As seen in

Paint Coatings Industry

Globally Serving Liquid and Powder Manufacturers and Formulators

1K Polyurethane
Dispersion
for Conventional 2K Applications

P olyurethanes are a unique class of poly-

mers due to their combination of both
hard and soft segment blocks within
the same polymer chain. This combi-
nation results in polyurethanes being
able to demonstrate high surface hardness, very good
chemical resistance and toughness along with excel-
lent flexibility, particularly at low temperatures where
other polymers may become brittle.1-3 Moreover, this
however, with government regulations limiting the
coating VOC, waterborne polyurethanes have gained
an ever-increasing market share, particularly as their
performance has been demonstrated to be comparable
to or better than their solventborne counterparts in
many applications.
Waterborne polymers are more user friendly than
their typical solventborne counterpart and provide
reduced flammability, health and odor concerns. Despite
combination of polymer characteristics leads to poly- the excellent properties exhibited by polyurethanes
urethanes displaying excellent durability and they typically need to have some degree of
abrasion resistance. The hard segment crosslinking to provide the required per-
of the polymer, made up of urethane formance needed for certain appli-
and urea linkages, provides the cations such as wood floor coat-
hardness and chemical resis- ings. The required crosslinking
tance through the formation is often conventionally done by
of strong hydrogen bonds; the introduction of an added
the hydrogen bonding can be crosslinking component to
considered a weak form of the polyurethane. This leads
self-crosslinking (compared to concerns on handling toxic
to covalent bond type cross- crosslinkers, limited pot life of
linking). The soft segment, the mixture, the need to mix
determined by the polyol components prior to applica-
from which the polyurethane tion, and the potential for waste
is made from, contributes to due to exceeded pot life or mix-
the low temperature flexibility, ing mistakes. This paper discusses
impact resistance and, to a large furthering the inherent advantages
extent, the film forming capabilities of of waterborne polyurethanes including
the coatings. This combination of proper- their user friendliness by way of a newly
ties has led to polyurethanes being the polymer of developed one-component (1K) self-crosslinking poly-
choice for wood floor coating applications, particu- urethane technology that performs on par with con-
larly for on-site application or refinish. Initially, these ventional commercial two-component (2K) waterborne
coatings were solvent, solution-based polyurethanes, PUDs for wood floor coatings.

By Anthony Pajerski and George Ahrens | Lubrizol Advanced Materials, Inc. Brecksville, OH
Reprinted with permission from theFebruary 2009 issue of Paint & Coatings Industry magazine
Waterborne Polyurethanes
2K Crosslinkers
There are several options available to formulators for
improving the performance of waterborne thermo-
plastic polyurethanes by crosslinking of the polymer.
Among these, polyaziridines and polyisocyanates have
found significant commercial application in contractor-
applied wood floor coatings, mainly due to their cure
effectiveness at ambient conditions in a reasonable
length of time. Polyaziridines can give very effective
crosslinking in carboxylic acid functionalized polyure-
thane dispersions with good property development after
as little as 1 day curing time at room temperature. More-
over, they are readily incorporated into waterborne
polymers due to their high degree of water solubility
and low viscosity. Polyaziridines have a reasonably
long pot life of at least one working day, or 8 hours,
and purportedly can be re-inoculated with a second
dose after the recommended pot life has expired. But
polyaziridines have issues with skin irritation and are a
suspected carcinogen/mutagen primarily based on the
fact that they give a positive result in the Ames bacterial
assay test. The use of water-dispersible polyisocyanates
as a crosslinking component of 2K PUD for floor coat-
ing applications is a somewhat newer technology that
is growing in popularity. It has gained some favor over
polyaziridine crosslinkers due to reduced toxicological
concerns, however, they are still of concern for allergic
reaction, skin irritation and asthma.4
Polyisocyanate crosslinkers can react with active
hydrogen groups, such as hydroxyl groups and primary
or secondary amines, on the polymer backbone or at the
end of the polyurethane chains. They can also provide
good properties with PUDs that do not carry significant
crosslinking functionality by self-condensation via reac-
tion with water followed by decomposition of the car-
bamic acid generated, releasing CO2 and generating an
amine that quickly reacts with any available isocyanate
to generate a urea linkage. It is generally believed that for
room temperature 2K polyisocyanate crosslinked PUDs
this self-condensation is the primary reaction resulting in
an IPN.5 Data we have gathered (discussed later) suggest
that polyisocyanate crosslinkers can provide improved
durability and can give close to the same resistance
properties as polyaziridine-crosslinked polyurethanes
but require longer cure times to achieve them. However,
water-dispersible polyisocyanates are know to be harder
to incorporate into waterborne dispersions due to their
higher degree of hydrophobicity and higher viscosity,
usually requiring them to be cut with solvent and the
need to use proper mixing. Water-dispersible polyiso-
cyanates also have a shorter pot life than polyaziridines
closer to ~4 h for optimal performance after which time
the resulting dispersion becomes unusable either due to
unacceptable performance, appearance or application
properties. Furthermore, the above-described reaction of
the polyisocyanate with water can result in foam genera-
tion and entrapment in the finished coating.
Self-Crosslinking Chemistries
A few options exist to incorporate functional groups into
a waterborne polyurethane that can crosslink at room
temperature upon application and have the potential to
provide a shelf stable system. The oldest self-crosslinking
technology and currently the most popular means to
provide a self-crosslinking polyurethane is via auto-oxi-
dation of an unsaturated functionality. The unsaturated
functional groups are obtained from fatty acids or natural
oils high in unsaturation such as linseed, sunflower, soy-
bean, tung and safflower oils. The auto-oxidative cross-
linking reaction is fairly complicated and goes through
a number of intermediates and leads to a large number
of final chemical structures. An abbreviated scheme is
shown in Figure 1 with the main final product believed
to be the coupling of free radical oxygen atoms.6, 7 To be
effective, oxidative curing requires the addition of a drier
or catalyst to push the cure. These driers tend to be based
on heavy metals that can be toxic, highly colored, and
difficult to incorporate in waterborne polymers and easily
affected by other components in the waterborne polymer
or in the wood, such as tannins.
The crosslinking can be very effective but is regarded
as somewhat slow unless high amounts of drier are
used with a high content of fast-drying unsaturated
groups, which can give the final dispersions and coat-
ings a high degree of color.6-8 Moreover, the side-chain
unsaturated functional groups attached to the polymer
backbone are typically C16-based esters, which make
the coatings much more brittle than typical polyure-
thanes due to less-effective polymer alignment and
packing. This is analogous to the effect of the side chains
in poly(meth)acrylate type polymers.
Carbonyl-amine crosslinking has also seen signifi-
cant use in waterborne polymer crosslinking and can
provide significant improvement in resistance properties
FIGURE 1 | Potential self-crosslinking chemistries that can be used for waterborne
polymers: auto-oxidation, carbonyl amine and acetoacetoxy reactions (enamine
formation and Michael reaction).
Auto-oxidative
OOH O
M+
O2 Crosslinking
R R R R' Drier R R
H H
H H
Carbonyl - Amine
R R
O + RNH2 N R
R -H2O/H + R
Acetoacetoxy Reactions (enamine formation and Michael reaction)
O O O NHR O O Base O O
+ RNH2 & +
RO -H2O RO RO RO
CO2R
CO2R
1K Polyurethane Dispersion for Conventional 2K Applications

