J. Coat. Technol. Res.
, 11 (5) 697–710, 2014
DOI 10.1007/s11998-014-9589-4
Characterization of clearcoats containing phosphoric
acid-functionalized acrylic polyols for automotive
precoated metal sheet coatings
Jae Young Lee, Myung Seon Yi, Ho Cheol Jeong,
Jung Teag Kim, Joon Hyun Nam, Seung Man Noh,
Hyun Wook Jung
 American Coatings Association 2014
Abstract In this study, the various physical and mechan-
ical properties of clearcoats prepared through a new
crosslinking method were investigated. The method was
aimed at developing clearcoat systems to improve the
deep-draw processing and formability performance in
precoated metal (PCM) sheets for automotive applica-
tions. From phosphoric acid-functionalized acrylic poly-
ols (PAFAPs) first synthesized in this study and glycidyl
methacrylate-modified acrylic copolymer (GMAMAC),
phosphoric acid-GMA modified acrylic polyols
(PAGMAPs) were newly prepared as new binders in
automotive clearcoats. Several clearcoats were formu-
lated with different molecular weights and hydroxyl
contents from PAFAPs and GMAMAC. Using clear-
J. Y. Lee, M. S. Yi, H. C. Jeong, S. M. Noh
PPG Industries Korea, Cheonan 330-912, Republic of Korea
H. C. Jeong
Department of Green Energy Convergence Engineering,
Yeungnam University, Gyeongsan 712-749, Republic of
Korea
J. T. Kim
Corrosion Engineering Division, Pohang Institute of Metal
Industry Advancement, Pohang 790-834, Republic of Korea
J. H. Nam
Research Center for Green Fine Chemicals, Korea
Research Institute of Chemical Technology, Ulsan 681-310,
Republic of Korea
S. M. Noh (&), H. W. Jung (&)
Department of Chemical and Biological Engineering, Korea
University, Seoul 136-713, Republic of Korea
e-mail: smnoh@ppg.com
H. W. Jung
e-mail: hwjung@grtrkr.korea.ac.kr
coats themselves, the crosslinking reactions for these
clearcoats were compared by evaluating the curing
behaviors with a rigid-body pendulum test (RPT) and
the changes of chemical structures via attenuated total
reflectance FTIR spectroscopy. The mechanical proper-
ties of the clearcoats were systematically characterized,
using dynamic mechanical analysis (DMA) and universal
testing machine analysis (UTM). Also, various tests were
carried out using PCM sheets by depositing clearcoats
above the same PCM-based primers and basecoat layers
on galvanized steel. The fracture and deformation
patterns related to surface damages on the clearcoat
surface were visualized using a nano-scratch test, in
association with atomic force microscopy. In particular,
deep-draw processing tests, based on forming process
simulations, were employed to scrutinize the effect of
clearcoats developed in this study on the forming feature
in PCM sheets. From the results of RPT, DMA, and UTM
tests, the primary crosslinking networks of PAGMAPs
from the synthesized PAFAPs and GMAMAC, and also
succeeding secondary crosslinking networks between
PAGMAPs and blocked isocyanates, were closely corre-
lated with the degree of crosslinking (Xc), in accordance
with the molecular weight between crosslinks (Mc), and
glass transition temperature (Tg). As a result, the
presented clearcoats with a long pendulum period, a
low rubbery modulus, and a large tensile strain value,
which are the significant factors for developing automo-
tive PCM sheet technology, have truly demonstrated
more superior formability during the deep-draw process.
It is confirmed that properties of clearcoats with tough-
ness and flexibility could be optimally controlled by
PAGMAPs for automotive coatings.
Keywords Automotive clearcoat, Precoated metal
sheet, Phosphoric acid-functionalized acrylic polyols,
Glycidyl methacrylate, Phosphoric acid-GMA
modified acrylic polyols, Deep-draw formability,
Crosslinking networks
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J. Coat. Technol. Res., 11 (5) 697–710, 2014
Introduction
The present original equipment manufacturer (OEM)
coating process in automotive industries includes the
coating applications of many different layers to uncov-
ered outer panels of preformed car body, e.g., pre-
treatment, electrocoat, primer, basecoat, and clearcoat.
Recent environmental problems associated with vola-
tile organic compounds (VOCs) of coatings in the
spraying process have driven the necessity for new
environmentally friendly automotive coatings that can
considerably reduce volatile materials by implement-
ing a shorter and more compact coating process. With
this in mind, the roll-to-roll continuous coating process
has been suggested as an alternative coating technol-
ogy to manufacture precoated metal (PCM) sheets for
future automotive applications. In other words, PCM
sheets could potentially be produced by depositing
coatings in a series onto a flat metal sheet via the roll
coating process,1–3 and then be transferred to forming
processes for making modularized outer panels of a car
body. Using the roll coating process can effectively
eliminate the negative environmental consequences
involved in the existing conventional coating methods,
such as dipping and spraying procedures, i.e., problems
with recycling sprayed mists and removing resulting
VOCs in coating operations. Furthermore, the roll
coating process for PCM sheets not only increases
production rates and requires less factory space, it also
reduces the quantity of sewage sludge and wastewater
in the pretreatment and electrocoating stages, due to
the simplification of the coating lines.1–3
Accordingly, extensive studies have been under-
taken to design automotive coatings and related
coating processes,1–3 based on PCM sheet technology,
for the optimization of the various properties of
coatings and their appropriate applications. In partic-
ular, researchers from various fields have sought to
clarify the relationship between mechanical properties
of PCM sheets and their formability.4–6 Roescher and
Tinnemans7 reported the good deep-drawing feature of
one coating system combined with anticorrosion and
lubrication functions. Ueda et al.8–10 correlated the
formability of polyester/melamine PCM sheets with
rheological and mechanical properties of coatings.
Amo et al.11 evaluated the performance of coated
steel systems with different pretreated galvanized steel/
primer/topcoat paint combinations; and thereafter,
Santos et al.12 recently characterized the properties of
coatings deposited on galvanized steel sheets for
automotive bodies. The mechanical properties of
clearcoats as an outer layer in automotive coating
systems, encompassing not only viscoelastic but also
scratch and marring characteristics, are of particular
significance.13–15 This is because the appearance, gloss
retention, and polymeric film breakage of clearcoats
are more important than those in bottom layers on
metal sheets such as the primer or basecoat. Moreover,
the balance between toughness and flexibility in
698
association with an aesthetic glossy finish under the
forming processes needs to be established in clearcoats
for automotive PCM sheets.
This study has focused on the mechanical proper-
ties of clearcoats produced by a new crosslinking
method to enhance the deep-draw formability in PCM
systems for automotive application. The new recipe
for formulating clearcoats was based on the combi-
nation of both synthesized phosphoric acid-function-
alized acrylic polyols (PAFAPs) and glycidyl
methacrylate-modified acrylic copolymer (GMAMAC)
and a commercially blocked aliphatic polyisocyanate
thermal crosslinker, i.e., 1,6-hexamethylene diisocya-
nate (HDI) with 3,5-dimethyl pyrazole (DMP) as a
blocking agent. It is noted that PAFAPs were
synthesized for the main binder for the first time in
this study, and also the crosslinking reaction between
PAFAPs and GMAMAC were first applied in auto-
motive clearcoat systems. Participation of hydroxyl
groups of phosphoric acid-based resins in association
with the ring opening reaction of the epoxy group
within GMAMAC can increase the adhesion and
flexibility features in a clearcoat by their unique bond
strength, and also corrosion resistance via a phospho-
ric acid functionality, leading to the advanced forming
performance and end-product quality of PCM
sheets.16–18
First, curing behaviors and various properties for
clearcoat samples themselves formulated in this study
were characterized. The clearcoat systems are naturally
affected by the curing process which induces a cross-
linking reaction between hydroxyl groups on the
acrylic copolymer and deblocked isocyanates on
HDI. The degree of crosslinking reactions of several
clearcoats with different molecular weights and hydro-
xyl values of PAFAPs was quantified by curing
behaviors, in accordance with a rigid-body pendulum
test (RPT) method and transitions of chemical struc-
tures, via attenuated total reflectance (ATR) FTIR
spectroscopy. The mechanical properties of free-stand-
ing clearcoat films were acquired by means of dynamic
mechanical analysis (DMA), and universal testing
machine analysis (UTM). Also, their water-swelling
and gel-fraction features were analyzed to measure the
density between crosslinks of clearcoats.
In addition, using PCM sheets where clearcoats
were deposited over PCM-based primers and basecoat
layers, mechanical tests for clearcoat layers in PCM
sheets were conducted. Results by pendulum, pencil
hardness, and impact tests were compared. The frac-
ture and deformation patterns of damages on clearcoat
surfaces were visualized using the nano-scratch test
(NST) and atomic force microscopy (AFM). Eventu-
ally, the deep-draw formability test, which produces a
square-type column from a flat PCM sheet as a
simulation of the real forming process, was also
employed to scrutinize the processing performance of
PCM sheets, i.e., to check cracking and delamination of
coated layers in deformed PCM sheets.8–10,19,20

