Scratch resistance of UV-cured acrylic

clearcoats

I Lrinczov1 and C Decker

Dpartement de Photochimie Gnrale (UMR-CNRS No 7525), Ecole
Nationale Suprieure de Chimie Universit de Haute Alsace, 3 rue
Werner 68200 Mulhouse, France
1 On leave from Department of Graphic Arts Technology and Applied
Photochemistry, Faculty of Chemical and Food Technology Slovak
University of Technology Bratislava, Slovak Republic

Keywords
Acrylic coatings, mar resistance, scratch resistance, UV curing

Summaries
Scratch resistance of UV-cured acrylic clearcoats
The scratch and mar resistance of UV-cured acrylic clearcoats was evaluated by means of the Taber
scratch and Scotch-Brite tests. The influence of the chemical structure of the acrylate oligomer, of
the photoinitiator and of the UV dose on the scratch resistance of various UV-cured coatings was
evaluated quantitatively. No direct correlation could be found between the scratch resistance and the
hardness of the UV-cured polymer. The scratch resistance was evaluated through measurements of
the ductile/brittle transition and was significantly enhanced by the addition of a siloxane slip agent
and of acrylated silica nanoparticles. A self-healing process of ductile scratches was shown to occur
in most of these coatings upon storage at ambient temperatures or upon moderate heating.

Rsistance la rayure de vernis acryliques photorticuls

La rsistance la rayure de revtements acryliques photorticuls a t mesure par les tests Taber
et Scotch-brite.On a valu quantitativement linfluence de la structure chimique de loligomre
acrylique, du photoamorceur et de la dose UV sur la rsistance la rayure de diffrents revtements
photorticuls. Aucune corrlation directe na t trouve entre la rsistance la rayure et la duret
du polymre rticul. La rsistance la rayure a aussi t value par des mesures de la transition
ductile/cassante ; elle a t nettement amliore par laddition dun agent glissant siloxane et de
nanoparticules de silice-acrylate. Un processus dauto-rparation des rayures ductiles a t mis en
vidence dans la plupart de ces revtements lors du stockage temprature ambiante ou par
chauffage modr.

Die Kratzresistenz von UV-gehrteten Acryl-Klarlacken

Die Kratzresistenz von strahlengehrteten Acryl-Klarlacken wurde durch den Taber Kratztest und den
Scotch-Brite-test bewertet. Der Einflu der chemischen Struktur des Acryloligomeres, des Fotoinitiators und der Strahlendosis auf die Kratzresistenz von verschiedenen UV-gehrteten Lacken wurde
quantitativ bewertet. Wir fanden kein direktes Verhltnis zwischen der Kratzresistenz und der Hrte
des strahlengehrteten Polymeres. Die Kratzresistenz wurde durch die Messung der Geschmeidigkeit/Sprdigkeitstransition bewertet. Wir fanden, da die Zugabe eines Siloxan-Gleitmittels und
von acrylierten Kieselsurenanopartikeln die Kratzfestigkeit deutlich verbesserte. Die Lagerung bei
normalen Aussentemperaturen oder leichter Erhitzung lste die Selbstheilung von geschmeidigen
Kratzern aus.
For correspondence contact

C Decker
Dpartement de Photochimie Gnrale (UMR-CNRS No 7525),
Ecole Nationale Suprieure de Chimie Universit de Haute
Alsace, 3 rue Werner 68200 Mulhouse, France
Tel: +33 3 89 33 68 42
Fax: +33 3 89 33 68 95

Email: C.Decker@uha.fr

Copyright OCCA 2006

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133

Scratch resistance of UV-cured acrylic clearcoats

I Lrinczov and C Decker

Introduction
One of the important properties
requested for the organic coatings used
to protect different types of materials
and improve their surface properties is
their resistance to mechanical damage,
such as abrasion and scratching. Given
its practical significance, the subject has
been thoroughly investigated,113 in particular the scratch resistance of thermoset clearcoats. In recent years, there
has been a growing interest in UV-cured
coatings (photoset resins) because of the
distinct advantages of this environmentfriendly technology with respect to both
processing and product performance.
Under intense illumination, a solventfree resin can be hardened within a fraction of a second at ambient temperature,
with
minimum
energy
consumption and no emission of volatile
organic compounds.1416 Most of the
properties of photo-cured clearcoats
were found to be equal or even superior
to those of thermally-cured clearcoats.
Well-selected UV-cured acrylic resins
were found to have a better scratch
resistance than thermoset resins.1733
The objective of the present work was to
assess the influence of various factors on
the scratch resistance of UV-cured
acrylic coatings in order to optimise their
performance in practical applications
(automotive topcoats, wood and floor
finishes, overprint varnishes). A number
of critical factors were investigated,
namely the effect of the chemical structure of the resins, the type of photoinitiators, and the presence of some additives on the scratch resistance of
UV-cured acrylic coatings, as well as on
the permanent deformation caused by
scratching. In order to study the effect of
the UV-curing conditions on the scratch
resistance, samples were cured at various UV doses and temperatures. The
influence of storage time, film thickness
and type of substrate was also evaluated,
as well as the healing process in some
selected polymers. The authors have
attempted to determine whether a possible correlation exists between the
hardness and the scratch resistance of
various UV-cured coatings. Before
reporting the results obtained, the type
of surface damage (mar and scratch)
caused by mechanical aggression of
organic coatings will be defined and the
state-of-the-art of this topic described.

