Progress in Organic Coatings 163 (2022) 106668

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Progress in Organic Coatings

journal homepage: www.elsevier.com/locate/porgcoat

Enhanced mar/scratch resistance in automotive clear coatings by

modifying crosslinked polyurethane network with branched
flexible oligomers
José M. Cuevas a, *, Rubén Cobos a, Lorena Germán a, Borja Sierra a, José M. Laza b,
José L. Vilas-Vilela b, c
a
GAIKER Technology Centre, Basque Research and Technology Alliance (BRTA), Parque Tecnológico de Bizkaia, Edificio 202, 48170 Zamudio, Spain
b
Macromolecular Chemistry Group (LABQUIMAC), Department of Physical Chemistry, Faculty of Science and Technology, University of the Basque Country UPV/EHU,
Barrio Sarriena s/n, 48940 Leioa, Spain
c
BCMaterials, Basque Center for Materials, Applications and Nanostructures, UPV/EHU Science Park, 48940 Leioa, Spain

A R T I C L E I N F O A B S T R A C T

Keywords: Mar and scratch resistance are a major concern for automotive and other industrial sectors from causing
Polyurethane inconvenient aesthetic changes on clear coats. Then, a series of two-component solvent-borne polyurethane
Clear coats coatings were formulated with branched polycaprolactone (PCL) oligomers. The effect of the partial substitution
Mar resistance
of acrylic polyols by tri- and tetra-functional PCL polyols on adhesion, chemical resistance, thermo-mechanical
Scratch resistance
Polycaprolactone
properties and aesthetic response was analysed. The PCL polyols drove to plasticised networks with lower glass
transition temperature (Tg) and promoted rubbery state at room temperature. The associated growth in chain
mobility did not appreciably affect the key performance of the coatings, apart from the chemical resistance of
formulations with PCL triols. Furthermore, remarkable improvement of wear resistance from promoted recovery
response was demonstrated. The clear coats with moderated content of PCL polyols yielded a reduced loss of
specular gloss with time after repeated scrubbing operations by an abrasive paper. The proposed approach, thus,
is presented as a versatile strategy to tailor the mechanical surface properties of clear coats.

1. Introduction
Automotive coatings comprise different layers to provide protective
and decorative surface performance to the components. Clear topcoats
are the outer layer to meet the very complex requirements from auto­
motive makers to cope with customers' demands and trends. This sector
considers fundamental to achieve excellent appearance and good me­
chanical properties. Then, the optimisation of the mechanical response
of clear coats keeps the surface appearing glossier and being more
attractive and protective [1–4].
Customer demands high damage resistance to permanently retain
durability and original first-class appearance. This appearance results
from the interaction between light and surface, where surface topog­
raphy plays a key role in light reflexion and refraction. Then, sub-micron
to millimetre scale surface damages detracts from the coating and
component aspect [5,6].
These mechanical damages can be caused by different external
elements and circumstances like car washing, handwashing, stone chips
or external impacts. In this scenario, mar and fracture scratches can be
considered according to the extent of damage to the coating. High
scratch forces produce high scale large and easily visible fracture dam­
ages. However, mar or marring refer to shallow scratches characterised
by few microns in depth and width without associated fracture from
lower mechanical forces. In this latter case, instead of the individual
light damages, the accumulation of mar defects causes the undesired
hazy visual defect from the scattering of light at scratches, losing the
first-class appearance [7,8].
Better performing clear coats are mandatory for Original Equipment
Manufacturers (OEMs) from a major number of complaints associated
with mar/scratch/chip imperfections on the surface [9]. Then, corre­
sponding improvement is a development focus of paint formulation, but
achieving an optimal solution is very challenging from several damage
mechanisms involved for different types of scratch [10]. Ductile and
brittle scratches are associated with different damage levels from a wide

* Corresponding author.
E-mail address: cuevas@gaiker.es (J.M. Cuevas).