Experimental
Materials
Synthesis of PAFAP and GMAMAC
Two key ingredients (PAFAP and GMAMAC) in
automotive clearcoats were synthesized, which newly
produce phosphoric acid-GMA modified acrylic polyol
(PAGMAP) through the ring opening reaction, to
effectively make up the processing performance of
PCM sheets16–18 by supplying increased adhesion and
flexibility to clearcoats.
The synthetic processes for PAFAPs and GMAMAC
are as follows: styrene monomer (Samsung Total, Korea),
2-hydroxyethyl methacrylate (2-HEMA, Nippon Shoku-
bai, Japan), methyl methacrylate (MMA, Lotte Chemi-
cal, Korea), normal butyl acrylate monomer (n-BAM,
Sasol, South Africa), 2-hydroxyethyl methacrylate phos-
phate (PIM, Kyoeisha Chemical, Japan), 2,4-diphenyl-4-
methyl-1-pentene (DPMP, G.O.I. Chemical, Japan), and
glycidyl methacrylate (GMA, Nippon Oil & Parts, Japan)
were dehydrated over molecular sieves at 50C for 48 h.
Extra pure grade dicumyl peroxide (DCP, Arkema
Yoshitomi, Japan) and dibutyltin dilaurate (DBTDL,
Aldrich) were used as received.
A 1-L round-bottomed, four-necked separable flask
was used as a reactor, equipped with a mechanical
stirrer, a thermometer, and a condenser connected to a
drying tube and an N2 inlet. The reaction was per-
formed in an oil bath at 50C. To synthesize the
PAFAPs, ethyl 3-ethoxypropionate (EEP) was charged
into the dried flask, under increasing temperature
conditions up to 145C. The premixture solution was
added at a constant rate into the flask for 5 h under N2
gas of 0.5 cm3/min, consisting of styrene (24 g), 2-
HEMA (17 g), MMA (10 g), BAM (13 g), 2-propenoic
acid-2-methyl (2-phosphonooxy) ethyl ester (Lightester
PM, Aldrich) (1 g), 2,4-diphenyl-4-methyl-1-pentene
(AMSD, Aldrich) (1 g), and DCP (4 g). After the
reaction process continued for 3 h under the fixed
conditions, the synthesized copolymer was diluted using
Kocosol #100 (10 g), to optimize viscosity in parallel
with cooling. Molecular weights of the three PAFAPs
synthesized as the above were preferentially measured
using gel permeation chromatography (GPC, e2695/
2414, Waters, USA) as shown in Table 1, respectively.
To produce the GMAMAC with a well-known
synthetic method as the next step, butyl acetate (BA,
Aldrich) was charged into the dried flask, by controlling
temperature conditions of steady temperature increase
to 110C, additional increase to 135C, and final
maintenance of 135C for 3 h. The premixture solution,
containing 16 g of n-butyl methacrylate (BMA, LG
Table 1: Molecular weights of phosphoric acid-functionalized acrylic polyols (PAFAP) A to C measured from GPC
Synthesized acrylic resin PAFAP A
Molecular weight (Mw) 7258
J. Coat. Technol. Res., 11 (5) 697–710, 2014
Chem), 7.5 g of n-BAM, and 16.5 g of GMA, was added
at a constant rate into the flask, and an additional
premixture, consisting of 0.41 g of DCP and 8.14 g of
BA, was likewise inserted over a period of 4 h.
PAFAPs with different molecular weights and
hydroxyl contents and GMAMAC synthesized as
above produce various PAGMAPs, through a hydroxyl
group of phosphoric acid-based resin in association
with the ring opening reaction of the epoxy group in
GMAMAC under 100C, which mainly participate in
subsequent polymerization reaction with the blocked
isocyanates on HDI. A more detailed reaction scheme
for the polyurethane crosslinking reaction is illustrated
in Fig. 1, starting from PAFAPs and GMAMAC.
Preparation of clearcoats and PCM sheets
To formulate the clearcoats, three different PAFAPs
were synthesized by changing the values of the hydroxyl
group from 0.6 to 2.2%, as listed in Table 2. Trixene BI
7982 (HDI with blocked DMP, Baxenden, Germany)
and DBTDL (Aldrich) were used as a crosslinker and a
tin catalyst for the thermally induced poly-addition
reaction between the polyol and isocyanate functional-
ities, respectively. The mole equivalent ratio of [OH]0
to [NCO]0 was approximately 1–1.1 for this study. Small
portions of Dynoadd F-1 (Dynea, Germany) and BYK-
052 (BYK, Germany) were added as silicone-leveling
and defoaming agents for surface leveling control,
respectively. Butyl acetate, PM acetate (propylene
glycol monomethyl ether acetate), and EEP were
inserted as volatile solvents (Table 2). Physical prop-
erties of the crosslinked clearcoats were measured after
being kept at room temperature for 24 h.
Galvanized steel panels [20 cm (length) 9 15 cm
(width) 9 0.8 mm (thickness)] with an alkaline-based
pretreatment (NC-Coat 3300, Nipsea Chemical, Kor-
ea) without chromate treatment were applied for
making PCM sheets. Two PCM-based primers with
90 s viscosity measured by Ford cup #4, i.e., corrosion-
resistant and barrier function ones, were deposited in a
series on the pretreated layer, with thicknesses of 15–
18 and 18–20 lm, respectively, using a bar coater. The
first primer includes high molecular weight polyester
with linear structure, e-caprolactam-modified polyes-
ter, and highly methylated melamine (Cymel 303,
Allnex, USA) and the second primer includes
e-caprolactam-modified polyester and blocked isocya-
nate with HDI (Trixene BI 7981, Baxenden, Ger-
many), supported by PPG Industries. The black PCM-
based basecoat with 80 s viscosity was also coated to a
thickness of approximately 10–13 lm, including
e-caprolactam-modified polyester and blocked
PAFAP B PAFAP C
11,875 19,529
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J. Coat. Technol. Res., 11 (5) 697–710, 2014