134

Definitions and evaluation

of the mar and scratch
resistance

testing. The parameters considered as

critical for the appearance of cracks are
the indenter shape,8 the applied stress
and the strain.42

A mar is a mark that is too small to be

seen by the human eye, but which
becomes visible when it is present in
large quantities. This type of surface
damage causes a loss of gloss and transparency of clearcoats. The term mar
resistance is often used to describe the
ability of the coating to resist scrubbing
and is evaluated by the loss of transparency (haze) or of gloss, expressed in
percentages. A scratch is a mark that
forms a visible groove or surface damage
caused by a sharp and hard moving
object. The scratch resistance is defined
as the minimum load applied to an
indenter of defined geometry, which
produces a continuous mark visible to
the naked eye at the surface of the coating (ISO 4586 standard). However, the
visibility of scratches depends on the
light intensity and angle of reflection, as
well as on the gloss and transparency of
the coating. As it also depends on the
observer, it is more reliable to evaluate
the scratch resistance by measuring the
size of the scratch, rather than in terms
of visibility. Consequently, different
methods and criteria are used to determine this type of surface damage.
Scratch resistance can be defined by the
load applied on the indenter, which
causes a visible single scratch having a
certain width, depth or geometry of profile.

To obtain consistent and reproducible

data characterising the damage of a surface, various shortcomings have to be
overcome. Scratch width and penetration depth need to be determined
experimentally, but it is not easy to
quantify them. Depth values may sometimes diminish with time because some
materials undergo elastic and viscoelastic recovery upon unloading, which can
be complete for some polymers.
Because of this self-healing process,
measurement of the scratch depth can
be subjective and difficult to reproduce.
Concerning the healing process, little
work has been reported on the extent
and kinetics of the scratch recovery in
organic coatings.41,45,46 For most materials, scratch width is less dependent on
the evaluation time than depth of
scratch. Some authors13 have suggested
evaluating the scratch resistance by measuring the geometry of the cross-sectional scratch profiles, rather than scratch
width or depth.

The deformation which is caused by

scratching8,3440 has three components:
elastic, ductile and brittle. The characteristic of a groove is given by the relative importance of these components,
which depends on the applied stress.
The elastic deformation is immediately
reversible so that only ductile and brittle
deformations remain on the sample.
Ductile scratches present no tearing and
heating can make them disappear, while
brittle scratches cause irreversible damage. Upon brittle deformation, cracks
appear, or tears at certain loads for some
particular materials. The human eye is
more sensitive to brittle deformation
than to ductile scratches. When the
indenter comes close to the substrate,
the stress produced leads to either
cracks or delamination of the coating.
By increasing the load during the
scratching test, the three processes occur
in the following order: elastic deformation, plastic deformation and brittle
deformation. Viscoelastic and viscoplastic behaviours during the scratch
process38,4144 have been studied, in particular via dynamic nano-indentation

Different test conditions can influence

the value of scratch/mar resistance of
polymer materials, such as the applied
load, the scratching velocity, geometry of
the scratch tip (indenter, grit particles
and special surface), as well as the time
lapse between the scratching and the
measurement. Several methods are currently used to determine the scratch/mar
resistance of clearcoats. Each application
field has its own tests, which makes the
results obtained difficult to correlate.
Scratch/mar testing is performed by
many commercially-built instruments
and homemade equipment like the
Hoffmann Test, the Taber scratch
tester,20,25,33 the Clemen test,33 the needle test,10 the single-pass pendulum sclerometer,9 the Revetest scratch tester,34
the Taber haze test,19,26,28,33 the Erichsen
test, the Scotch-Brite test,21,26 the Rota
Hub,22 and the steel wool test.26,28,33 Different testers are available to evaluate
the scratch resistance at a macro, microor nanometre scale.8,12,13,23,25,3539,47 The
applied load (up to 1000g) and scratch
speed (30mm/s) become much smaller
when going from macroscratch testers
towards nanoscratch testers (20N and
1m/s, respectively).

Experimental
The UV-curable formulations used in
this study consisted of solvent-free or
water-based resins made of acrylatefunctionalised oligomers containing a

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Scratch resistance of UV-cured acrylic clearcoats