https://doi.org/10.1016/j.porgcoat.2021.106668
Received 4 May 2021; Received in revised form 2 December 2021; Accepted 9 December 2021
Available online 22 December 2021
0300-9440/© 2021 Elsevier B.V. All rights reserved.
J.M. Cuevas et al.
Fig. 1. Tri-functional and tetra-functional PCL polyols.
range of chemistries and mechanical properties. Related scratch failure
mechanisms can vary, thus, from elastic to plastic deformation or frac­
ture [11,12].
However, understanding how coating composition influences the
surface damages from different sources of mechanical aggressions re­
mains considerably unknown, although crosslinking density plays a key
role from storing and releasing part of the mechanical energy transferred
to the coating [13,14]. Therefore, increasing crosslinking density by UV
cured systems produces harder clear organic coatings and enhances
scratch and abrasion resistance compared to conventional thermal
curing systems [15–18]. Other approach is based on combining silane
chemistry with the performance of organic clear coats [19]. The intro­
duction of hybrid crosslinkers able to produce interpenetrating polymer
network (IPN) combining, for example, a polyurethane network and a
siloxane network, creates a new crosslinked structure with improved
mechanical response [20–22].
A well know strategy to increase scratch resistance is based on
incorporating inorganic fillers into the polymer matrix at different
weight fractions depending on the size, the nature and the properties of
the filler [23]. Nanofillers have appeared as an advanced and potentially
optimal solution since enhanced properties at nanoscale, increased
interfacial area towards improved properties at low loadings and
required transparency in clear coats come together [24–26].
An outstanding family of industrial high-quality clear coats in
automotive components are based on solvent-borne and water-borne
two-component (2 K) acrylic-urethane formulations [37–39]. Poly­
urethane chemistry provides coatings with a very broad portfolio of
properties from tuneable molecular structures by controlled chemical
groups and reaction conditions [40]. Acrylic polyesters functionalized
with hydroxyl-groups produce very tough polyurethane films under
proper curing conditions when combined with polyisocyanates. An
adjusted cross-linking degree and composition, where other components
have their importance, play crucial role to control the thermo-
mechanical and chemical performance of the coating [41–42]. Since
the cross-linking density and the hard/soft segment ratio of coatings
greatly affect the flexibility and the mar resistance, the adjustment of the
molecular weight, chemical structure and functionality of the reactants
can provide different polyurethane solutions. Then, the coating can
cover from hard and stiff surface, by using short chain polyols of high
2
Progress in Organic Coatings 163 (2022) 106668
functionality, to more flexible and soft solutions by introducing long-
chain polyols with low functionality [43].
An alternative to the described strategies to prevent from the damage
is to heal the damage on the coating [27]. Extrinsic self-healing mech­
anisms are generally based on incorporating a healing agent contained
in a protective carrier within the polymer matrix. The produced damage
breaks the carrier and the healing product flows and repairs the material
by distinct mechanisms from different nature and reactivity of the
healing liquid [26,28]. Intrinsic self-healing occurs from incorporating
self-healing features in the polymer backbone. Some tuneable self-
healing properties have been obtained from reversible bond/interac­
tion like covalent bonds, h-bonds or ionic, which play a key role in the
effective management of the damage [29–31]. However, these ap­
proaches do not usually fulfil requirements, and can be far from com­
mercial availability.
An intrinsic recovery strategy to improve the mar resistance, un­
derstood as bond deformation of coatings, is to achieve a balanced
viscoelastic behaviour combining elastic and plastic deformation from
tuneable composition of the organic coatings [12]. The adjustment of
molecular motion in coatings can be a low to moderate cost innovative
approach for recovering marring deformations, where bonds are
stretched, and the coat is plastically deformed [32–36]. However, as any
other strategy, viscoelasticity-driven surface recovery must achieve a
compromise between dynamic healing at ambient temperature related
to Tg (glass transition temperature) [31–33] and the overall perfor­
mance of the clearcoat related to chemical nature of polyols and cross­
linking degree of the polyurethane [33,44] (mechanical strength,
chemical resistance, weathering, glossy and transparent appearance….).
Therefore, in order to create a polyurethane clearcoat system with
the potential to recover from marring deformation as an intrinsic
mechanism, the crosslink density should be increased while keeping the
glass transition temperature (Tg) of the polymer around or below poly­
urethane performance temperature. When the flexible polyurethane
coating is marred, the bonds are stretched due to the particular visco­
elastic behaviour around Tg. At those temperatures, the bonds can return
to their original shape by an intrinsic mechanism of recovery from
polymer segments movable enough [33].
Linear and branched hydroxyl-terminated polycaprolactones (PCL)
are biodegradable polyesters polyols extensively studied in poly­
urethane applications like biomedical, biodegradable or super­
hydrophobic coatings, among others. PCL is a soft semicrystalline
polymer, which has a melting temperature of around 60 ◦ C and a glass
transition temperature well below room temperature. Thus, it behaves
as a flexible plastic at room temperature [44,45]. Adequate ring-opening
reaction of ε-caprolactone with a different hydroxyl-terminated com­
pounds allows targeting a wide range of molecular weights, poly­
dispersity (PDI) and functionalities [46–51]. Furthermore, the use of
star-like PCL polyols in 2 K polyurethane coatings (2 K-PU) could
modulate the viscoelastic response of clear coats from flexible hex­
a‑carbon chains within the macromolecular structure [52,45].
The present study describes the development of automotive-like 2 K-
PU based clear coats with improved mar resistance due to enhanced
recovery of polymer network. The PU coatings were formulated with
multifunctional PCL polyols substituting different molar fractions of
acrylic polyols of soft segment in order to study its effect on increasing
the crosslinking and decreasing the Tg of the polyurethane. The influ­
ence of the molar ratios and the structure of the PCL polymers on the
overall performance of the PU clear coats was investigated. Thus, the
work demonstrates the potential application of these star-like flexible
polyols to easily achieving totally functional protective clear coats with
increased healing response of mar defects, based on commercially
available raw material.
J.M. Cuevas et al. Progress in Organic Coatings 163 (2022) 106668