R2
O O H
O
OH H O
R1 O O
O H
HO P O + Phosphoric acid – glycidyl
reaction HO
O O O
R1 P
O R2 100°C O
O
O

PAFAP GMAMAC PAGMAP

O H O
R2 OR, O
O H DMP
N(H2C)6 (CH2)6NH C
O
O N N
H R1 O
DMP
O HO +
P O N O
O
O (CH2)6NH
O
C DMP
O

PAGMAP Blocked polyisocyanate based on HDI

O
O
O DMP
R2 O
P H O C
OH O O
N O N(H2C)6 (CH2)6NH
HN OH O R1 N N
160 – 240°C O

O N O
DBTDL
(CH2)6NH

C
O DMP
OR,

R2
O O
HO H O C DMP
R1 O O
N(H2C)6 (CH2)6NH
O HO N N
P O
O
O O N O
O

(CH2)6NH
C DMP
O

Fig. 1: Schematic of reactions between phosphoric acid-functionalized acrylic polyol (PAFAP), glycidyl methacrylate-
modified acrylic copolymer (GMAMAC), and blocked 1,6-hexamethylene diisocyanate (HDI) with 3,5-dimethyl pyrazole as a
blocking agent

isocyanate with HDI (Trixene BI 7961, Baxenden, in Table 2 were twice coated onto the black basecoat
Germany), also supported by PPG Industries. Finally, layer at total thickness of 30–35 lm, and subsequently
the clearcoats (A to C) with 70–75 s viscosity as shown cured by a thermal curing sequence, considering the