of polyurethanes, however, it has been noted that the (either 1 or 7 days) at ambient conditions before testing.
chemistry suffers from sub-par water resistance in the One-hour spot tests are run on the surface of the finish.
cured coatings.8 The reaction of carbonyls with amines Sections of cotton facial pads are soaked in the test agent
is triggered by a drop in pH and loss of water; an abbrevi- on the surface of the finish. After removal of the pad and
ated depiction of the reaction is also shown in Figure 1 test agent, the surface of the coating is blotted dry and
and involves several intermediates (not depicted) to get observed for damage. The tested surface is re-evaluated
to the final imine or azomethine product. after a one-hour recovery. Ratings are: 5 = no effect on
A third option for crosslinking waterborne polymers finish; 4 = finish is slightly swelled or surface of finish is
depicted in Figure 1 is through acetoacetoxy function- permanently changed; 3 = finish surface is changed and
ality either by enamine formation via reaction with wood color has been impacted; 2 = more severe damage
polyamines or Michael reaction by nucleophilic addition than 3; 1 = very severe damage to film or discoloration
to a Michael acceptor such as an acrylate group. These of wood; and 0 = finish is removed from the substrate.
reactions can be a rapid and very effective means of cross- Tests for specific applications or customer end uses
linking, however, issues revolve around hydrolytic stabil- may dictate longer exposure times. Chemical resistance
ity of the ester, premature crosslinking and the potential evaluations run for longer than an hour are covered,
to obtain undesirable color in the dispersion and applied using either watch glasses or a similar device to keep
coating.9, 10 The formation of the chromophore respon- the test agent from evaporating. The rating system used
sible for the color is likely related to the reaction of various above is also used for this testing. Chemical test agents
amines with the acetoacetoxy groups,10, 11 some of which that are typically evaluated for longer exposure times
are typically present in polyurethane synthesis. are: water, water/alcohol combinations, red wine, cof-
fee, hand creams, and strong acids and bases.
Experimental
Formulation Black Heel Mark, Mar and Scuff Resistance
The Lubrizol 1K self-crosslinking (SCL) PUD was for- The apparatus consists of a pivoting pendulum arm
mulated with 13.7% diproplylene glycol n-butyl ether with a 2-lb weighted piece of hard, black rubber (such
versus polymer solids and reduced to 30% solids; the as that of a hockey puck) at the end meant to simulate
final dispersion has a VOC of ~269 g/L and is a film a hard shoe sole capable of producing black heel mark-
former at 4 C on uncoated paper (porous substrate). ings. This is the striking surface to the test panel. The
The commercial 2K PUDs were purchased from a local total length of the pendulum device from the arm pivot
contactor supply outlet and used as is; the containers to the striking surface is ~38. The test consists of strik-
indicated the VOCs were <350g/L. ing the coated maple panel six times on different areas
and direction on the panel with the pendulum black
Chemical Resistance heel marking device. Striking is done by raising the
Testing followed ASTM method D 1308. Coatings are pendulum arm to an angle of 90 94 of the coated
tested by applying three coats of similar weight to maple panel, which is placed on the floor, and then releasing
veneer panels that are cured for the designated time the arm under the force of gravity to strike the coated
panel at the designated area. Results are expressed by
TABLE 1 | Chemical resistance of 1K SCL PUD versus 2K commercial controls after 7 visual assessment of the panel (scratching, scuffing, and
days at room temperature (0 = highly effected/damaged, 5 = no effect/damage).
black markings/discoloration) and gloss measurements.
1K SCL 2K Thermoplastic The test was evaluated and supported by statistical
Test 2K NCO
PUD Aziridine PUD experimental analysis to other methods for predicting
Water (16 hr) 5 5 5 5 real floor wear resistance. Coating test samples were
409 Cleaner (1 hr) 5 5 5 4 prepared as above for chemical resistance testing.
Spic & Span (1 hr) 5 5 5 4
Windex (1 hr) 5 5 5 4 Abrasion Resistance
1.4% Ammonia (1 hr) 5 4 5 4 Testing was conducted as per ASTM D 4060 on wood
Vinegar (1 hr) 5 5 5 5
panels. Pairs of panels are finished with three coats of
the test subject and aged seven days at ambient condi-
Grape juice (1 hr) 5 5 5 5
tions. Actual Taber testing is performed in a climate-
50% Clorox bleach (1 hr) 5 5 5 5
controlled environment (70 F/50% RH). Test panels are
Olive oil (16 hr) 5 5 5 5 conditioned to this environment for 16 to 24 hours before
3 3 3 3 testing. Taber test is performed using CS17 wheels. Each
Mustard (6 hr) (fades to pass) (fades to pass) (fades to pass) (fades to pass)
test panel is weighed initially and after each 250 cycles
50% Ethanol (1 hr) 4 4 5 1
on a scale that measures to four units to the right of the
70% IPA (1 hr) 4 4 4 1
decimal point. Each panel is run for a total of 1000 cycles.
Red Wine (6 hr) 5 5 5 5 Taber abrasion values are expressed as milligrams weight