Table 1 2.2. Coatings

Formulations of polyurethane coatings.
Coating PUref PU- PU- PU- PU- Five polyurethane clear coats were prepared by varying the type of
20PCL4101 40PCL4101 20PCL3091 40PCL3091 PCL and the ratios of polycaprolactone to acrylic resin (Table 1). Control
Acrylic polyola 100 80 60 80 60 topcoat (PUref) was the formulation without PCL using a ratio [NCO]/
(wt% with [OH] = 1.1.
respect to the Black colour Polycarbonate/poly(acrylonitrile-co-butadiene-co-sty­
PCL content) rene) (PC/ABS) specimens degreased with a mixture of deionized water
4-funct. PCL 20 40
and ethanol (1:1) were used as the substrate. The coatings were prepared
– – –
4101 (wt%
with respect to by mixing the resinous components, the catalyst, and the solvent. The
the acrylic formulations were applied by a conventional spray coating method to
polyol) achieve a 20–30 μm dry coating thickness (Fig. 2) after flash-off for 10
3-funct. PCL 20 40
– – –
min at 23 ◦ C and curing at 80 ◦ C for 30 min. Subsequently, all the
3091 (wt%
with respect to physical properties of the clear coats were measured after being main­
the acrylic tained at laboratory conditions (23 ◦ C and 50% HR) for 1 week.
polyol)
DBTDL catalyst 0.015 0.016 0.015 0.015 0.015
2.3. Characterization of coatings
(wt% based on
dry resin
content) Dry coating thicknesses were measured by ultrasonic reflection on
[NCO]/[OH] 1.1 1.1 1.1 1.1 1.1 aluminium substrates (Elcometer 456 IPC Dry Film Thickness Gauge)
ratio painted in parallel to the respective PC/ABS substrates with the same
Butylacetateb 14.1 13.4 13.7 13.0 11.5
process conditions. A non-ferrous measuring probe for non-conductive
(wt% with
respect to the coatings on non-ferrous metal substrates was used.
total The dry coatings were analysed by Attenuated total reflectance -
formulation) Fourier-transform infrared spectroscopy (ATR-FT-IR) to evaluate the
Dry thickness 27.7 28.3 ± 0.8 25.0 ± 0.6 24.2 ± 0.9 22.7 ± 0.4
reaction process by monitoring the conversion of -NCO groups. Fourier
± 0.4
transform infrared spectra were obtained by using Shimadzu MIRacle 10
a
Solid content: 60 wt%. spectrometer equipped with ATR (Attenuated total reflection). Spectra
b
For setting the viscosity to 13 s (Ford No 4 Viscosity Flow Cup at 23 ◦ C). were recorded in a range of 4000–400 cm− 1 and 20 scans were average
with a nominal resolution of 4 cm− 1.
The adhesion of coatings was measured by cross-cut tests according
to the ISO 2409 standard. Besides, the determination of resistance to
water and chemicals (xylene and ethanol) was evaluated by assessing
the adhesion and the damage to the substrate after immersion in water
and surface contact with solvents (following the procedure and rating of
ISO 2812-2 and PSA D27 5437A, respectively). In the first case, coated
samples were immersed in deionized water at 40 ◦ C for 240 h. After­
wards, the adhesion was evaluated (crosshatch test with adhesive tape),
and the rating scale of blistering was performed by comparing to cali­
brated views in normative. On the other hand, the chemical resistance
was evaluated by analysing the potential removal of the coating after
180 s of direct contact of a cotton soaked with the solvent on the coated
surface and scratched with the fingernail (45◦ angle) after gently
removing the cotton and the surface solvent.
The thermal stability of the dry coatings was evaluated by ther­
mogravimetric analysis (TGA) with a Mettler Toledo TGA/DSC 1 ther­
Fig. 2. Spray coated PC/ABS samples. mobalance. The experiments were performed with a 20 ◦ C min− 1
heating rate from 25 to 600 ◦ C under a nitrogen atmosphere to calculate
2. Materials and methods the degradation temperatures.
Differential scanning calorimeter (DSC) tests of coatings under a
2.1. Materials and chemicals constant nitrogen flow (50 ml min− 1) (Mettler Toledo DSC 1) were
conducted to evaluate the thermal properties. First heating scan was
Domacryl 504 60 X/BAc (Helios) is a hydroxyl acrylic resin dissolved performed from − 80 to 130 ◦ C at a rate of 10 ◦ C min− 1. Consecutive
in xylene (X) and butyl acetate (BAc) (X/BAc: 3/1) with a hydroxyl value cooling scan from 130 to − 80 ◦ C and a second heating scan to 130 ◦ C
on solid resin between 55 and 65 mg KOH g− 1. Polyisocyanate Desmo­ were conducted at the same cooling and heating rate, respectively. The
dur N 3580 BAc (Covestro AG) is a hexamethylene diisocyanate (HDI) glass transition temperature (Tg) was calculated from the second heating
allophanate trimer dissolved in butyl acetate with a NCO-content of scan [53,54].
about 15.4%. The thermomechanical properties of dry polyurethanes were char­
PCL Capa 3091 (Perstorp) is a polyester triol with a molecular weight acterised by dynamical–mechanical–thermal analysis (DMTA) in the
of 900 g mol− 1 and a OH value of 183 mg KOH g− 1. PCL Capa 4101 shear mode (DMA/SDTA861e Mechanical Thermal Analyser, Mettler
(Perstorp) is a tetra-functional polyol with an average molecular weight Toledo, Switzerland). The tests were accomplished with circular samples
of 1000 g mol− 1 and a hydroxyl value of 216–232 mg KOH g− 1 (Fig. 1). (free standing coating of 2 mm thick and 10 mm diameter manufactured
Anhydrous butyl acetate and dibutyltin dilaurate (DBTD) were pur­ by casting) at a deformation frequency of 1 Hz, a strain of 64 μm and a
chased from Sigma Aldrich and were used without any further heating rate of 3 ◦ C min− 1 from − 50 to 100 ◦ C. The glass transition
purification. temperature (Tg) of the coatings was defined as the maximum in the
damping peak (tan δ) [50] and from the storage modulus onset [56].