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 J. Coat. Technol. Res., 11 (5) 697–710, 2014

Table 2: Formulations of clearcoat systems containing the synthesized PAFAPs and GMAMAC
Contents NV (%) OH (%) Clearcoat A Clearcoat B Clearcoat C

Butyl acetate 7.0 7.0 7.0

PM acetate 8.0 8.0 8.0
PAFAP A 75.0 2.2 45.0
PAFAP B 69.0 1.1 51.0
PAFAP C 70.0 0.6 55.0
GMAMAC 44.0 5.0 5.5 6.1
Trixene BI 7982a 70.0 30.0 27.5 28.0
BYK-052 1.0 1.0 1.0
Dynoadd F-1 0.5 0.5 0.5
DBTDL 0.2 0.2 0.2
EEP 3.5 3.5 3.5
Total 100.2 100.2 100.3
OH equivalent 0.046 0.036 0.029
NCO equivalent 0.051 0.040 0.032
Mole equivalent ratio of NCO/OH 1.108 1.094 1.102
a
Trixene BI 7982 includes 10.2% of NCO

peak metal temperature (PMT) within the range of 225
to 241C, as summarized in Fig. 2.
Various characteristics of clearcoats possessing
phosphoric acid and GMA functionalities in PAG-
MAP, i.e., mechanical properties of clearcoat films and
deep-draw formability in PCM sheets, were systemat-
ically compared with those of the conventionally
thermal curable one-component clearcoat based on
acrylic polyol and melamine crosslinkers for automo-
tive application from PPG Industries, under different
thermal curing sequence conditions (140C for
20 min).
Characterization methods
FTIR analysis
FTIR spectroscopy (Spectrum 100 FTIR, PerkinElmer,
USA) was involved to figure out the difference of
chemical reaction between the hydroxyl functional
groups in PAGMAPs and the dissociated isocyanate
functional groups on the HDI crosslinker within cured
clearcoats under different PMT conditions. Spectra
acquisition of absorption bands was based on eight
scans with a wavelength spacing of 1 cm1 in the range
of 650 to 4000 cm1, using ATR technology. The
absorption peaks at 2270 cm1 and at 1685 cm1 were,
respectively, assigned to –NCO and –COO bands in
the urethane bond (–NHCOO–).

Curing patterns using RPT Water-swelling and gel-fraction measurement

A rigid-body pendulum tester (RPT-3000 W, A&D,
Japan) was employed to characterize the curing behav-
ior of the clearcoats. It is based on the same principle as
pendulum or rocker hardness tests in which a pendulum
rocks back and forth in contact with a wet coating
surface. With the RPT, the pendulum is in contact with
the test surface via a cylinder (cure coatings) or knife
edge (wet coatings). The platen on which the painted
coupon is placed has a heating element and the
temperature can be programmed. Pendulum swinging
motion is initiated automatically and the rate at which
motion dies out (damping) and the period of motion are
measured. [Refer to ISO methods 12013-1 and 12013-2
and references (13,15,19,20) for details].
RPT measurements were done here on wet clear-
coats on the platen by gradually raising the curing
temperature from room temperature to 300C for
30 min. A knife-edge shape swinging pendulum was
installed.
The crosslinking density of clearcoats can be inferred
from the information of water-swelling and gel-fraction
measurement. The cured clearcoat films with dimen-
sions of 50 mm (length) 9 50 mm (width) 9 0.3 mm
(thickness) were prepared, then dried in a vacuum
oven at 140C for 30 min to completely remove
remnant solvents. For the water-swelling test, each
film was swollen in double distilled water at room
temperature for 10 days. The degree of water swelling
of the crosslinked films was periodically measured for
10 days, using the following equation.21,22
W  W0
Degree of water-swellingð%Þ ¼  100; ð1Þ
W0
where W0 denotes the weight of the dried film and W is
the weight of the water-absorbed one.
The gel fraction in films was regularly measured, by
immersing them in toluene or N,Ń-dimethylacetamide

701
J. Coat. Technol. Res., 11 (5) 697–710, 2014
Galvanized steel panel
Pretreatment (1–2 μ m)
Corrosion-resistant primer (15–18 μ m)
Barrier primer (18–20 μ m)
Black basecoat (10–13 μ m)
Clearcoat (total 30–35 μ m, twice-coated)
Fig. 2: Preparation of PCM sheet panels through 5-coat and 5-bake (5C5B) procedures
PCM
Die sheet
Punch
Fig. 3: Scheme diagram of deep-draw processing test
for dissolving unreacted binder left in the film, during
the duration period of 10 days, as given by
W0  W
Degree of gel-fractionð%Þ ¼  100;
W0
where W0 and W represent the weights of the dried film
before and after immersion in a solvent, respectively.21,22
702
• Bath temp. 45°C/10 min for oil free
• PMT 80°C
• Ambient temp. 200°C/curing time 7 s
(Holding time 10 sec after bar coating)
•PMT 224°C
•Ambient temp. 300°C/curing time 30 s
(Holding time 10 sec after bar coating)
•PMT 232°C
•Ambient temp. 300°C/curing time 30 s
(Holding time 10 sec after bar coating)
•PMT 232°C
•Ambient temp. 300°C/curing time 30 s
(Holding time 10 sec after bar coating)
•PMT 241°C
•Ambient temp. 300°C/curing time 30 s
Die
Punch
Deep
drawing
Viscoelastic properties using DMA
To determine the change in viscoelastic properties of
ð2Þ clearcoats with respect to the measuring temperature,
the small amplitude oscillatory shear (SAOS) test
using DMA (MARS II, ThermoScientific, Germany)
was carried out in this study with 0.1 Hz frequency and
0.1% strain. The resulting storage modulus, E¢, and tan
 J. Coat. Technol. Res., 11 (5) 697–710, 2014