Overall Total 61 60 62 51 loss per 1000 cycles (averaged over the pair of panels).
Scratch Resistance and commercial applications that are known to be
The test coatings are prepared by making 6-mil aggressive toward coatings were evaluated on the self-
draw-downs on Mylar sheets (typically scrub charts). crosslinking PUD and compared against two commer-
The scratch resistance of the coatings is determined cial 2K-crosslinked controls based on polyaziridine and
by subjecting the coating to 200 double rubs with a polyisocyanate crosslinkers. The exposure time of the
Scotch-Brite sponge weighted with 350 g. The sponge coatings to the substance is given in parentheses next
is rotated by 180 after 100 double rubs to attain a to the substance. The results shown in Table 1 illustrate
more uniform scratch/abrasion. The coatings are the SCL PUD performs favorably compared to the com-
analyzed for final gloss at 20, 60 and 85 and com- mercial 2K controls in the gloss compositions that were
pared to the starting gloss at the same area. Results tested. In particular, the performance of the 1K PUD
are reported as percent gloss retention. is particularly impressive toward alcohol resistance
where common thermoplastic PUDs tend to be weak.
Test Floor Evaluation Moreover, the water resistance is excellent for the 1K
Each coating to be tested is prepared by applying three SCL PUD, which was found to be a weakness for ketone-
coats of similar weight to four separate oak panels that amine self-crosslinked PUDs.8
are cured for 7 days at ambient conditions before assem-
bly into the test floor. The test floor evaluates up to 24 Solvent Swells
coatings at one time. There are four statistically deter- Another way to look at how effective crosslinking is
mined varied positions for each test coating that allows in a polymer based on an objective measurement is
for equal foot traffic and wear patterns for each coating through solvent swell experiments. The main drawback
and statistical analysis of the data. Five gloss readings is that they do not take into consideration the adhesion
are taken of each coating at each position on the test or discoloration of the coating on a wood substrate
floor. 60 gloss readings are taken initially when the being subjected to chemical attack. As mentioned in
floor is installed and once a month after that. A template the experimental section, cured films of known dimen-
is used for placing the gloss meter on the test positions to sion are submerged in the swelling solvent, and the
ensure that the same location is read each time a read- maximum degree that the film swells is recorded. The
ing is taken. Monthly readings are usually discontinued degree of swelling is related in large part to the degree of
after about five months usage. Most gloss loss occurs in crosslinking particularly for highly aggressive solvents.
the first two months of usage. About one to two thou- The swelled films are measured and compared to the
sand people cross this floor every workday. Each coating starting film size; the lower the swell the more effective
at each location on the floor is also monitored for black the crosslinking and solvent resistance. Several solvents
heel marking and other damage that may occur to the were examined that are typically aggressive toward
finish (high heel indentions as an example). PUD coatings to determine consistency of results.
We thought it also might be useful to determine
Solvent Swell cure speed by looking at the effect of cure time (1 day
Data generated for solvent swells were based on disper- vs. 7 days) at ambient conditions on solvent swell
sions at ~30% solids drawn-down 10-mil wet on Mylar results. The results, in Table 2, show that the 1K SCL
film that was pre-coated with a Teflon release coating. PUD performs very well in comparison to the com-
The resulting films (~2-mils dry) are cured for a given
time period (1 day or 7 days) at ambient conditions, after TABLE 2 | Solvent swell results.
which time a 25-mm diameter circular film is punched
Thermoplastic
out using a die. The 25-mm circular film sample is then Cure Time at 1K SCL PUD 2K NCO 2K Aziridine
PUD
submerged in the solvent being tested in a small glass jar RT- Solvent (% Increase) (% Increase) (% Increase)
(% Increase)
for a 24-hour time period before being tested for swell. 1 Day RT Cure
Solvent swell was determined by measuring the diam- 8 (moderate
eter of the swollen film in a petri dish containing some IPA 6 10 (slight white) 6
white)
of the solvent using digital calipers and double checked MEK 12 24 (slight white) 18 30
with a standard metric ruler. Methanol 10 20 (slight white) 8 dissolved
NMP 64 62 46 dissolved
Discussion of Results
Chemical Resistance 7 Day RT Cure
For adequate protection against commonly used clean- 8 (moderate
IPA 6 9 (slight white) 6
white)
ers, food stuff and alcohol-based materials, floor coat-
ings need to have excellent resistance properties in MEK 12 24 (slight white) 17 30
order to prevent unsightly stains and blemishes to the highly
Methanol 10 12 (slight white) 8
deteriorated
coating as well as the substrate. A number of materials
expected to be potentially encountered in residential NMP 64 52 40 dissolved
 1K Polyurethane Dispersion for Conventional 2K Applications