3
J.M. Cuevas et al. Progress in Organic Coatings 163 (2022) 106668

Fig. 3. ATR-FT-IR spectra of the polyurethanes: final coatings (left) and detail of the reaction of NCO groups in PU ref. and PU-40PCL3091.

Fig. 4. DSC second heating scanning of coatings as a function of content and

functionality of PCL.

Fig. 5. Thermogravimetric analysis of cured coatings with different type and

Table 2 content of PCL polyols.
Thermal properties of clear coats.
Coating DSC 2nd heating scan TGA
Table 3
Tg (◦ C) Tonset (◦ C) Tmax (◦ C) TPCL (◦ C)
Aesthetic performance of clear coats.
PUref 32.7 271.9 429.1 –
Coating Colour Gloss
PU-20PCL4101 26.6 277.4 399.5 470.6
PU-40PCL4101 19.4 280.5 399.7 470.6 ΔL* Δa* Δb* ΔELAB at 20◦ at 60◦
PU-20 PCL3091 23.0 270.7 399.5 470.7
PUref – – – – 82.6 ± 0.1 88.7 ± 0.2
PU-40PCL3091 13.2 277.3 406.1 472.7
PU- − 0.08 0.02 − 0.20 0.22 83.8 ± 0.1 89.9 ± 0.02
PCL4101 polyol – 374.4 413.4 475.1
20PCL4101
PCL3091 polyol – 371.2 414.9 466.1
PU- − 0.03 0.01 − 0.22 0.22 83.2 ± 0.1 89.5 ± 0.09
40PCL4101
PU- − 0.12 0.03 − 0.17 0.21 83.6 ± 0.04 89.5 ± 0.06
Scratch resistance of coatings was measured by pencil scratch test 20PCL3091
according to ISO 15184 standard with pencil hardness instrument PU- − 0.01 0.01 − 0.33 0.33 83.5 ± 0.1 89.5 ± 0.07
(Ref. 0300200, Neurtek, Spain). 40PCL3091
The colour and the gloss at 20◦ and 60◦ of coated specimens (ISO
11664 and ISO 2813, respectively) were evaluated to observe any po­
Mar resistance of coatings was analysed by crockmeter test under dry
tential effect of introducing the PCL on the aesthetic response. The
conditions based on ISO 11998. Repeated scrubbing operations by a
colour was measured with the multi-angle spectrophotometer X-Rite
silicon carbide abrasive paper (P2400 type M with 10 μm grain size) on a
MA-98 (X-Rite) using D65/10◦ as the illuminant/observer angle com­
cylindrical pad (29 mm diameter and 4.55 mm height) under the action
bination. The micro-TRI-gloss μ (BYK-Gardner) was used to analyse the
of a mechanical arm were performed. After 15 going/return abrasions
specular gloss.
(abraded length of 12 cm) with 9 N force, the initial specular gloss of