Table 3: Surface hardness and impact resistance properties of clearcoat samples A to C and a reference sample
Properties Clearcoat A Clearcoat B Clearcoat C Ref.

Pendulum hardness (6–3) 159 117 21 136

Pencil hardness (grade) H H HB H
Impact (cm) 30 30 50 25

300 0.8
(a)
BI @ RT
0.10 250
BI @ 241°C
Sample B @ 224°C 0.6
Sample A

Temperature (°C)
Sample B @ 232°C 200

Period (sec)
0.08 Sample B
Sample B @ 241°C
Sample C
Reference
Absorbance

150 0.4
0.06

100
0.04
0.2
50
0.02

0 0.0
0.00 0 500 1000 1500
Time (sec)
2320 2300 2280 2260 2240 2220
Wavenumber (cm–1) Fig. 5: Curing patterns of samples A to C and a reference
sample using a rigid-body pendulum tester (RPT) between
25°C and 300°C
(b) 0.3
Sample B @ 224°C
Sample B @ 232°C
Sample B @ 241°C

Tensile property
0.2
Absorbance

The tensile strength for the same clearcoat films as

used in the DMA analysis, according to ASTM D-638,
was measured using a universal testing machine (UTM
0.1 Z005, Zwick-Roell, Germany), with a crosshead speed
of 10 mm/min at room temperature.

0.0 Scratch deformation using NST/AFM

1710 1700 1690
Wavenumber (cm–1)
Fig. 4: FTIR spectra of clearcoat sample B thermally
crosslinked at different peak metal temperatures: (a)
–NCO peaks at 2270 cm21 at the deblocked 1,6-hexameth-
ylene diisocyanate and (b) –COO peaks at 1685 cm21 in the
urethane bond
d data of free-standing films of prepared clearcoats
were compared in the temperature range of 60 to
150C at an acceleration rate of 2C /min. Clearcoats
were cured by gradually increasing the temperature
from 100 to 200C to make uniform films [40 mm
(length) 9 10 mm (width) 9 2 mm (thickness)] for
this test and also to prevent the occurrence of bubbles
or popping inside the clearcoat.
1680 1670
A nano-scratch tester (NST, CSM, Switzerland) was
utilized to scrutinize the surface damage of cured
clearcoats deposited on undercoats of primers and
basecoats in PCM sheets. Note that the interrelation
between the patterns of surface damage and the
intrinsic properties of crosslinked clearcoats can be
tuned up for their optimal mechanical properties for
automotive PCM technology. This test utilized a
sphero-conical stylus with a 90 conical indenter of
2 lm radius, to generate artificial damage on clearcoat
surfaces. During nano-scratch testing, the normal force
acting on the clearcoat surface was progressively
increased from an initial load of 1.0 mN to a final load
of 20 mN, with a scanning load speed of 1 mm/min, for
the relative comparison of deformation and damage
generated on the clearcoat surfaces. Damage patterns
involving depth and pile of the nano-scratches at Lc1

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J. Coat. Technol. Res., 11 (5) 697–710, 2014

(first fracture load) were directly captured using AFM (a) 1010
(Nanos, ScanPanel, Brucker, Germany), with a nano-
scratch indenter, under 6 mN load force and 1 line/s
scan speed conditions. 9

Storage modulus (Pa)

10

Deep-draw formability
8
10
The formability of PCM sheets was examined via the
deep-drawing test.8–10,19,20 the schematic diagram for
deep-drawing test is delineated in Fig. 3. PCM panels Sample A
7
10 Sample B
were pressed in the form of a square column with
50 mm 9 50 mm size, corresponding to the dimen- Sample C
Reference
sions of a square punch in a deep-drawing machine
6
(Woochang Instrument, Korea), under conditions of 10
–50 0 50 100 150
16 mm/s drawing speed and 130 kgf/cm drawing
pressure. Temperature (°C)

(b)
Surface hardness and impact resistance properties 25.09°C Sample A
1.6
Sample B
The hardness of cured clearcoat surfaces in PCM 55.42°C Sample C
sheets with overall coating layers was measured by Reference
the pendulum hardness tester (REF 707, Sheen, 1.2
UK), according to DIN 53157 and EN ISO 1522, 4.47°C
with a triangular Konig pendulum, and the pencil
tan δ

hardness test, based on the application standard of 0.8 40.06°C

ASTM D 3633, using Mitsubishi pencils ranging from
2B to 3H, respectively. Furthermore, the DuPont
impact tester, in accordance with JIS K 5600 and 0.4
ISO 6272, was utilized to evaluate the impact
resistance at drop heights ranging from 5 to 50 cm,
0.0
using an impact head with a mass of 500 g. These
–50 0 50 100 150
values, averaged from 10 times tests in each exper-
iment (Table 3), are later correlated with data of the Temperature (°C)
glass transition temperature (Tg), and the degree of
crosslinking of clearcoats. Fig. 6: Effect of temperature on (a) storage modulus and
(b) tan d for thermally crosslinked clearcoat samples A to C
and a reference sample from DMA tests