Auto-oxidative
OOH O 10000
Auto-oxidative
Auto-oxidative M+

of Cycles)
O2 O Crosslinking 10000
R mercial
OOH
R 2K-crosslinked ORThe 10000
Black Heel Mark and Mar Resistance
MPUD
+ R controls. large differ-
R OOH
R' Drier
M +

Cycles)
O

ofCycles)
O22 H H
Crosslinking
Crosslinking 8000
R
R H H R ence for
R R the aziridine-crosslinked
R R' Drier
R' Drier R
R PUD R in
R NMP might One of the most important performance aspects of
H 8000
8000 is their ability to resist against
H
H H
H be related HHto its crosslinking through
H the
acid groups wood floor coatings
Carbonyl - Amine 6000

(No.
of
on the polymer.
R Carbonyl - Amine R As expected, the 2K polyisocyanate- aesthetically unpleasing marks from shoe soles, often
Carbonyl - Amine 6000

(No.
6000

(No.
O + RNH crosslinked PUD gave
N R the most significant improve- termed black heel mark resistance or scuff resistance.

Through
R R
RR
2
R 4000
O -H2O/H + R
O ++ RNH N R

Through
ment
RNH in crosslinked N performance
R after 1-week cure Along with scratching or abrasion, shoe scuffing rep-

Through
2
2
R
R -H
-H22O/H
+ R
R
O/H(enamine
+ 4000
4000
Acetoacetoxy Reactions
time, particularly formation and Michael
with respect reaction)
to NMP swell. However, resents the main modes of floor failure in terms of
2000
Acetoacetoxy Reactions (enamine formation
1-dayOandvs.OMichael reaction)

Wear
Acetoacetoxy
O O the difference
Reactions (enamine
O NHRin
formation and 7-dayBase
Michael cure O is not
reaction) O as large change in gloss2000and aesthetics. If a coating does not
& 2000

Wear
O + RNHas

Wear
O O anti c ipated
O NHRfor the 2K polyisocyanate-cured
O O PUD, develop strong resistance against shoe sole scuffing in
RO O O O
+
2
-H2O RO O NHR RO O O Base RO O O 0 1K SCL PUD 1K SCL PUD 1K Aziridine 1K Aziridine 1K NCO A
+ &
& Base
+ RNH
RNHif22 the cure is largely CO2R
self-condensation after reaction +
+
a relatively short period of time,(Satin)
a beautifully finished 1K N
RO
RO -H
-H2O
2O RO
RO RO
RO RO
RO 0 (Gloss) (Gloss) (Satin) (Satin)
0 1K SCL PUD 1K SCL PUD 1K Aziridine 1K Aziridine 1K NCO A
(Gl
CO
CO22R
Rmuch of CO 2R cure is 8500PUD 1K Aziridine
6750PUD 1K SCL
1K SCL 1K Aziridine 1K 5500
NCO A 1K N
1K 43
N
with moisture and suggests that the wood floor canWt.quickly
Loss
start to look unsightly. This
Wear Through
(Gloss)
(Gloss)
30.0
(Satin)
(Satin)
24.0
3000
(Gloss)
(Gloss)
69.0
3250
(Satin)
(Satin)
66.0
(Satin)
(Satin)
40.0
(Gl
(Gl4
complete early on. The SCL PUD did notCO 2 R
2R
COshow any is particularly Wear
true
Wear Through
Wt.
Through
Wt. Loss
in 6750
commercial
6750 8500
8500 3000
settings
3000 3250
such
3250
as 5500
5500 43
43