4
J.M. Cuevas et al. Progress in Organic Coatings 163 (2022) 106668

Fig. 6. Cross-cut test of clear coats (from left to right: PUref, PU-20PCL4101 and PU-20PCL3091).

samples was compared to the specular gloss of the damaged surface.

Table 4 Then, the gloss retention after the abrasion was calculated by following
Scratch resistance of clear coats by pencil hardness. the Eq. (1),
Coatings Pencil hardness Pencil hardness (24 h after) Bf
Gloss retention (%) = × 100 (1)
PUref B B Bi
PU-20PCL4101 B B
PU-40PCL4101 B B where Bi is the value of average initial gloss and Bf is the value of average
PU-20PCL3091 B B
final gloss at 48 h after crockmeter test with samples stored at 23 ◦ C and
PU-40PCL3091 B B
humidity of 50%.
Study of abrasion surface topography was carried out using an PLu
neox optical profiler from Sensofar. Confocal scanning technology was
used to analyse the abrasion surface in three different points at three

Fig. 7. Resistance to water immersion (left: PUref, right: PU-40PCL3091).

Fig. 8. ATR-FTIR spectra of polyurethane, peak of H-bonded urethane.

5
J.M. Cuevas et al.
Fig. 9. Resistance to ethanol (up) and xylene (down) (from left to right: PUref, PU-40PCL4101, PU-20PCL3091 and PU-40PCL3091).
Fig. 10. Shear storage modulus (G′ ) of PU clear coats.
‘recovery times’ t1 = 0.5 h; t2 = 3 h t3 = 24 h. The surface topography
obtained was treated and roughness parameters were calculated by
Sensoview software according to ISO 25178.
3. Results and discussion
3.1. Curing and thermal properties
The conducted infrared experiments (Fig. 3) demonstrated that full
conversion of isocyanate was achieved under curing conditions. In all
cases, the absence of the band corresponding to N–
– C–
– O group at 2274
cm− 1 confirmed that the isocyanate fully reacted. The spectra of the
polyurethane-urea reference and modified coatings were characterised
by the same relevant bands corresponding to N–H stretching band at
3340–3360 cm− 1, CN–NH stretching band at 1531 cm− 1 and C– –O
6
Progress in Organic Coatings 163 (2022) 106668
Fig. 11. Evolution of tan δ with temperature for PU clear coats.
stretching from urea at 1690 cm− 1. There was simply observed a slight
increased intensity of these representative bands from higher wt% of
isocyanate as the PCL content increased to keep the NCO/OH ratio
constant.
Fig. 4 shows the thermal properties of formulated coatings from the
second DSC heating scan. The calorimetry analysis indicated that cured
polyurethanes were amorphous systems with glass transitions near room
temperature. The addition of aliphatic low Tg PCL decreased the glass
transition temperature of the coatings (Table 2). This effect was also
accentuated for the tri-functional PCL characterised by lower function­
ality and longer aliphatic PCL chains for similar molecular weight if
compared to the tetra-functional polyol. Therefore, enhanced plasti­
cizing effect and potentially increased rubbery character is promoted by
the aliphatic tri-functional polyol.
J.M. Cuevas et al. Progress in Organic Coatings 163 (2022) 106668

Table 5
Key thermo-mechanical properties and crosslink density of clear coats by DMTA analysis.
Coatings Tg (◦ C) (tanδ peak) Tg (◦ C) (G′ onset point) G′ storage modulus at 25 ◦ C (MPa) Tan δ at 25 ◦ C Crosslink density (mmol/cm3)

PUref 50.0 33.4 123 0.352 0.580

PU-20PCL4101 35.3 23.8 96 0.569 0.797
PU-40PCL4101 28.7 16.6 29 0.753 1.017
PU-20PCL3091 35.4 21.5 65 0.59 0.731
PU-40PCL3091 19.6 8 7 0.774 0.896

