Progress in Organic Coatings 73 (2012) 392400

Contents lists available at ScienceDirect

Progress in Organic Coatings
j our nal homepage: www. el sevi er . com/ l ocat e/ por gcoat
A photo-curing study of a pigmented UV-curable alkyd
P. Chittavanich, K. Miller, M.D. Soucek

Department of Polymer Engineering, University of Akron, 250 South Forge Street, Akron, OH 44325, USA
a r t i c l e i n f o
Article history:
Received 29 October 2010
Received in revised form25 January 2011
Accepted 3 February 2011
Available online 11 March 2011
Keywords:
UV-curable
Alkyds
Pigments
Photochemistry
Reactive diluents
a b s t r a c t
The photo-curing of a pigmented UV-curable tung oil alkyd system (UVTA) was investigated. The UV-
curable alkyd was a DielsAlder Adduct of trimethylolpropane trimethacrylate with a tung oil-based
alkyd. A mixture of yellow iron oxide, red iron oxide, titanium dioxide and lamp black pigments were
chosen to obtain an observed yellow color. The pigment mixture, UV-curable alkyd and a reactive diluent
were formulated together and photo-cured via a free radical mechanism. The through and surface cure
was assessed by thumb twist, blocking resistance and MEK single rub. The through cure and surface cure
assessment showed that optimum cure was achieved using UV-A as a source with two photoinitiators:
phenylbis(2,4,6-trimethylbenzoyl-phosphine oxide) at 2 wt% and 1-hydroxy-cyclohexyl-phenyl-ketone
at 4wt%. The effect of reactive diluent was also investigated. Ten different reactive diluents were used.
After curing, pencil hardness, conical mandrel, impact resistance, cross cut adhesion and gloss were mea-
sured. In addition, dynamic mechanical thermal analysis (DMTA) was used to evaluate selected systems.
The coatings tests showed that the use of long chain linear structure diluents, such as isodecyl methacry-
late, provided UV-curable paint lms with better impact resistance, exibility, and adhesion over other
reactive diluents.
2011 Elsevier B.V. All rights reserved.
1. Introduction
Studies have demonstrated that UV-curing coatings reduce
energy use and hazardous emissions over conventional coatings
[1,2]. The interest in bio-based UV-curable material is spread-
ing. Many oil-based UV-curable materials are available that cure
via either the cationic-initiated method or free radical initiated
method; for instances, UV-curable palm-based resin [3], epoxy
norborane linseedoil [4], epoxy soybeanoil acrylate [5], epoxidized
cyclohexene derivatized linseed oil [6] and epoxidized soybean oil-
based ceramer coatings [7] have already been developed.
Alkyd resins today are still one of the most important classes of
coating resins. Alkyds are usedinbothclear andpigmentedcoating.
UV technology would result in low energy consumption and no-
VOCs. Furthermore, the material is derived from renewable and
easy-to-nd natural bio-based resources, further emphasizing the
environmental friendly concept.
Formulation of pigmented UV-curing coatings has been a major
challenge since the earliest stage of their development. The reec-
tion and absorption characteristics of pigment particles are the
main reason for this. Pigments prevent sufcient penetration of
UV energy to efciently activate the photo-initiated crosslinking
systems, resulting in the amplication of the cure gradient in the

Corresponding author. Tel.: +1 3309722583.