No
30.0
Added
24.0 69.0
Aziridine
66.0 40.0
NC4
Loss 30.0 24.0 69.0 66.0 40.0 4

additional improvement in solvent swell after the 1-day clothing stores, which can not stay
Crosslinker closed for extended
Crosslinked Crossl
No
No Added
Added and undergoAziridine
Aziridineheavy NC
NC
cure time, suggesting a fast crosslinking reaction. time periods (for floor finishing),
Crosslinker
Crosslinker Crosslinked
Crosslinked Crossl
Crossl
customer traffic wearing a variety of shoes. The pen-
dulum black heel mark (BHM) and scuffing device test
FIGURE 2 | Black heel mark resistance of Lubrizol 1K SCL PUD vs. commercial 2K described above was used to test the SCL PUD against
10 wood floor finishes.
crosslinked popular contractor-applied 2K PUD wood floor fin-
Rating:

109
10 ishes. This test is deemed one of the better bench top
8
Rating:
Marking

9
Rating:

9 12
tests for determining actual real world floor coating
7
8
Marking

8
= Marking

12
Mark

6
7
7 performance based 12 on a statistical analysis in compari-

as Oscillations
5
Mark

6 10
Mark

6 son to other potential lab test methods available.

No

Oscillations
asOscillations
4
Heel

5
5 10
10
Results for pendulum BHM test results are displayed
No

3
No

4
Heel

4
Heel
10

2 8
Black
10==

3
3 in Figure 2 and show that that SCL PUD performance 1K
1 8
10

2 8 professional-grade commercial
Black

2
Black

0 is on par with the 1K

Co
1K
1
1 6 Cr

Hardness
1K Self- 1K Self- Commercial Commercial Commercial Commercial
2K PUD systems both in a gloss and satin finish.
as
0 Co
Co
0 Crosslinking Crosslinking 2K NCO PUD 2K NCO PUD 2K Aziridine 2K Aziridine
1K Self- 1K Self- Commercial Commercial Commercial Commercial 6
6Hardness
Hardness Co
Cr
Cr
PUD
1K (Gloss)
Self- PUD
1K (Satin)
Self- (Gloss)
Commercial (Satin)
Commercial (Gloss)
Commercial (Satin)
Commercial
Crosslinking Crosslinking 2K
2K NCO
NCO PUD 2K
2K NCO
NCO PUD 2K
2K Aziridine 2K
2K Aziridine
Moreover, the cure speed for the SCL PUD is also found Cr
Crosslinking
PUD
Crosslinking PUD PUD Aziridine Aziridine 4 Co
Co
PUD (Gloss)
(Gloss) PUD
PUD (Satin)
(Satin) (Gloss)
(Gloss) (Satin)
(Satin) (Gloss)
(Gloss) (Satin)
(Satin) to be comparable to the commercial 2K, as seen in Fig- Cr
Cr
4
4
Koenig

ure 3. The 2K isocyanate-cured

2
sample demonstrated
Koenig
Koenig

slower property development,

2 which was a consistent
FIGURE 3 | Black heel mark resistance and finger nail mar of Lubrizol 1K SCL PUD vs. 2
observation of multiple0 applications testing. The fast
commercial 2K crosslinked polyurethane wood floor finishes versus cure time. development of mar and 1 7
scuff resistance 14 21
is important
After 1 day After 7 days After 1 day After 7 days 0
0
10 for applications that receive 1
1 7
Cure
significant 14
7 Time -traffic
Days
14 21
21
shortly
Resistance

After
After 11 day
day After
After 7
7 days
days After
After 1
1 day
day After
After 7
7 days
days
10 10 Cure
10 after application, typical for a commercial Cure Time
Time -- Days
Days
application
Resistance
Resistance

8 10
10
8 such as a shopping mall.
MarMar

8
8
6 8
8 We also compared the performance of the Lubrizol
Mar
Fingernail

6
Mark

6
6 SCL PUD to some commercially 100 available 1K PUD-based
Fingernail

6
Mark

Fingernail

4 6
Mark

4 floor coatings for pendulum 100

100 BHM resistance. The results
Heel

4
4 4
2 4 (Figure 4) demonstrate the superior BHM resistance
Heel

2
Heel

80
Black

2
2 2
2 obtained for the Lubrizol SCL PUD compared to avail-
0 80
80
Black

0
Black

Gloss

1K SCL PUD 2K Aziridine 2K NCO 2K NCO 1K SCL PUD 2K Aziridine 2K NCO 2K NCO able commercial 1K PUD-based products in a gloss
0
0 (Gloss) 0
Gloss

(Gloss) (Satin) (Gloss) 0 (Gloss) (Gloss) (Satin) (Gloss)

Gloss

1K
1K SCL
SCL PUD
PUD 2K
2K Aziridine
Aziridine 2K
2K NCO
NCO 2K
2K NCO
NCO 1K
1K SCL
SCL PUD
PUD 2K
2K Aziridine
Aziridine 2K
2K NCO
NCO 2K
2K NCO
NCO after 1-week cure at room 60 temperature. This is a likely
6060