Table 6
Specular gloss of coatings after abrasion processes.
Coatings At 60◦ At 20◦

Initial gloss (UB) Gloss after abrasion (UB) Gloss retention (%) Initial gloss (UB) Gloss after abrasion (UB) Gloss retention (%)

t = 0 min t = 48 h t = 0 min t = 48 h

PUref 88.7 46.8 52.2 58.9 82.6 18.1 24.9 30.1

PU-20PCL4101 89.9 64.4 80.6 89.7 83.8 30.9 69.1 82.4
PU-40PCL4101 89.5 77.5 83.3 93.2 83.2 58.2 74.9 90.0
PU-20PCL3091 89.5 64.1 76.3 85.2 83.6 34.0 64.5 77.2
PU-40PCL3091 89.5 84.6 85.5 95.6 83.5 77.1 78.5 94.0

Fig. 12. Specular gloss with time of clear coats after abrasive crockmeter test.

The thermal stability of the coatings was hardly affected by the PCL
type and content (Fig. 5). There was a slight improvement in the initial
decomposition temperature, but the main thermal decomposition at up
to 430 ◦ C slightly decreased and an extra decomposition stage at 470 ◦ C
appeared (TPCL), which resulted from PCL segments (Table 2). PCL
polyols were characterised by a main thermal decomposition at up to
414 ◦ C, for both tri- and tetra-functional PCL, and a secondary degra­
dation stage at 466 ◦ C and 475 ◦ C for tri- and tetra-functional polyols,
respectively.
3.2. Adhesion, aesthetics and pencil scratch
The L*, a*, b* colour space coordinates (CIELAB) of reference and
modified coatings were measured by multi-angle spectrophotometry.
The variations in the lightness (L*) and the chromatic colours (a*: green-
red field; b*: blue-yellow field) from the reference coating were calcu­
lated to analyse the potential effect of the incorporation of PCL polyols
in the clear coat. The ΔELAB difference between the colours, thus, was
calculated by the Eq. (2), considering that an observer does not notice
any difference for ΔELAB < 1 [57]. Then, as the results demonstrated
(Table 3), the PCL polyols within the structure of the crosslinked coat­
ings did not have any significant effect on the colour perception of
coated black substrates (colour space of PUref: L* = 4.35 ± 0.14, a* =
− 0.38 ± 0.01, b* = − 1.53 ± 0.02).
√̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅
ΔELAB = (ΔL* )2 + (Δa* )2 + (Δb* )2 (2)
As the visual properties have much importance in automotive in­
dustry, the surface optical quality of the coatings was evaluated too by
examining the specula gloss at two different angles of incidence. The
results (Table 3) proved that the modification of the clear coats with the
branched aliphatic polyols had barely any effect and the clear coats kept
excellent appearance.
The resistance of the clear coats to separate from substrates was
evaluated by performing lattice pattern cut into the coating and per­
forming peel test to evaluate delamination. The adhesion is classified
from 0 to 5 by analysing the amount of delamination. The 0 value refers