I Lrinczov and C Decker

radical-type photoinitiator. All the chemicals used were commercially available

and are listed in Table 1. The formulations, containing typically 1 to 3wt%
photoinitiator, were cast on to glass, steel
or plastic plates at different thicknesses
between 40 and 100m. Water-borne
coatings were dried at ambient temperature until a clearcoat was obtained. The
samples were cured on a UV line (IST
Minicure) equipped with a mediumpressure mercury lamp (80W/cm) (see
Figure 1). The UV dose received by the
sample was controlled through the conveyor speed and the number of passes
under the lamp. Its value was typically
2Jcm2, as measured by radiometry
(International Light IL-390), which corresponded with five passes at a speed of
5m/min and a total exposure time of 5
seconds. The UV exposure was performed in the presence of air, either at
ambient temperature for conventional
clearcoats, or at 80C for water-borne
coatings. The degree of conversion was
evaluated by infrared spectroscopy on
samples coated on a BaF2 crystal, from
the decrease of the characteristic IR
band at 812cm1 of the acrylate double
bond.23
The scratch resistance was measured by
means of a shear/scratch tester (model
551) from Taber Inc Company (see Figure 2) on coatings cast onto a glass plate
at a dry film thickness of 100m. After
UV curing, the coatings were stored for
24 hours before testing for their scratch
resistance. With the Taber scratch tester,
a single scratch is generated by a conical
diamond indenter with an angle of 90.
The indenter is mounted on a balanced
calibrated scale, which is calibrated in
grams. A calibrated sliding weight provides an adjustment in load from 0 to
500 grams. A second calibrated weight
may be attached to the end of the beam,
thus increasing the load capacity to a
total of 1,000 grams and changing the
scale from 500 to 1,000 grams. The load
was constant during the experiment.
The scratch speed is dependent on the
rotation speed of the disc, typically
5r/min. All measurements were carried
out at ambient temperature.
The scratch resistance value (expressed
in grams) was determined by the minimal load applied to an indenter which
produced a scratch of a width of 75m,
observed with a magnifier immediately
after scratching (see Figure 3a). This
parameter allowed one to quantify and
compare the scratch resistance of different coatings in order to eliminate the
subjectivity of the evaluation. An additional way to assess the surface damage
of the coating entails monitoring the

Table 1: Characteristics of the materials used

Abreviation

Resin

Supplier

Ebecryl 830
Ebecryl 605
Ebecryl 8402
Laromer LR 8987
Laromer LR 8983

PEA
PPA
PUA1
PUA2
PUAw1

UCB
UCB
UCB
BASF
BASF

Laromer LR 8949

PUAw2

Laromer LR 9005

PUAw3

Laromer PE55WN

PEAw1

Laromer PE22WN

PEAw2

Polyester acrylate
Polyphenoxyl acrylate
Polyurethane acrylate
Polyurethane acrylate
Water-based polyurethane acrylate dispersion;
water content 60wt%
Water-based polyurethane acrylate dispersion;
water content 60wt%
Water-based polyurethane acrylate dispersion;
water content 60wt%
Water-based polyester acrylate emulsion;
water content 50wt%
Water-based polyester acrylate emulsion;
water content 50wt%

-hydroxyphenyl ketone
Bisacylphosphine oxide
Bisacylphosphine oxide
Monoacylphosphine oxide
Monoacylphosphine oxide

Ciba SC
Ciba SC
Ciba SC
BASF
BASF

Slip agent
Colloidal silica acrylate 50% SiO2
in HDDA (50nm)
Colloidal silica acrylate 30% SiO2
in HDDA (13nm)
Trimethylol propane triacrylate

Byk
Clariant

Tradename

Photoinitiator
Darocur 1173
Irgacure 819
Irgacure 819DW
Lucirin TPO
Lucirin TPO-L
Additive
Byk-VP 133
Highlink OG 103-53

A
B1

Highlink OG 103-31

B2

TMPTA

BASF
BASF
BASF
BASF

Clariant
UCB

HDDA = hexanedioldiacrylate

Figure 1a: Schematic representation of the UV-curing line

ductile/brittle transition (ie the appearance of cracks along the scratch groove)
(see Figure 3b). The crack density rises
gradually as the applied load is
increased. The scratch is considered to
become brittle when the first cracks are
observed. The appearance of cracks is
strongly dependent on the type of material tested, but it generally occurs after
the scratch width has reached the value
of 75m.
The mar resistance of the UV-cured
polymers coated on glass plates was
evaluated by means of the Scotch-Brite
test, using a scotch-brite pad (type
07442) which was loaded with a 350g

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Vol 89, B2, 99192, June 2006

Figure 1b: Picture of the minicure set-up

135

Scratch resistance of UV-cured acrylic clearcoats

I Lrinczov and C Decker

oscillation angle of 12 to a final angle of

4. Persoz values range from 30s for soft
elastomeric materials up to 400s for very
hard and glassy polymers.

Calibrated sliding weight

Precision scale arm

Diamond tool
Specimen holder

The surface energy of the cured coatings

was determined by measuring the contact angle of a drop of water (W) and of
tricresylphosphate (TCP) by means of a
Digidrop GBX equipment. The dispersive (d) and polar (p) components of the
surface energy (tot) were calculated by
using the Young equations (see Equation
1).48

Results and Discussion

Influence of the UV dose

Figue 2: Picture of the Taber scratch tester used for evaluation of the scratch resistance

Figure 3: Images of a scratch made by a conical indenter: a) ductile scratch (width 75m);
b) brittle scratch with cracks (density 16/mm) the arrow shows the scratch direction

d =

1 TCP
2 cos TCP + 1

d
TCP

p = water cos TCP

+ 1 water
d
TCP

1
2

TCP

d
where : TCP = 40.9mJm2 , TCP
= 39.7 mJm2 ,
d
water = 72.8mJm2 , water
= 21.8mJm2