Results and discussion

Reactivity analysis by FTIR spectroscopy
The dissociation reaction of the blocking group in
the HDI crosslinker can be elucidated by the
absorption bands of the isocyanate (–NCO) group
at 2270 cm1, and the carbonyl (–COO) group at
1685 cm1 in the urethane (–NH–COO–) bond.
Figure 4a shows the absorption band of the unre-
acted dissociated free-isocyanate group in clearcoat
sample B finally cured at different PMTs from 224 to
241C, representing that the deblocking reaction was
gradually promoted, i.e., increasing urethane bonds,
as the PMT increased. The conversion rate of the
isocyanate group in sample B under different PMT
conditions was estimated by comparing the heights of
the –NCO peak at 2270 cm1 on the basis of the
maximum peak height for Trixene BI 7982 as a
blocked isocyanate (called BI) at 241C, i.e., 54% at
PMT 224C, 65% at PMT 232C, and the consider-
ably high 92% at PMT 241C. Accordingly, the PMT
241C condition was chosen as the optimal curing
condition for this study.
It is mentioned here that absorbance variations
between the single BI and clearcoat sample B in
Fig. 4a clearly proved the different dissociation
patterns and reactivity of the deblocked –NCO group
in each cured sample, relying on PMT. For the single
BI case, the –NCO group was scarcely deblocked at
room temperature; however, it was dissociated to the
fullest in the unreacted state under high temperature
conditions, due to no counterpart for the crosslinking
reaction, i.e., a hydroxyl group. Meanwhile, in the
case of the clearcoat sample containing blocked
isocyanate, most of the dissociated –NCO group
takes part in the formation of the urethane bond by
reacting with the –OH group in PAGMAP, mak-
ing the absorbance peak at 2270 cm1 decrease

704
 J. Coat. Technol. Res., 11 (5) 697–710, 2014

Table 4: Glass transition temperature (Tg), molecular weight between crosslinks (Mc), and degree of crosslinking
(Xc) of clearcoat films from DMA tests
Clearcoats Tg (C) by DMA Mc (g/mol) Xc (9102)

Sample A 55.42 15.102 6.622

Sample B 25.09 80.394 1.224
Sample C 4.47 168.880 0.592
Reference 40.06 36.725 2.723

14 (a) 35

30
12

25

Gel fraction (%)

10
Water swelling (%)

20
8

15
6

10
4
Sample A Sample A
Sample B 5 Sample B
2 Sample C
Sample C
0
0 0 2 4 6 8 10
0 2 4 6 8 10
Time (days)
Time (days)

Fig. 7: The degree of water swelling of clearcoat films as a (b)

function of immersing time into water
40

significantly along with the temperature. Full forma-

tion of crosslinking at a high temperature (241C) by
30
the reaction between –OH in PAGMAP and –NCO
Gel fraction (%)

functionality is notably practical for this technique to

desirably control clearcoat properties in automotive
20
PCM sheets.
Figure 4b shows that the absorption peak at
1685 cm1 assigned to the carbonyl group in the
urethane bonds increased gradually with increasing 10 Sample A
PMT, due to the vigorous dissociation of blocking Sample B
groups. The generation of –NH–COO– bonds in Sample C
PAGMAP also implies that the formation of cross- 0
linking networks in clearcoats is considerably influ- 0 2 4 6 8 10
enced by curing conditions related to PMT. Time (days)

Fig. 8: The gel fraction of clearcoat films as a function of

Curing behavior by RPT
The curing behaviors of clearcoat samples A to C
shown in Table 2, formulated for automotive PCM
sheets, as well as 1 K thermal cure clearcoat (called
‘‘reference sample’’ here), were investigated by means
of the RPT (Fig. 5). The evolution of the curing
reaction could be interpreted by the oscillation period
of the pendulum, directly indicating the degree of
crosslinking network formed inside a clearcoat during
thermal curing. As depicted in Fig. 5, the curing
immersing time into (a) toluene and (b) N,N¢-dimethylacet-
amide
periods for all samples significantly decreased as the
curing temperature gradually increased over 175–
180C nearby for samples A to C and 150C for 1 K
thermal cure clearcoat. The slope and pattern of the
swinging period curves were shown to be dependent on
the formulation of clearcoats. Sample A was more
reactive than samples B and C under the given curing
temperature condition in that the curing curve for

705
J. Coat. Technol. Res., 11 (5) 697–710, 2014

sample A had a steeper slope, and implied the more
reactive curing reactions between the higher hydroxyl
content contained in PAGMAP and thermal cross-
linker HDI. It was substantiated that the crosslinking
density increased with the hydroxyl content in
PAGMAP, triggering the formation of denser cross-
linking networks. Generally, enhanced crosslinking
networks increase mechanical properties of a clearcoat.
For an optimal deep-draw processing and formability
in PCM sheet technology, however, other properties
such as toughness and ductility need to be carefully
balanced during the curing process. It is notable that
the 1 K thermal cure clearcoat exhibited much faster
clearcoat, respectively, from DMA measurements. It
was found that sample A had a larger modulus at the
rubbery plateau, and higher glass transition tempera-
ture (Tg), in comparison with other samples, reflecting
the higher crosslinking density of sample A, due to its
effectual curing reactivity. It would be better to
(a)
0
–2