7
J.M. Cuevas et al.
Fig. 13. Crockmeter test (up: PUref, down left: PU-40PCL4101 and down right: PU-40PCL3091).
Table 7
Gloss 60◦ and roughness measurements.
Coatings Gloss after abrasion (UB) at 60◦ (48 h)
PUref 52.2
PU-20PCL4101 80.6
PU-40PCL4101 83.3
PU-20PCL3091 76.3
PU-40PCL3091 85.5
to no delamination and the increased detachment area of the crosscut of
less than 5%, whereas 5 corresponds to high delamination with
increased detachment area of the crosscut higher than 65% [58]. In all
the cases, i.e. in the reference clear coat and in the modified systems,
maximum adhesion performance was determined (0 value in grading
scale) and non-detrimental effect on the adherence from introducing the
PCL polyols was observed (Fig. 6).
The analysis of the scratch resistance of the coatings was performed
by pencil scratch test. The highest pencil hardness that did not produce
scratches on the coating surface was evaluated and no differences be­
tween reference and modified coatings were observed. Furthermore, the
analysis of the same scratches 24 h after the execution of the test indi­
cated not efficient enough autonomous healing process with this
scratching aggression in all cases (Table 4).
3.3. Chemical resistance and thermo-mechanical properties
The resistance to water immersion was not affected by the content
and the functionality of the polycaprolactones. After immersion, all the
samples did not show any blistering or decolouration effects on the
surface, as well as the adherence achieved 0 value according to grading,
i.e., non delamination occurred. Therefore, the PCL was not counter­
productive to water resistance of coatings (Fig. 7).
Nevertheless, a difference in the chemical resistance was observed as
function of the PCL polyol, where polyurethane based on tri-functional
PCL was not characterised by resistance to xylene. As demonstrated by
thermal analysis, the incorporation of PCL polyols shifted the Tg to lower
8
Progress in Organic Coatings 163 (2022) 106668
Surface roughness (nm) t = 0.5 h Surface roughness (nm) t = 24 h
26 24
13 ≈8
4 ≈4
6 ≈6
5 ≈4
temperature and increased the chain mobility of the polymer at room
temperature. However, PU with 20 wt% of tri-functional PCL
substituting acrylic polyols was characterised by lower urethane
hydrogen bonds than that of PU with 20 wt% of tetra-functional PCL (H-
bonded urethane at 1687 cm− 1 from appearing at a lower wavenumber
than that of free carbonyl [44–45]) (Fig. 8). This reduction, together
with the increased spacing between knots by longer PCL chains, which
are partially soluble in aromatics like xylene, seemed to comparatively
diminish the integrity of the network. This behaviour was also observed
in formulations with 40%wt of PCL (Fig. 8). Therefore, according to the
chemical structure of the PCL used, the enhanced chain mobility and
associated free volume promoted higher solvent uptake that led to
chemical attack and delamination of the coating. As can be seen below
(Section 3.4), this higher chain mobility and potentially enhanced
rubbery characteristics could improve the resistance to mar defects but
undermined the chemical resistance of the coatings to meet automotive
specifications.
Then, the reference coating and the formulations with tetra-
functional PCL polyol did not suffer any removal of the coating after
3 min of direct contact of both ethanol and xylene. Nevertheless, clear
evidence of coating removal when scratched with the fingernail after 3
min contact with a cotton soaked with xylene was observed in the for­
mulations modified with the tri-functional PCL polyol (Fig. 9).
DMTA analysis confirmed the results from calorimetric analysis
(Figs. 10 and 11). The increased chain mobility within the PU network
shifted the Tg to lower values as the PCL content increased and the
functionality of the polyol decreased (Table 5).
J.M. Cuevas et al.
Fig. 14. Microscopy images: a) PUref t = 0.5 h b) PUref t = 24 h c) PU-40PCL3091 t = 0.5 h d) PU-40PCL3091 t = 24 h.
The storage modulus of the polyurethanes decreased at temperatures
close to the Tg due to the transition from glassy state to less stiff amor­
phous rubbery state of crosslinked network. Then, the mar resistance at
room temperature (Section 3.4) of the reference coating was performed
on stiffer and harder glassy surface, whereas in PCL based formulations,
the viscous performance, with associated different deformation and
energy management, grew in importance under abrasion test as the Tg
dropped from the PCL content increasing.
The crosslinking density (Table 5) in terms of elastically effective
network chains per cubic centimetre of film was calculated using Eq. (3):
′ affected by the dropped Tg. Then, both the instant recovery and the final
G
Ve =
RT
where storage modulus value, G′ , is obtained in the rubbery plateau
(80 ◦ C in the storage modulus curve), T is the temperature in degrees K
corresponding to the storage modulus value, and R is the gas constant
[55].
3.4. Mar resistance
The analysis of mar resistance of the coatings was performed by
evaluating the loss of specular gloss due to remained damage surface
after repeated scrubbing with the abrasive paper. The reference coating
demonstrated a limited mar resistance from stable loss in gloss with time
up to a 41% and a 69% at 60◦ and 20◦ , respectively. Once scratched, the
coating barely recovered the gloss with time due to permanent mar
damages on the surface. At room temperature, below the corresponding
glass transition temperature, the produced surface defects were not
recovered by any potential elastic response of the coating at vitrified
status.
The clear coats formulated with PCL polyols demonstrated an
improved mar resistance (Table 6). Independently of the type and con­
tent of PCL within the crosslinked network, the coatings exhibited an