136

In the case of tack-free UV-cured samples, an additional exposure to light can

delay the appearance of cracks. For
100m-thick coatings, brittle scratches
were observed already for a small
applied load (< 50g) if the UV dose was
less than two passes at 5m/min (<
0.8Jcm2). For higher doses (> three
passes at 5m/min), the scratches made
with the same load were ductile and
became brittle at higher loads (>100g).
It should be noted that while the conversion of acrylate double bonds and
scratch resistance characterised by ductile scratches tended to level off at UV
doses above 1Jcm2 (at 95% conversion
and 100g respectively for the PUA-2
sample), higher UV doses (up to 3Jcm2)
were needed to obtain a coating resistant to brittle scratches (see Figure 5). For
water-borne coatings, increasing the
irradiation temperature has the same
effect as increasing the UV dose because
it leads to a more complete cure.

Hardness - scratch resistance

correlation

Equation 1
weight and pulled 200 times across the
coated surface being tested. The mar
resistance was quantified through the
loss of transparency measured at 600nm.

The polymer obtained after UV exposure was highly cross-linked and became
more resistant to mechanical stress. As
expected, the scratch resistance was
found to increase with the UV dose
received by the sample. Figure 4 shows
how the scratch resistance and Persoz
hardness of a polyurethane acrylate and
a polyester acrylate are increasing upon
UV exposure. It can be seen that, while
the hardness of these coatings is in the
same order of magnitude (in the 180 to
230s range), their scratch resistance is
quite different, extending from 80g to
150g.

The hardness of the UV-cured coatings

was evaluated on 100m-thick films
coated onto glass plates by means of a
Persoz pendulum, measuring the damping time required to pass from an initial

Table 2 reports the scratch resistance values of various acrylic clearcoats cured by
five passes under the UV lamp at a
speed of 5m/min (UV dose of 2Jcm2).
Also reported in this table are the load
values for the appearance of cracks and

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Scratch resistance of UV-cured acrylic clearcoats

I Lrinczov and C Decker

100

50

Resin [PI] Scratch Cracks Hardness

(g)
(g)
(s)

150

PEA
PUA2

PEA
PUA2
0

0
0

0.4

0.8
1.2
UV dose (Jcm2)

1.6

1
2
3
UV exposure time (s)

Figure 4: Influence of UV dose on the scratch resistance and Persoz hardness of UV-cured
acrylic coatings. The width of a scratch was 75m [Darocur 1173] = 3wt%; light intensity:
400mW/cm2. PEA = polyester acrulate; PUA2 = polyurethane acrylate
100

PEA
PPA
PUA1
PUA2
PUAw1
PUAw2
PUAw3
PEAw1
PEAw2

2% TPO

200

160
110
80
100

250
180
120
200

290
320
150
290

1% Irgacure 819 DW

Scratch resistance (g)

Perspz hardness (s)

100

Table 2: Scratch resistance and Persoz

hardness of UV-cured acrylic polymers
coated on glass plates. UV dose:
2Jcm2. Thickness of coating: 100m.
The width of ductile scratches was
75m and the crack density was 8 per
mm

200

300

100
100
140
80
110

100
100
140
100
180

320
345
335
190
275

PEA = polyester-acrylate; PPA = polyphenoxy-acrylate; PUA = polyurethane-acrylate; PUAw = waterborne polyurethane-acrylate; PI = photoinitiator

200
80

Conversion (%)

60
100

40
Ductile

Scratch resistance (g)

150

Brittle

50

20

0
0.0

0.5

1.0

1.5

2.0

2.5

3.0

UV dose (Jcm2)

Figure 5: Influence of UV dose on the scratch resistance of a polyurethane acrylate coating

(PUA2) [Darocur 1173]= 3wt%
400
PUAw2
PPA

Hardness (s)

300

PEA

For a given UV-cured sample, the

scratch resistance increases as the coating becomes harder upon UV exposure,
as shown in Figure 6. For a given Persoz
hardness (eg 250s), the water-based
polyurethane-acrylate (PUAw1 and
PUAw2) proved to be less resistant to
scratching than the polyester acrylate
(PEA) (ie a load of 50g versus 125g,
respectively).

200
PUAw1

100
PEAw1
0
0

25

50

the Persoz hardness values. The highest

values for both ductile and brittle
scratches were obtained for the polyester acrylate (PEA) coating, which was
not the hardest polymer. This PEA coating was also found to have the greatest
mar resistance. It can be seen in Table 2
that there was no simple correlation
between the scratch resistance and the
hardness for these clearcoats. While a
relatively soft material like the waterbased polyester acrylate (PEAw1) was
easily scratchable, hard materials like the
polyphenoxy acrylate (PPA) or the waterbased polyurethane acrylate (PUAw2)
showed a similar poor resistance to
scratching. The brittle deformation
occurred at a load of about 100g, for
both PEAw1 and PUAw2, while their
hardness values were quite different:
190s and 345s, respectively. Similarly, it
can be seen that the PEA and PUA2
coatings had the same Persoz hardness
(290s), but the scratch resistance of PEA
was significantly greater.