E-mail address: msoucek@uakron.edu (M.D. Soucek).
lm, which is responsible for the creation of wrinkles on the lm
surface.
Recently, UV-curable tungoil alkyds (UVTA) have beenprepared
and reported by Thanamongkollit and Soucek [8]. The objective of
this work was to further develop the UVTAconcept into a complete
pigmented formulation. The color of Caterpillar yellowwas chosen
for this study. The light source, photoinitiator, and reactive diluent
were evaluated and optimized for through and surface cure. After
curing, pencil hardness, conical mandrel, impact resistance, cross
cut adhesion and gloss were measured. In addition, the viscoelas-
tic properties of the optimized formulations were investigated by
dynamic mechanical thermal analysis (DMTA).
2. Materials and methods
2.1. Materials
Tung oil was purchasedfromAlnor Oil Company. Phenothiazine,
lithium hydroxide monohydrate, para-xylene, phthalic anhydride
(99%), and glycerol (99%) were obtained from SigmaAldrich.
Trimethylolpropane trimethacrylate (TMPTMA), tripropylene
glycol diacrylate (TPGDA), propoxylated trimethylolpropane
triacrylate (POTMPTA), propoxylated neopentyl glycol diacrylate
(PONPGDA), neopentyl glycol diacrylate (NPGDA), 1,6 hexane-
diol dimethacrylate (HDMA), dicyclopentadienyl methacrylate
(DCPDMA), lauryl acrylate (LA), isodecyl methacrylate (IDMA)
and isobornyl acrylate (IBOA) were received from Sartomer
0300-9440/$ see front matter 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.porgcoat.2011.02.005
P. Chittavanich et al. / Progress in Organic Coatings 73 (2012) 392400 393
Company. Disperbyk-145 (phosphoric ester salt), BYK-377
(polyether-modied polydimethylsiloxane) and BYK-UV 3500
(polyether-modied acryl functional polydimethylsiloxane) were
given by BYKAdditives &Instruments. Photoinitiators Irgacure 819
(phenylbis(2,4,6-trimethylbenzoyl)-phosphine oxide), Darocure
1173 (2-hydroxy-2-methyl-1-phenyl-1-propanone), Irgacure
184 (1-hydroxy-cyclohexyl-phenyl-ketone), Irgacure 2100 (a
blend of acyl phosphine oxides which contains Irgacure 819
as a major component), Irgacure 2022 (a blend of Irgacure
819 with other nondisclosed materials) and Darocure TPO
(diphenyl(2,4,6-trimethylbenzoyl)-phosphine oxide) were
obtained from Ciba Company. Methyl ethyl ketone was pur-
chased from J.T. Baker. Chroma-Chem titanium white (titanium
dioxide pigment), Chroma-Chem Red iron oxide (red iron oxide
pigment), Chroma-Chem Yellow iron oxide (yellow iron oxide
pigment) and Chroma-Chem Lampback (carbon black pigment)
were received from Valspar Inc. Unpolished cold roll steel panels
fromACT Test Panel Technologies Company. Leneta opacity charts
were obtained from the Leneta Company, Inc. All materials were
used as received.
2.2. Instrumentation
Varian Mercury-300MHz spectrometer was used to record
1
H and
13
C NMR spectra at room temperature with CDCl
3
+TMS
(0.01%) as reference solvent. Size exclusion chromatography was
carried out with a Wyatt Dawn EOS equipped with a multi-angle
laser light scattering (MALLS) detector plus waters model 410 dif-
ferential refractometer concentration detector and a set of three
columns, HR Styragel in THF performed at 35

C and 1mL/min
ow rate. A Brookeld DV-II+ Pro programmable viscometer with
spindle SC4-25 was used to measure the viscosity of tung-oil
based alkyd and UVTA. Matrix assisted laser desorption ioniza-
tion mass spectroscopy (Bruker MALDI-TOF REFLEXIII) was used to
determine the exact molecular weight of the products fromtrans-
estericationreaction. Hewlett PackardUV/Vis Spectrophotometer
Model 8453 was operated to obtain the UVabsorbance spectrumof
the pigments. Omni General Laboratory Homogenizer (GLH), MIS-
ONIX SONICATOR 3000 and Thinky vacuum mixer ARV-310 were
used to disperse the pigments particles in the formulated coatings.
LC6E Benchtop Conveyor and a F300S UV-curing system consist-
ing of a I300M Irradiator model, a P300MT Power supply model
and two electrodeless lamps (lamp power 300W/in., 1800Wtotal)
fromFUSIONUVSystems, Inc. were usedinthe radiationof wet lm
samples. The two lamps were standard type BF9 mercury H-bulb
and an iron doped D-bulb. Dry lmthickness was measured using
Elcometer 456 Coating thickness gauge. FEI Quanta 200 Environ-
mental Scanning Electron Microscope (ESEM) from FEI Company
and Leitz Laborlux 12 POL S microscope from B&B microscopes,
Ltd. were usedto observe the degree of dispersionof pigment parti-
cles. Brookeld DV-II+ Pro programmable viscometer with spindle
SC4-25 was used to measure the viscosity of formulations. Gloss
measurements were performed using Elcometer 401 Novo-Gloss
Glossmeter. Perkin-Elmer Rheometric Scientic dynamic mechan-
ical thermal analyzer in tension mode was utilized to investigate
the viscoelastic properties of the lms.
2.3. Synthesis of UV-curable tung oil based alkyd (UVTA)
A tung oil based alkyd was synthesized via the monoglyceride
process. Tung oil (100g), glycerol (34.55g, 0.375mol), and lithium
hydroxide (0.04g) were charged into a 500mL four-necked round
bottom ask equipped with a mechanical stirrer and reux con-
denser. The reactionaskwas thoroughly ushedwithnitrogengas
and the system was rapidly heated to 300

C (>13min) and main-

tained at 300

C for another 8min. The monoglyceride product was

Fig. 1. Mass spectrumof the monoglyceride of tung oil.
conrmed by mass spectrometry, peak at 375.2 m/z is indicative of
the tung-monoglyceride product. The mass spectra are shown in
Fig. 1.
In the next step, the temperature was decreased to 170

C and
a 20mL Dean-Stark trap was connected to the ask and the con-
denser. Phthalic anhydride (37g, 0.25mol), phenothiazine (0.05g),
andxylene (80mL) were addedto the system. The reactiontemper-
ature would drop to about 120

C after the addition of chemicals.