(Gloss)
(Gloss) (Gloss)
(Gloss) (Satin)
(Satin) (Gloss)
(Gloss) (Gloss)
(Gloss) (Gloss)
(Gloss) (Satin)
(Satin) (Gloss)
(Gloss)
and expected result, particularly 60
60 if the 1K PUD coating
60

remains in a thermoplastic state. 1K, Gloss

40 1K, Gloss
2K Aziridine,
1K, Gloss Gloss
FIGURE 4 | Black heel mark resistance of Lubrizol 1K SCL PUD vs. commercial 40
40
2K Aziridine,
Accelerated and Real-Life Floor Wear Durability
2K NCO, GlossGloss
Testing
Aziridine, Gloss
1K coatings. 2K NCO, Gloss
(Abrasion Resistance) 20 2K NCO, Gloss
10 Initial 1-month 2-month 3-month
20
Another critical performance
20 parameter for wood floor
Rating:

9
10
10 88
Initial
Initial 80
1-month
1-month 75
2-month
2-month 68
3-month
3-month
coatings is their ability to withstand abrasion.66As
Rating:

8 81 71 58
Marking
Rating:

9
9 88
88 80
80 75
75 68
68
7
8 mentioned previously, polyurethanes
86
81 in78
general have
71 71
66 65
58
Marking

8 81 71 66 58
= Marking
Mark

6
7
7 very good abrasion resistance, 86 78
and crosslinking 71
likely 65
86 78 71 65
Mark

5
6
Mark

6 improves the coating performance toward resistance

No

4
Heel

5
5
No

3 against chemicals and scuffing or marring. However,

=No

4
Heel

4
Heel
10=10

2
Black

3
3 upon crosslinking the coating system still needs to
1
10

2
Black

2 retain or show improved abrasion resistance and the

Black

0
1
1 1K SCL PUD Commercial Commercial Commercial Commercial Commercial
0 ability to withstand scratching that would be experi-
0 Hybrid Hybrid Acrylic/PUD Commercial
PUD PUD/Acrylic
1K
1K SCL PUD Commercial
SCL PUD Commercial Commercial
Commercial Commercial
Finish #1 Commercial
Blend Commercial Commercial
Finish #2 Commercial
Blend enced by a floor coating, particularly in a commercial
Hybrid
Hybrid Hybrid
Hybrid Acrylic/PUD
Acrylic/PUD PUD
PUD PUD/Acrylic
PUD/Acrylic
Finish
Finish #1
#1 Finish
Finish #2
#2 Blend
Blend Blend
Blend
 setting where shoe soles can carry abrasive materials.
Figure 5 shows the data for both gloss and satin formu-
las of the Lubrizol SCL PUD in comparison to the com-
mercial 2K floor coatings using either a polyaziridine
or polyisocyanate crosslinker. The data was examined
both from a mg coating loss per 1000 cycles and as a
OOH O 10000
OOH M
function of++ the amountO of cycles
ever, the differences are smaller between the 1K SCL
PUD versus the 2K polyisocyanate-cured commercial
PUD coating at 20 mg and 22 mg loss respectively
FIGURE 5 | Taber Abrasion data for 1K SCL PUD versus commercial 2K crosslinked
polyurethane
10000 wood floor finishes (ASTM D 4060, with 1000 g weight 3 coats 100
on
100
necessary to obtain

Cycles)
M Crosslinking maple similar total coat weight).

ofCycles)
Crosslinking
wearR'

Weight
R Drier
Drier R
R'through. R

Weight
R R In both cases R the 1K SCL PUD proved 8000 100
H OOH H O 10000
8000 75
H superior M +both of Hthe 2K commercial finishes with the
to 75

Cycles)
Crosslinking

of
R'

Weight
R Drier R being the R
ne polyisocyanate next best and the polyaziri-

Loss
6000
8000

(No.
ne

Loss(mg)
6000

(No. of(No.
H R H 75
dine
R being the worst for abrasion. 50
N R 50

Through

(mg)
The Nrelationship
R

WearThrough
ne in abrasion resistance could be a 4000

Lossper
H
H22O/H
O/H+
+ R
R 6000
4000
R
reflection of the coating hardness as the crosslinked 50

per
tions
tions (enamine formation and
and Michael reaction) 25

(mg)
N R

Through
(enamine formation
polyaziridine
R
Michael
was byreaction) far the hardest and developed 2000
4000 25
H2O/H+ 2000

1000
1000
O

Wear Wear
O NHR O O
O ByO
its hardness
NHR O O Othe quickest.
Base O contrast, the 1K SCL