75
100
Scratch resistance (g)

125

150

175

Figure 6: Scratch-hardness profiles for UV-cured acrylic resins. UV dose: between 0.046
and 2.6Jcm2; conventional systems: curing temperature: 25C; [Lucirin TPO] = 2wt%;
water-based systems: curing temperature: 80C; [Irgacure 819 DW] = 1wt%

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Vol 89, B2, 99192, June 2006

Influence of the substrate and

the film thickness
The nature of the substrate is another
factor which should be taken into
account when evaluating the scratch

137

Scratch resistance of UV-cured acrylic clearcoats

I Lrinczov and C Decker

Some tests were also carried out on

coatings applied onto a glass plate at different thicknesses. The initial thickness
should be more than 38m, which is the
depth of the scratch at the selected
width (75m). For 40 to 120m-thick
coatings, the value of the ductile scratch
resistance was almost constant, while
the load causing brittle deformation was
increasing with thickness, depending on
the type of polymer, as shown in Table 3.
An increase of the coating thickness was
found to delay the appearance of cracks
in the same way as a decrease of the
substrate hardness. It should be noted
that for 1mm-thick samples, cracks
appeared only for very high loads (above
600g).
To evaluate the scratch resistance of less
than 40m-thick coatings, the scratch
depth had to be reduced, and therefore
the scratch width as well. As expected,
thinner scratches were already detected
at a lower load (eg 100g for a 50mwide scratch, instead of 150g for a
75m-wide scratch, and only 70g for a
25m-wide scratch - see Table 4).

Influence of additives
The objective of this work was to evaluate and enhance the scratch resistance
of UV-cured coatings typically used to
protect metallic substrates (automotive
finishes) or wooden furniture. To achieve
this goal, the ductile/brittle transition
had to be delayed as much as possible
because it causes some irreversible
deformation of the film. The authors
have therefore tried to decrease the proportion of brittle scratches and to favour
the healing of ductile scratches.
One way to delay the appearance of
cracks is to increase the cross-link density of the coating by applying a higher UV
dose to achieve a more complete curing.

138

Table 3: Effect of the coating thickness on the performance of ductile/brittle

scratching for three UV-cured coatings on a glass support
Ductile/brittle scratches (g)

Thickness

40m

50m

60m

70m

100m 120m

1mm

PEA+3% Darocur117
150/150 150/150 150/150 150/150 150/180 150/190 220/600
PUA2+3% Darocur 1173
100/150 100/150 100/170 100/190 100/200 100/210 110/980
PEAw2+1% Irgacure 819DW 80/80 80/100 90/110 110/150 110/180 110/180

Table 4: Dependence of the scratch resistance of UV-cured coatings on the scratch

width for two thicknesses of the coating
Ductile scratches (g)

Ductile/brittle

Sample thickness

100m

30m

Scratch width
PEA+3% Darocur 1173
PEA+2% Lucirin TPO-L

25m

50m

75m

50m

70
60

100
100

150
160

90/120
90/140

Table 5: Surface tension characteristics of UV-cured coatings [Darocur 1173] 3wt%

Resin
PEA
PEA+0.5wt% A
PEA+1%wt A
PEA+2%wt A
PEA+15%wt B1
PEA+30%wt B1
PEA+50%wt B2

W()

TCP()

p(mJm2)

d(mJm2)

tot(mJm2)

57
75
85
99
63
61
77

18
33
43
50
18
22
32

13.7
6.2
3.4
0.6
10.5
11.9
5.3

40.6
36.1
32.0
28.8
40.6
39.6
36.4

54.3
42.3
35.4
29.4
51.1
51.5
41.7

A = Byk-VP133; B1 = Highlink OG 10353; B2 = Highlink OG 10331

Another way is by incorporating an inorganic filler or slip agent with the aim of
enhancing the toughness and slipperiness of the surface. Additive A (siloxyl
slip agent) was added at increasing concentrations up to 2wt%, and additive B
(colloidal silica acrylate) at concentrations up to 50wt%. Both types of additives were found to delay the
ductile/brittle transition and thus
improved the scratch resistance of a UVcured polyester-acrylate coating, as illustrated by the scratch resistance versus
UV dose profiles shown in Figure 7.
The slip agent had a marked beneficial
effect on the ductile/brittle transition,
with cracks appearing at a much higher
load (see Figure 8). In the case of the
PUA2 coating, the slip agent prevented
the formation of cracks, which appeared
only when the indenter reached the substrate. The load needed to reach the
substrate depended on the toughness of
the coating. It can be seen in Table 5
that the surface energy calculated from
contact-angle
measurements
was
markedly reduced by the presence of
the slip agent, especially its polar component. The contact angle of a water
droplet was increased from 57 to 99,
the value of the polar component (p)
dropping from 13.7 to 0.6mJcm2. A
similar but less pronounced trend was

250
200
Scratch resistance (g)

resistance of a coating. As expected, this

effect is more pronounced in the case of
thin films, while for thick films (100m),
there is no significant influence of the
substrate on the ductile scratch profile.
For example, the ductile scratch resistance of a 100m-thick PEA coating was
measured to be 150g for all the substrates tested (glass, metal, plastic). For
the ductile/brittle transition, some differences were observed depending on the
type of substrate. The load causing brittle scratch was higher (250g), in the case
of a PVC substrate, than for metal or
glass (180g), probably because a soft
substrate will better contribute to dissipate the applied strain. This behaviour
highlights the detrimental effect of hard
substrates on the scratch resistance of
topcoats.