Heating was resumed and the reactor was heated back to 170

C
and maintained for 1.5h; at this point the acid number of the alkyd
was 23. The acid number of the alkyd was determined according
to ASTMD 1639-90 by titration with 0.1MKOH in xylene solution.
Xylene was reuxed continuously throughout this step. Oil length
of the alkyd was calculated at 59. The alkyd was characterized by
1
H and
13
C NMR. The NMR spectra were obtained at ambient tem-
perature in CDCl
3
. The assigned chemical shift of the
1
H and
13
C
NMR are given in Figs. 2 and 3, sequentially.
Finally, the modication was conducted; the reaction system
was cooled from 170

C to 150

C. The Dean-Stark apparatus was

removed but the condenser was retained. Trimethylolpropane
trimethacrylate (TMPTMA) (35g, 0.104mol) was charged into the
reactor. The temperature was heated up and maintained at 170

C
for another 1.5h. After that, the modied alkyd product was cooled
down to room temperature. Xylene was then removed from the
modied alkyd by evaporation. Acid number at this point was 19.
The modied alkyd or the UV-curable tung oil-based alkyd (UVTA)
was characterized by
1
H and
13
C NMR. Figs. 2 and 3 show the
assigned chemical shifts of
1
H NMR and
13
C NMR of UVTA, respec-
tively.
2.4. Formulation of UV-curable alkyd based paints
UVTA was formulated with photoinitiators, reactive diluents,
silicone additives and dispersing additive. For the reaction scheme
and chemical structure of UVTA along with the structures of the
photoinitators see Fig. 4. The formulations were then radiated
by UV sources. To prepare a mixture of pigments, four different
pigments, all in paste form, were weighed up to 200g with the
composition according to Table 1. The mixture was put in a 120mL
bottle and hand-mixed and mixed in the homogenizer for 3min at
394 P. Chittavanich et al. / Progress in Organic Coatings 73 (2012) 392400
Fig. 2.
1
H NMR spectra of (a) tung oil alkyd, (b) UV-curable tung oil alkyd.
Table 1
Compositions of pigment mixture.
Trade name Description % by weight
CHROMA-CHEMTITANIUMWHITE TiO
2
pigment 22.42%
CHROMA-CHEMRED IRON OXIDE Red iron oxide pigment 0.38%
CHROMA-CHEMYELLOWIRON OXIDE Yellowiron oxide
pigment
77.15%
CHROMA-CHEMLAMPBLACK Carbon black pigment 0.05%
11,400 revolutions per minute (rpm). The dispersion process was
repeated twice for a total homogenizing time of 9min.
2.5. Substrates and lmpreparations
Film preparation was prepared using a draw down bar to cast
1 mil thick (25.4m) lms on unpolished cold roll steel panels
from ACT Test Panel Technologies Company. The wet lms were
thenimmediatelyplacedonaconveyor topass throughaUV-curing
system that utilizes an electrodeless mercury lamp (H-bulb) as a
radiator, total irradiation time was 150s. Films for DMTA inves-
tigation were cast by a draw down bar on glass panels (8mils wet
lm) and passed through the UV-curing system.
Fig. 3.
13
C NMR spectra of (a) tung oil alkyd, (b) UV-curable tung oil alkyd.
After radiation, through cure and surface cure were assessed.
Surface cure was assessedby (1) doing thumbtwist test: press a n-
ger on the irradiated surface, twist and determine whether there
is a deformation after removal or not and (2) performing block-
ing resistance test according to ASTMD 3003-01. For through cure
assessment, a test method based on ASTM D 4752 the standard
MEK rub test was used. In the blocking resistance test, two panels
with the coating samples were pressed together to a pressure of
700kPa with the coated side facing each other. The pressure was
removed after 2h and the panels were pulled apart. The surface of
the tested coating was considered well cured if the panels pulled
apart easily. When 200 single rubs did not lead to any visible dam-
age to the coating, the coating was considered well cured. All the
coatings tests were performed a minimum of 5 replicates and an
arithmetic mean was used to determine the value.
2.6. Formulations with reactive diluents
To nd a suitable reactive diluent, UVTA was formulated with
various mono-functional and multi-functional reactive diluents,
Fig. 5 shows the structures of the monomers. Formula composi-
tion is shown in Tables 26. The test methods were based on (1)
ASTMD3363-00 standard test method for lmhardness by pencil
P. Chittavanich et al. / Progress in Organic Coatings 73 (2012) 392400 395
O O O
O
O
O
n
O O O
O O
O
n
O
O
O
O
O
O
Tung oil-based
alkyd Resin
UV-curable
Tung Oil Alkyd
TMPTMA
O
O
O
O
O
O
+
150
o
C, 90 min
P
O
C
O
C
O
P
O
C
O
b
a
c
C
O
OH
C
O
OH
d e
Fig. 4. Chemical structures: (a) UV-curable tung oil based alkyd (UVTA), (b) Irgacure 819, (c) Darocure TPO, (d) Irgacure 184, (e) Darocure 1173.
Table 2
Formulations using TMPTMA or POTMPTA as a reactive diluent.
Components Name
REA-1 REA-2 REA-3 REA-4
phr wt% phr wt% phr wt% phr wt%
UVTA 100 60.24 100 54.79 100 60.24 100 54.79
TMPTMA 60 36.14 60 32.88 0 0.00 0 0.00
POTMPTA 0 0.00 0 0.00 60 36.14 60 32.88
IRGACURE 819 2 1.20 2 1.10 2 1.20 2 1.10
DAROCUR 1173 2 1.20 2 1.10 2 1.20 2 1.10
CY pigment 0 0.00 15 8.22 0 0.00 15 8.22
DISPERBYK-145 0 0.00 1.5 0.82 0 0.00 1.5 0.82
BYK-UV 3500 2 1.20 2 1.10 2 1.20 2 1.10
test, (2) ASTMD522-93a standard test methods for Mandrel Bend
Test of attached organic coatings, (3) ASTMD3359-02 standard test
methods for measuring adhesion by tape test, (4) ASTM D 2794-
93 standard test method for resistance of organic coatings to the
effects of rapid deformation and (5) ASTMD 523-08 Standard test
method for specular gloss. The dry lms of the remaining formulas
were visually observed for lmshrinkage.
Finally, lms from each formulation were prepared for DMTA
investigation. Geometry of each sample is 0.3mm 1cm2cm.
The viscoelastic properties of the samples were evaluated by a
DMTA instrument The DMTA instrument was set for a tempera-
ture range of 25