per 1000
&
& Base
tions (enamine formation and Michael reaction)
+
25
O RO
2O RO PUD and
RO
RO the polyisocyanate-crosslinked
+
RO
RO system had 20000
0 0
0
2
O NHR CO2R
CO R 1K SCL PUD 1K SCL PUD 1K Aziridine 1K Aziridine
SCL PUD 1K(Gloss)
SCL PUD 1K(Satin)
1K(Gloss) Aziridine 1K (Satin)
Aziridine
1K NCO A
1K NCO A
1K NCO B
1K NCO B
1K NCO B
1K NCO B
very &similar O O hardness Base
2 O O with respect to time,
profiles (Gloss) (Satin) (Gloss) (Satin)
(Satin)
(Satin)
(Gloss)
(Gloss)
(Satin)
(Satin)
+ CO
CO22RR Wear Through
Wear Through
6750
6750
8500
8500
3000
3000
3250
3250
5500
5500
4375
4375
4750
4750
2O RO as depicted RO in Figure 6.RO It was surprising to find that Wt. Loss 0 30.0 24.0 69.0 66.0 40.0 46 45 0
CO2R Wt. Loss 24.0PUD 1K Aziridine
30.0PUD 1K SCL
1K SCL 69.0 1K Aziridine
66.0 1K NCO
40.0 A 1K NCO
46 B 1K NCO
45 B
(Gloss) (Satin) (Gloss) (Satin) (Satin) (Gloss) (Satin)
1K SCL PUD starts off so low CO in Rhardness, but yet the No
2 Wear Through No Added
6750 Added
8500 Aziridine
Aziridine
3000 3250 5500 NCO
NCO
4375 4750
black heel mark and fingernail mar resistance are Wt. Loss Crosslinker
Crosslinker
30.0 24.0 Crosslinked
Crosslinked
69.0 66.0 40.0 Crosslinked
Crosslinked
46 45

very good even after a 1-day cure time as discussed No Added Aziridine NCO
earlier. The low initial hardness is likely due in large Crosslinker Crosslinked Crosslinked
part to the retention of slow/high boiling solvent that
plasticizes the coating, which already has a signifi- FIGURE 6 | Hardness development of 1K SCL PUD versus 2K crosslinked commercial
cant degree of crosslinking providing the good early controls.
(1 day cure) properties. 12
12
Actual real floor wear data was gathered on a heav-
Oscillations

ily traveled hallway that would be similar in environ-

asOscillations

10
12
10
ment to a commercial application setting. The gloss
as Oscillations

self-crosslinking 1K and commercial 2K coatings gave 8

10
8 1K Self-crosslinking PUD (Gloss)
results that were reflective of those found in the Taber 1K Self-crosslinking PUD (Gloss)
as

Commercial 2K Isocyanate
abrasion test, however,Commercialthe differences were not quite as 6
8 Commercial 2K Isocyanate
Crosslinked PUD (Gloss)
Hardness

1K
1K Self- Commercial Commercial Commercial Commercial 6 Crosslinked PUD (Gloss)
Hardness

Self- Commercial Commercial Commercial 1K Self-crosslinking PUD (Gloss)

Crosslinking large.
Crosslinking 2K NCOThe
2K NCO PUD test
PUD 2K floor
2K NCO
NCO PUD was
PUD 2K based on
2K Aziridine
Aziridine 2K a statistical derived
2K Aziridine
Aziridine Commercial 2K Aziridine
Commercial 2K Aziridine
PUD
PUD (Satin)
(Satin) (Gloss)
(Gloss) (Satin)
(Satin) (Gloss)
(Gloss) (Satin)
(Satin) Crosslinked PUD (Gloss
Commercial 2K Isocyanate
Crosslinked PUD (Gloss
distribution of similar coated oak wood panels on the 4
6
4 Crosslinked PUD (Gloss)
Hardness

1K Self- Commercial Commercial Commercial Commercial

Crosslinking test area
2K NCO PUDto 2K obtain
NCO PUDan 2K equal degree
Aziridine of
2K Aziridine foot traffic and Commercial 2K Aziridine
Koenig

PUD (Satin) (Gloss) (Satin) (Gloss) (Satin) Crosslinked PUD (Gloss

Koenig

wear on each coating being tested. The average gloss 2

4
2
retention measured across the panels was monitored
Koenig

every four weeks; the results of the floor test are shown 20
0
7
7 14
14 21
21 1
1
After 7 in Figure 7. As can
days
After 7 days Afterbeen
After 1 day seenAfter
1 day from
After 7 the data, all of the
7 days
days
Cure
Cure Time
Time -- Days
Days
coatings10show a gradual loss of gloss over time due 0
10 1 7 14 21
After 7 daysto floor wear; again After 1theday 2K polyaziridine-crosslinked
After 7 days
8 Cure Time - Days
Mar

8 shows a greater overall loss of gloss with FIGURE 7 | Floor wear data as a function of gloss over a period of 6 months for the
Mar Mar

PUD coating 10
1K SCL PUD versus 2K crosslinked commercial controls.
the 1K SCL PUD and 2K isocyanate PUD more or less
Fingernail