150
100
+1wt% A
+30wt% B
PEA

50
0
0

UV dose (Jcm )
Additive A = siloxyl slip agent
Additive B = Colloidal silica acrylate
PEA = polyester acrylate

Figure 7: Influence of additives on the

scratch resistance of PEA coating.
Photoinitiator [Lucirin TPO] = 2wt%;
acrylated nanoparticles [B1] = 30wt%; slip
agent [A] = 1wt%
observed by the addition of colloidal silica acrylate to the formulation.
The type of photoinitiator used and the
addition of a trifunctional acrylate were
found to have no major effect on the
ductile scratches (see Table 6). The ductile/brittle transition occurred at higher

Surface Coatings International Part B: Coatings Transactions

Vol 89, B2, 99192, June 2006

Scratch resistance of UV-cured acrylic clearcoats

I Lrinczov and C Decker

Table 6: Influence of the photoinitiator and additives on the scratch and mar resistance of UV-cured acrylate coatings. a: [3wt% Darocur 1173]; b: [2wt% Lucirin
TPO-L]; c: [2wt% Irgacure I819]; d: [2wt% TPO]
Formulation

PEA + a
PEA + a + 0.5% A
PEA + a + 1% A
PEA + a + 2% A
PEA + a + 15% B1
PEA + a + 30% B1
PEA + a + 50% B2
PEA + b
PEA + b + 1% A
PEA + b + 30% B1
PEA + b + 50% B2
PEA + b +15% C
PEA + c
PEA + d
PUA2 + a (in air)
PUA2 + a (in CO2)
PUA2 + a + 1% A
PUA2 + a + 50% B2

Taber scratch
resistance
ductile/brittle (g)

Mar resistance
loss of transparency (%)
after Scotch-Brite test

150/180
180/200
240/300
260/360
180/250
180/190
150/150
160/250
250/430
250/300
160/180
170/250
150/160
160/250
100/200
100/200
150/650
150/400

7
10
18
20
0
0
7
9
13
9
5
30
10
6
38
22
18
13

The inhibitory effect of atmospheric oxygen on the radical-type photopolymerisation of the acrylates had a detrimental
effect on the surface properties (top
layer of a few microns) of the coatings
that were UV cured in the presence of
air. The transparency of the PUA2 coating UV-cured in air decreased by about
38% after the Scotch-Brite test, but only
by 22% when the UV curing was per-

700
Resin + Pl

+30wt% B

While the slip agent gave a better performance than the acrylated silica with
respect to the Taber scratch resistance,
the opposite trend was found for the
mar resistance evaluated by the ScotchBrite test, which caused only a few
micrometre-deep surface grooves (see
Table 6). Microphotography of the PUA2
coating after the Scotch-Brite test is
shown in Figure 9, and clearly proves the
positive effect of added SiO2 nanoparticles. Incorporation of SiO2 nanoparticles
made the surface more resistant to mar,
and no loss of transparency was
observed after the test for the PEA coatings. It may yet cause some brittleness of
the coating, which became less resistant
to deep scratches. The influence of different additives is compared in Figure 10
for the Taber test and the Scotch-Brite
test. Increasing the SiO2 particle content
from 7.5 to 15wt% caused a decrease in
the value of the ductile/brittle transition.

+1wt% A

600

Permanent deformation (g)

500

400

300

200

100

0
PEA

PPA

PUA2

PEAw1

Figure 8: Influence of additives on delaying occurrence of the permanent deformation

(brittle scratch). Conventional systems: curing temperature: 25C; [Darocur 1173] = 3wt%;
water-based systems: curing temperature: 80C; [Irgacure 819 DW] = 1wt%
loads with the photoinitiators Lucirin
TPO and TPO-L, which provided a better deep through-cure (see Figure 8).

The same trend was found with the

addition of a triacrylate monomer
(TMPTA).

Surface Coatings International Part B: Coatings Transactions

Vol 89, B2, 99192, June 2006

Figure 9: Microphotography of acrylic

coating after Scotch-Brite test: a) PUA2; b)
PUA2 + 50wt% B2 (15wt% of SiO2
particles)

139

Scratch resistance of UV-cured acrylic clearcoats

I Lrinczov and C Decker

formed in a CO2 atmosphere (see Table

6). The Taber scratch resistance was not
affected by the curing atmosphere.

