method)

Tack Free Time

2-4 hours (ASTM D 1640)

HB-2H (ASTM D 3363)

Persoz Pendulum Hardness

150-300 seconds (ASTM D 4366)

Adhesion to Treated Steel

80-160 inch-lb (ASTM D 2794)

MEK Double Rubs

200+ (ASTM D 4752)

Resistance to Common Solvents

Excellent (Spot Test)

95+ (ASTM D 523)

Gloss Retention (2,000 hrs, UV-B)

70-90 percent (ASTM G 53)

Journal of Protective Coatings & Linings

The popularity and importance of these

Developments in Water-Borne Urethanes

functionality and glass transition temperature than their unmodified counterparts.

Two critical issues with these 2K

Developments in Water-Borne Urethanes

Solvent content (percent by weight)

Gloss 60 degrees/20 degrees

Cross cut test on steel or electro

Erichsen (proprietary) indentation

Tack free dry time (hrs)

ASTM D 4366, Method A, Knig

* grams/liter=pounds/gallon of VOC x 119.8

tion, addressed in more detail later. They

Journal of Protective Coatings & Linings

As with solvent-borne polyurethanes,

Developments in Water-Borne Urethanes

Evaluation Test Results of the Two-Component

Copyright 1996, Technology Publishing Company

Developments in Water-Borne Urethanes

Property Comparison of Solvent-Borne vs

by altering the polyol, isoElongation (percent)

cyanate, or the NCO/ OH ratio

Journal of Protective Coatings & Linings

Copyright 1996, Technology Publishing Company

Developments in Water-Borne Urethanes

Properties of High Solids Pigmented

Solvent Resistance (ASTM D 4752)

>200 Double Rubs

Impact Resistance (ASTM D 2794)

>160 in. lbs

Flexibility (ASTM D 4145)

a balance of properties can be obtained

Developments in Water-Borne Urethanes