immediate outstanding retrieval of caused deformation and associated
Progress in Organic Coatings 163 (2022) 106668
gloss by reflow effect. This instant recovery effect and the evolution of
gloss with time varied according to the formulation (Fig. 12).
As detected in the thermo-mechanical analysis, in addition to
increasing the cross-linking density, higher content of PCL promoted
shifting Tg to temperatures near or below room temperatures (operating
temperature). Therefore, PCL provided a plasticizing effect that favours
the chain mobility and enhances the reflow recovery of surface de­
formations. Accordingly, higher cross-linking density resulted in lower
plastic deformation (higher immediate gloss retention after abrasion),
although with less influence in the reflow capacity, which was mostly
(3) gloss retention with time were enhanced with the PCL content. Even­
tually, improved mar resistance without external energy application
from autonomous and almost instantaneous recoveries was achieved.
At lower fractions of PCL, the instant and the time dependent re­
covery of mar damages was similar for both tri- and tetra-functional
polycaprolactones. Just seemed that the long-term retrieval worked
better for tetra-functional PCL from more crosslinked network with
enhanced stability. Just at higher contents, the introduction of PCL
based triol upgraded the instant healing from less crosslinking and
higher flexibility and mobility due to lower functionality and longer
aliphatic PCL chains within the PU structure. The final gloss was
improved too, although the long-term healing starting from lower
specular gloss was more effective in case of tetra-functional aliphatic
polyols.
The PCL polyols, thus, contributed to a better management of mar
defects, eventually minimising surface fracture, healing light de­
formations and improving the aesthetic response of clear coats from
reducing hazy visual defects (Fig. 13).
As it was expected, the confocal results showed a correlation be­
tween final gloss and surface roughness of marred areas. Since the re­
covery mechanism was nearly instantaneous, the evolution of roughness
with time was not detected, unless in PUref and PU-20PCL4101, which
suffered a slight reduction of roughness value (Table 7). Then, no sig­
nificant evolution of abrasion surface took place from 0.5 h to 24 h after
9
J.M. Cuevas et al.
abrasion (Fig. 12 and Fig. 14). On the other hand, the final gloss and
roughness values of marred areas of modified coating were close to these
parameters in coating without abrasion damage, which revealed a fast
and effective recovery of abrasion for polyurethanes modified with
PCLs.
4. Conclusions
Aesthetic and durability related demands placed upon clear coats by
manufacturers and customers are more demanding. These requirements
continually drive coatings technology into finding new and more
effective solutions. In this scenario, the described incorporation of hy­
droxyl functional polycaprolactones allows handily adjusting the sur­
face resistance of 2 K-PU based clear coats towards improved mar
resistance. Then, partial substitution of acrylic polyols by tri- or tetra-
functional low molecular weight PCL polyols results in more flexible
network able to recover the shallow mar defects towards more lasting
glossy surfaces.
The content of the PCL polyols affects the thermo-mechanical
properties of the PU coatings by increasing the cross-linking density
and the plasticizing effect. This last one decreases the glass transition
temperature and enhances the autonomous reflow response at operating
temperatures from promoted viscous response and effective elastic
behaviour. This effect is promoted by the tri-functional polyols with
lower functionality than tetra-functional polyols and longer aliphatic
chains between knots that increases chain mobility within the cross­
linked network.
This enhanced mobility and lower Tg from introducing PCL polyols in
2 K-PU clear coats result in effective recovering of mar defects. Then, as
the PCL content increases the gloss retention after mar abrasion grows.
The tetra-functional PCL provides gloss retentions at 60◦ above 89 and
93% for low and high PCL content, respectively. The tri-functional PCL
polyol raises the gloss retention at 60◦ above 85 and 95%, for low and
high concentrations, respectively. Furthermore, this response to abra­
sion does not noticeably compromise other key aesthetic and chemo-
mechanical features of the topcoats from incorporated PCL polyols
even though excessive plasticizing effect involves limited chemical
resistance. The potential effect of excessive PCL triol on the integrity of
crosslinked polymer network can drive to unsuitable resistance to
chemicals that automotive and other sectors require for clear coats.
The present work, thus, can provide an effective approach to
straightforwardly improve the abrasion resistance of clear coats by
minimal modification of composition with branched PCL polyols.
CRediT authorship contribution statement
José M. Cuevas: Conceptualization, Methodology, Writing – orig­
inal draft, Project administration, Funding acquisition. Rubén Cobos:
Methodology, Investigation, Validation, Writing – original draft. Lorena
Germán: Investigation, Writing – original draft. Borja Sierra: Investi­
gation. José M. Laza: Investigation, Writing – review & editing. José L.
Vilas-Vilela: Writing – review & editing, Supervision.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgements
This work was supported by the Ministerio de Ciencia e Innovación
[RTC-2016-4887-4] and the Department of Economic Development,
Sustainability and Environment of the Basque Government [ELKARTEK
KK-2019/00077 (FRONTIERS V)].
10
Progress in Organic Coatings 163 (2022) 106668
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