Scratch depth ( μ m)
curing behavior, and also the formation of stronger –4
crosslinking networks, than the others at relatively
lower temperature, ascribed to the n-butylated mela- –6
mine as a crosslinker with a catalyst initiating thermal
curing near 150C.
–8
Pd Rd
Sample A
Sample B
Viscoelastic and mechanical properties –10
Sample C
Ref.
Figures 6a and 6b display the storage modulus, E¢, and –12
tan d curves along with the temperature for thermally 0 5 10 15 20
cured clearcoat samples A to C, and the reference Normal force (mN)

(b) 0.6

30 0.3
Scratch depth ( μ m)

Sample A
25 Sample B 0.0
Sample C
Tensile stress (MPa)

Reference
20 –0.3

15 –0.6
Sample A
Sample B
10 –0.9
Sample C
Reference
5 –1.2
–4 –2 0 2 4
0 Scratch width ( μ m)
0 1 2
10 10 10 Fig. 10: (a) (Color online) Penetration depth (Pd) and
Strain (%) residual depth (Rd) of samples A to C and a reference
sample using nano-scratch tests under progressive mode
Fig. 9: Tensile behavior of the free-standing films prepared from 1 to 20 mN, and (b) their residual damage shapes at
with samples A to C and a reference sample the first fracture load (Lc1) via AFM

Table 5: Tensile properties of clearcoat films from UTM tests

Properties Clearcoat A Clearcoat B Clearcoat C Ref.

Young’s modulus (MPa) 1271.84 2.76 0.45 26.16

Elongation at break (%) 4.96 112.60 30.68 25.61
Strength at break (MPa) 22.33 2.11 – 3.96

706

(a)
2.1 μm
0.1 μm
y: 21 μm x: 21 μm
(c)
1.79 μm
0.81 μm
y : 21 μm
x: 21 μm
Fig. 11: 3D images of residual damages by AFM at the first fracture load (Lc1): (a) clearcoat sample A, (b) sample B, (c)
sample C, and (d) reference
describe here the correlation of these results with the
crosslinking properties, such as the degree of cross-
linking (Xc) and molecular weight between crosslinks
(Mc), to discern the primary features between clear-
coats formulated with different molecular weights and
hydroxyl contents of PAFAPs.21–24 Mc and Xc data for
clearcoat samples, including Tg, were calculated from
the following equations,21–24 and are listed in Table 4.
qRT 1 immersion time for up to 10 days, as seen in Fig. 7. The
Mc ¼ ; Xc ¼ ; ð3Þ
G0N Mc
where G0N denotes the rubbery plateau modulus at
120C from Fig. 6a, q is the density of a clearcoat film,
R is the gas constant, and T is the absolute tempera-
ture.
As seen in Table 4, Mc increases but Tg decreases, as
expected, with increasing molecular weight and
decreasing hydroxyl content (from samples A to C).
It is clearly confirmed that the storage modulus is in
inverse proportion to the molecular weight between
crosslinks (Mc).21–24 tan d clearly shifted to higher
temperatures as Xc increased.
It is worthwhile to mention here the relationship
between crosslinking properties and surface hardness
properties shown in Table 3. Increased Tg and Xc of a
clearcoat improved the pendulum and pencil hardness.
Regarding impact resistance data, sample C with
relatively low Xc gave an excessive ductile value. The
J. Coat. Technol. Res., 11 (5) 697–710, 2014
(b)
2.3 μm
0.4 μm
y : 21 μm
x: 21 μm
(d)
2.18 μm
1.43 μm
y : 21 μm
x: 21 μm
hardness and flexibility of clearcoats for automotive
PCM sheets should be balanced with Xc and Tg.
Water-swelling and gel-fraction properties
Transitions of water-swelling capacity of clearcoat
films for samples A to C were plotted against the
water-swelling feature is significantly affected by the
molecular weight between crosslinks and degree of
crosslinking addressed in the previous section.21–23 For
all clearcoat samples, water absorption increased
rapidly until 1 day and was then slowly saturated.
The degree of water swelling from samples A to C was
raised with decreasing hydroxyl content inside the
clearcoat and Xc, due to the decreased crosslinking
density.
Figure 8 represents the gel-fraction patterns of
clearcoat samples A to C immersed in two solvents,
i.e., toluene and N,Ń-dimethylacetamide, for dissolving
unreacted binder left in the film, as a function of
immersion time of up to 10 days. In general, the degree
of gel fraction of all clearcoat samples calculated from
equation (2) increased consistently until 5 days for
both solvent applications, and then each slowly
reached its own equilibrium. The gel-fraction tendency
for clearcoat samples was quite analogous to the water-
swelling one. The levels of water swelling and gel
707
J. Coat. Technol. Res., 11 (5) 697–710, 2014
(a)
(c)
Fig. 12: Comparison of deep-draw formability of clearcoats from deep-drawing tests: (a) clearcoat sample A, (b) sample B,
(c) sample C, and (d) reference
fraction of sample A were the lowest; validating that
sample A had denser crosslinking networks or a higher
degree of crosslinking, in comparison with the other
samples.
Tensile properties
The tensile stress–strain curves of the crosslinked
clearcoat films are shown in Fig. 9. The averaged
results of Young’s modulus, elongation at break, and
strength at break from five times tests are also summa-
rized in Table 5. The initial modulus and maximum
tensile strength increased, but the elongation at break
point decreased from sample C to sample A, along with
the increase of Xc and Tg properties. Regarding these
results, it turns out that sample A with the highest Xc
produced greater film hardness, compared with samples
B and C, due to the increased crosslinking networks
within the clearcoat. Interestingly, sample B, among
our clearcoat systems, exhibited quite a long strain
property with respect to external stress, resulting in the
708
(b)
(d)
highly favorable deep-draw formability as will be
explained below.
Deformations of clearcoat surfaces
The fracture and deformation patterns by clearcoat
surface damage can be evaluated using the NST
method, by acquiring the following damage properties:
load at the first fracture, damage shape, pile-up, and
penetration (Pd) and recovery depths (Rd). In general,
the load at the first fracture is closely related to the
intrinsic damage resistance of coatings, whereas the
residual depth and the recovery of surface damage
are linked with the viscoelastic behavior of coat-
ings.13–15,25–29
The penetration and residual depth profiles for
samples A to C and the reference sample are portrayed
in Fig. 10a. Sample A with relatively higher Tg and Xc
gave the shallower penetration depth, whereas sample
C with lower Tg and Xc strikingly recovered its
penetration depth, finally, to residual depth. This