6
Fingernail

6
8 100
100
showing a parallel trend. As mentioned previously, the
4
increased46wear or loss of gloss for the 2K aziridine may
Fingernail

be related22 to the higher hardness or coating stiffness 100

4 80
80
producing0 more micro-scratches or abrasion.
Gloss

0 1K SCL PUD 2K Aziridine 2K NCO

60Gloss

e
e
2K NCO
2K NCO
(Satin) 2K Evaluation
2K NCO
NCO
(Gloss)
2 of PUD
the2K1K
1K(Gloss)
SCL SCL 2KPUD
Aziridine
(Gloss) NCO versus
(Satin)
2K NCO the 2K-cross-
2K NCO
(Gloss) 80
(Satin) (Gloss) (Gloss) (Gloss) (Satin) (Gloss) 60
60
linked commercial
0 controls by an MFMA-approved
60 Gloss
60

e 2K NCO
(Satin) independent
2K NCO
(Gloss)
1K testing lab for2K(Satin)
SCL PUD 2K Aziridine
(Gloss) (Gloss) wear
NCO performance
2K NCO
(Gloss) sup-
60 1K,
1K, Gloss
Gloss
ported our findings. All of the coatings tested using the 40
40 2K
Snell accelerated soiling capsule (MFMA specifica- 2K Aziridine,
Aziridine, Gloss
Gloss
2K
1K,NCO,
2K GlossGloss
NCO, Gloss
tion group 5) found them to rate excellent; an excel- 40
20 2K Aziridine, Gloss
lent rating is when the coating exhibits 0.7% +/- 0.34% 20 Initial 1-month 2-month 3-month 6-month
Initial2K NCO, Gloss 2-month 3-month 6-month
1-month
or less of surface area that shows markings. The Taber 88
88 80
80 75
75 68
68 65
65
20 81 71 66 58 50
abrasion test results obtained from the independent 81
Initial 71
1-month 66
2-month 58
3-month 50
6-month
86
86 78
78 71
71 65
65 60
60
test lab exhibited a similar trend to our results; how- 88 80 75 68 65
81 71 66 58 50
86 78 71 65 60
1K Polyurethane Dispersion for Conventional 2K Applications
after 1000 cycles. The 2K polyaziridine- TABLE 3 | Gloss retention after 200 double rubs
crosslinked PUD gave a 48 mg loss. of weighted scrub pad.
1K SCL
Scratch Resistance Gloss Angle
PUD
Another procedure for testing coatings 20 23.3
in an accelerated manner to determine
60 52.1
actual floor wear performance is a scrub
pad scratch test, which looks at gloss 85 74.0
retention after a given number of double
rubs using a weighted Scoth-BriteTM scrub pad. We evaluated
the same 1K SCL PUD versus the commercial 2K aziridine-
and isocyanate-crosslinked PUDs in a gloss formulation as
were tested in the real floor test described above for gloss
retention in the scratch test. Interestingly, a similar pattern
of performance was seen as in the above test floor evaluation.
The results for gloss retention of the coatings after 200 double
rubs of the weighted scrub pad are shown in Table 3. The 1K
SCL PUD performed as well or better at the lower angle gloss
retention. Oddly, the 2K aziridine PUD coating that performed
the worst at the low angle gave the best gloss retention at the
very high angle of 85 degrees.
Summary
Lubrizol has developed a new self-crosslinking polyurethane
dispersion technology that has demonstrated performance com-
parable to that of commercial 2K contractor-applied wood floor
finishes. Performance of the new 1K PUD was evaluated in
terms of chemical, scuff or black heel mark, scratch and abra-
sion resistance against commercial 2K-crosslinked waterborne
polyurethane coatings along with current commercial 1K PUD
floor coatings. Furthermore, statistically designed test floor
data along with outside lab MFMA performance specifications
Lubrizol Advanced Materials Inc.
216-447-5000
www.lubrizolcoatings.com
qualification data supports the lab bench
top test results that the performance of
2K the Lubrizol 1K PUD is on par with com-
2K NCO mercial 2K PUD wood floor coatings. The
Aziridine
23.1 9.9 advantages of the new self-crosslinking
1K PUD are its user friendliness, which
49.1 43.3
eliminates potential for waste and perfor-
78.9 92.6 mance issues resulting from poor mixing,
limited pot life, and health issues related to
handling the crosslinking component. Combined with the fact
that the new 1K SCL PUD is easy to apply and quick to dry, this
can save time and money for application of the coating at a wood
floor coating job site. n
References
1 Dietrich, D, Adv. Org. Coat., Sci. Technol. Ser., 1, 55, 1979.
2 Rosthauser, J. W.; Nachtkamp, Klaus. Waterborne Polyurethanes,
Advances in Urethane Science and Technology, 10, 121 - 162,
1987.
3 Tirpak, R.E; Markusch, P.H. Journal of Coatings Technology 1986, 58,
49.
4 Dhimiter Bello et al; American Journal of Industrial Medicine 2004,
Vol.46, Issue 5, 480 491.
5 Hesselmans, LCJ; Derksen, A.J.; van den Goorbergh, J.A.M. Progress
in Organic Coatings 2006, 55, 2, 142 148.
6 Brown,C.E.H, J. Col. Chem. Assoc. 1957, 40, 1027.
7 Oyman, Z.O., Toward Environmentally Friendly Catalysts for Alkyd
Coatings, Thesis, Eindhoven University, 2005.
8 Tennebroek, R.; Geurts, J.; Overbeek, A.; Harmsen, A. Surface Coat-
ings International 2000, 83(1), 13-19.
9 Geurink, P.J.A.; vanDalen, L; van der Ven, L.G.J.; Lamping, R.R. Prog-
ress in Organic Coatings 1996, 27, 73-78.
10 US2006/0247374
11 Eastman Chemical technical publication; N-348.