400

Influence of storage and

temperature

350

Healing process
In some samples, the deformation of the
scratched resin was a time-dependent
property because of plastic relaxation.
140

250

200

150

100

50

0
Without

0.5% A

1% A

2% A

7.5% B

15% B

Figure 10a: Comparison of additive influence on the scratch resistance evaluated by Taber
test for a UV-cured polyester acrylate coating (PEA) [Darocur 1173] = 3wt%
100

80

Transparency (%)

To further improve the scratch resistance, one can submit the UV-cured
coating to a thermal treatment. Data are
reported in Table 8. For some samples,
ductile and brittle scratches appeared at
higher applied loads after heating, while
for the more resistant samples (like those
containing the slip agent or the silica),
such thermal treatment had hardly any
effect. It should be noted that when the
cured coating containing no light-stabiliser was exposed to UV radiation in an
accelerated QUV-A-weatherometer, the
value of the ductile/brittle transition
decreased slightly, possibly because of
some degradation process, which may
cause the embrittlement of such unstabilised acrylic coatings. It could also be
due to some deformation and crazing
followed by generation of cracks.

Cracks (8 per mm)

300

Scratch resistance (g)

The ageing of coated materials upon

storage is another important issue
because it may affect the scratch resistance of the coating. UV-cured samples
were stored in the dark at an ambient
temperature for up to one month. Such
storage was found to improve the
scratch resistance and to delay the permanent deformation, as shown by the
data reported in Table 7. The beneficial
effect of slip agent A and of nanoparticles B was found to be more pronounced for brittle scratches than for
ductile deformation, especially for samples stored during one month. The
improvement was more pronounced for
some coatings (from 150g to 260g for
PEA) than for others (from 100g to 150g
for PUA2), depending on the chemical
structure of the acrylate oligomer. A possible reason for this behaviour is that the
degree of cross-linking increased slowly
during storage (through the reaction of
trapped radicals), together with some
reorganisation and stress relaxation in
the polymer network. Experimental evidence of this beneficial effect had been
obtained by making brittle scratches on
the same sample at different times after
UV curing. For example, with a PEA
clearcoat, the same crack density was
obtained by using loads of 180, 220 and
300g when the UV-cured sample was
stored during one day, two weeks and
one month, respectively.

Ductile scratch (width: 75m)

60

40

20

0
Without

0.5% A

1% A

2% A

7.5% B

15% B

Figure 10b: Comparison of additive influence on the scratch resistance evaluated by

Scotch-Brite test for a UV-cured polyester acrylate coating (PEA) [Darocur 1173] = 3wt%
The scratch will become thinner upon
storage and eventually disappear completely. Such a self-healing process is
highly desirable for polymers used as
protective coatings, especially for automotive finishes. Ductile scratches may

undergo a self-healing or a heat-induced

healing process, which would result
from a slow damage recovery through
polymer chain repetition. If the sample
does not possess brittle scratches, a pristine surface is recovered after the heal-

Surface Coatings International Part B: Coatings Transactions

Vol 89, B2, 99192, June 2006

Scratch resistance of UV-cured acrylic clearcoats

I Lrinczov and C Decker

Table 7: Effect of storage on the scratch resistance of UV-cured clearcoats

a: [3wt% Daracur 1173]; b: [2wt% Lucirin TPO-L]; c: [1wt% Irgacure I819DW]
Scratch testing after storage (ductile/brittle) (g)

Storage time

0 hour

24 hours

15 days

1 month

PEA+a
PEA+1%A+a
PEA+30%B1+b
PPA+a
PUA2+a
PUA2+1%A+a
PEAw1+c
PEAw1+1%A+c
PUAw3+c

150/180
240/300
250/300
110/130
100/200
150/650
70/90
80/350
130/120

150/180
240/300
250/300
110/140
100/200
150/650
80/100
80/350
140/140

180/220
240/300
250/300
130/170
130/250
150/650
80/100
80/350
140/170

260/300
250/340
300/630
160/280
150/650
180/650
80/130
100/450
150/180

Table 8: Effect of thermal treatment on the scratch resistance. a: [3wt% Darocur

1173]; b: [2wt% Lucirin TPO-L]; c: [1wt% Irgacure I819DW]
Scratch testing after thermal treatment (ductile/brittle) (g)

Treatment

without

1 h at 50C

1 h at 80C

1 h at 120C

6 h at UVA

PEA+a
PEA+1% A+a
PEA+30% B1+b
PPA+a
PUA2+a
PUA2+1% A+a
PEAw1+c
PEAw1+1% A+c
PUAw3+c

150/180
240/300
250/300
110/130
100/200
150/650
80/100
80/350
140/140

160/190
240/320
250/310
110/130
100/200
150/650
80/110
80/350
140/150

160/190
240/320
250/310
110/130
110/220
150/650
80/110
80/350
140/150

170/190
240/320
250/310
130/150
130/290
170/650
90/110
80/350
140/150

140/160
240/280
250/310
100/120
100/180
170/650
70/80
80/250
140/150

Table 9: Healing of ductile scratches. Long-term recovery and healing by temperature. a: [3wt% Darocur 1173]; b: [2wt% Lucirin TPO-L]; c: [1wt% Irgacure I819DW]
Healing of scratches by heating