clearly shows that the Tg and Xc of a clearcoat endow
distinct self-recovery characteristics, which are capable
of separating out various deformation types by frac-
ture, plasticity, and elasticity. Various two- and three-
dimensional images at the Lc1, including depth, width,
and topography of the residual deformation after the
recovery, were captured by AFM, as illustrated in
Figs. 10b and 11. The depth and width of residual
surface damage at Lc1 for sample A with higher Tg and
Xc were comparatively larger than those of other
cleacoat samples, due to the more extensive fracture-
like deformation pattern caused by the augmented
crosslinking networks. These results were clearly iden-
tified by three-dimensional images of surface damages
at the Lc1, for clearcoat samples (Fig. 11). Note that
the residual damage pattern of sample C was some-
what rough due to its very soft characteristics.
Deep-draw processing formability
Figure 12 displays the photos of PCM sheets coated
with the prepared clearcoats as the outmost layer after
deep-draw tests, for directly comparing the deep-draw
processing formability of PCM sheets. Sample B
showed excellent deep-draw formability. Tiny cracks
in coating layers were observed at the edges of samples
A and C. It was found that the clearcoat with higher
toughness led to the increased damage in the PCM
panel under typical processing conditions for the
formability test. On the other hand, excessive ductile
clearcoats tended to provide improved formability in
the deep-draw processing (e.g., sample C in Fig. 11);
however, they also have lower performance with
regard to mechanical properties that are critically
important in automotive coating, such as scratch
resistance and viscoelastic properties. As a matter of
fact, the formability of the 1 K thermal cure reference
clearcoat was unsatisfactory for PCM application, due
to the comparatively higher crosslinking networks
inside the clearcoat. Therefore, the crosslinking net-
work of a clearcoat developed by introducing PAG-
MAP produced better formability, as a result of the
optimized crosslinking density through the Xc, Mc, and
Tg. In addition, the polymeric structure of the phos-
phate functional groups enhanced flexibility, allowing
superb production of PCM sheets, compared with the
commercial 1 K thermal cure clearcoat.
Conclusions
PAFAPs were first synthesized, and utilized to evalu-
ate various properties of clearcoats for automotive
PCM coatings, in company with GMAMAC and
blocked HDI polyisocyanate. Clearcoats with different
degrees of crosslinking were prepared, through the
primary reaction for PAGMAPs from PAFAPs with
J. Coat. Technol. Res., 11 (5) 697–710, 2014
different molecular weights and hydroxyl contents and
GMAMAC, and the subsequent secondary reaction
between PAGMAPs and blocked isocyanates. Proper-
ties of clearcoats, which should be optimally controlled
for PCM technology, were systematically characterized
and compared from various tests for clearcoats them-
selves—crosslinking reactivity by FTIR; curing behav-
ior by RPT; rheological data by DMA; mechanical/
tensile properties by UTM—and for the clearcoat layer
in PCM sheets—hardness and impact tests; surface
deformation by NST and AFM; and PCM sheet
formability by deep-draw process. It was clarified that
the crosslinking density formed inside thermally cured
clearcoats was successfully correlated with the theo-
retical degree of crosslinking and molecular weight
between crosslinks, and also was further identified
from the water-swelling and gel-fraction results. A
strong relationship was found between a clearcoat’s
properties and its surface damage behaviors. Clear-
coats with a lower degree of crosslinking and glass
transition temperature showed superior recoverable
feature from surface damage. Specifically, the formu-
lated clearcoats with a short pendulum period, a high
rubbery modulus, and a small tensile strain value
exhibited denser crosslinking networks, whereas those
with a long pendulum period, a low rubbery modulus,
and a large strain value showed moderate crosslinking,
providing the better formability of PCM sheets in
deep-draw process. It was corroborated that the
properties of a clearcoat, considering the toughness
and flexibility indispensably required in automotive
PCM sheets, could be ingeniously designed by con-
trolling the molecular weight and hydroxyl content of
PAGMAP therein.
Acknowledgments This study was supported by
research grants from the Industrial Strategic
Technology Development Program (10035163) and
the Human Resources Development program (No.
20134010200600) of Korea Institute of Energy
Technology Evaluation and Planning (KETEP).
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