Healing

Hardness

Scratch1

25C

50C

80C

Hair drier

6h UVA

PEA+a
PEA+1%A+a
PEA+30%B1+b
PPA+a
PUA2+a
PUA2+1%A+a

270 s
270 s
320 s
320 s
235 s
235 s

170 g
290 g
290 g
120 g
190 g
640 g

No
No
No
No
10 min
30 min

10 min
10 min
1h
No
15 min
20 min

5 min
5 min
35 min
1h
5 min
8 min

3 min
2 min
10 min
No
3 min
5 min

Yes
Yes
Yes
Yes
Yes
Yes

PEAw1+c
PEAw1+c+1%A
PEAw2+c
PUAw3+c

190 s
190 s
275 s
335 s

90 g
340 g
170 g
130 g

7 min
7 min
No
No

2 min
2 min
1h
No

30 sec
30 sec
10 min
No

30 sec
30 sec
7 min
No

Yes
Yes
Yes
No

1 This value represents the highest applied load which is able to disappear

ing process. Ductile scratches may disappear completely and the residual
depth of the groove is not visible any
more by the naked eye. This healing
process at ambient temperature was
only observed with the relative hard
polyurethane-acrylate coating PUA-2
(Persoz hardness of 235s) and the softer
water-borne polyester-acrylate coating
(Persoz hardness of 190s). The best
recovery was observed with the
polyurethane coating PUA2+A, where a
scratch made with a 640g load disappeared completely within 30 minutes at
ambient temperature and 40% relative
humidity (at higher load, the indenter
reaches the substrate). For the waterborne PEAw1+A coating, the scratch
made at a 340g load disappeared within
seven minutes after unloading. This
healing process can be accelerated by
heating for a few minutes at a moderate
temperature (up to 80C), as shown by
the results reported in Table 9 for various
temperatures. Scratches on the polyester
acrylate coating (PEA) and water-borne
PEAw 2 were then also removed within
minutes.
Similar results were obtained by using a
hair drier to accelerate the healing
process. The surface of the sample was
found to reach a temperature of 63C
after five minutes of heating, and 75C
after ten minutes. Scratches which are
permanent at ambient temperatures (eg
for PEA coatings) can thus be removed
within minutes by this simple treatment
(see Figure 11). Instead of the hair drier,
one can use a stronger heating gun to
obtain higher temperatures and further
accelerate the healing process. This
technique is easy to apply and well suited to repair surface damage of a ductile
character on clearcoats and automotive
finishes.
A scratched surface can also be renovated by placing the sample in a humid
environment, the absorbed water acting
as a plasticiser. For example, a groove of
75m made on a PEA coating was found
to completely disappear within 48 hours
in a 100% humid atmosphere at ambient temperature. By contrast, samples
submitted to the Scotch-Brite test did
not undergo any healing process, even
when the grooves were only a few
microns deep. This fact can be attributed to a loss of weight upon testing by
abrasion of the superficial layer of the
coating. Such surface damage does not
present a ductile character and appears
to be irreversible, thus preventing the
healing process.

Figure 11: Healing of ductile scratch by heating of UV-cured PUA2 coating [Darocur 1173]
= 3wt%, slip agent [A] = 1wt%; a) ductile scratch: width 118m, load 300g; b )
disappearance of the scratch after heating by hair drier, heating time: 4 minutes

Surface Coatings International Part B: Coatings Transactions

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141

Scratch resistance of UV-cured acrylic clearcoats

I Lrinczov and C Decker

Conclusion
Organic coatings used to protect different types of materials (metal, plastic,
wood, paper) against mechanical stress
need to exhibit a great resistance to
scratching and wear. Acrylic-based coatings produced by UV radiation curing
proved to be quite resistant to scratching, depending on their chemical structure and regardless of their hardness.
The best performance, based on some
ductile/brittle transition data, was
achieved with photocured polyesteracrylate by using an acylphosphine
oxide photoinitiatior. The scratch resistance was significantly enhanced by
incorporating in the liquid resin a small
amount (2wt%) of a siloxane slip agent,
which also made the coating surface
very hydrophobic. For the mar resistance, the best results were obtained by
the addition of relatively large amounts
(30wt%) of acrylate-functionalised silica
nanoparticles.
Most samples were found to become
more resistant to scratches upon storage
at room temperature, a process which
was accelerated by a thermal treatment.
A slow reduction in the scratch width
was observed in some samples due to
plastic relaxation, leading eventually to a
complete disappearance of the scratch
for polyurethane-acrylate coatings. This
highly desirable feature can be
enhanced by moderate heating, thus
allowing relatively large scratches (up to
300m wide) to be repaired, as long as
cracks formed by the brittle transition
have not appeared.
Based on present achievement with
respect to both ease of processing and
product quality, one can expect the UVcuring technology to further expand and
attract more attention in an ever-growing number of sectors of applications, in
particular in the coatings industry. Producing high-performance protective
coatings by an ultra-fast hardening of a
solvent-free resin will be a great step
towards the assigned objective of meeting the constraints of the international
regulations to preserve the environment.

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