C to 145

C at the frequency of 1Hz with the

heating rate 3

C/min. The gap distance of the specimens was set at

1mm.
396 P. Chittavanich et al. / Progress in Organic Coatings 73 (2012) 392400

O
O
O
O
O
O
TMPTMA
O
O O
O
NPGDA
O O
O
O
O
O
TPGDA
O
O O
PONPGDA
O
O
O
O
O
C
10
H
21
IDMA
O
O
DCPDMA
O
O CH
2
LA
CH
3
11
O
O
IBOA
O
O
O
2
O
O
O
2
O
O
O
2
POTMPTA
O
O
O
O
HDMA
Fig. 5. Chemical structures of the monomers used in formulations.
Table 3
Formulations using HDMA or TPGDA as a reactive diluent.
Components Name
REA-5 REA-6 REA-7 REA-8
phr wt% phr wt% phr wt% phr wt%
UVTA 100 60.24 100 54.79 100 60.24 100 54.79
HDMA 60 36.14 60 32.88 0 0.00 0 0.00
TPGDA 0 0.00 0 0.00 60 36.14 60 32.88
IRGACURE 819 2 1.20 2 1.10 2 1.20 2 1.10
DAROCUR 1173 2 1.20 2 1.10 2 1.20 2 1.10
CY pigment 0 0.00 15 8.22 0 0.00 15 8.22
DISPERBYK-145 0 0.00 1.5 0.82 0 0.00 1.5 0.82
BYK-UV 3500 2 1.20 2 1.10 2 1.20 2 1.10
P. Chittavanich et al. / Progress in Organic Coatings 73 (2012) 392400 397
Table 4
Formulations using PONPGDA or NPGDA as a reactive diluent.
Components Name
REA-9 REA-10 REA-11 REA-12
phr wt% phr wt% phr wt% phr wt%
UVTA 100 60.24 100 54.79 100 60.24 100 54.79
PONPGDA 60 36.14 60 32.88 0 0.00 0 0.00
NPGDA 0 0.00 0 0.00 60 36.14 60 32.88
IRGACURE 819 2 1.20 2 1.10 2 1.20 2 1.10
DAROCUR 1173 2 1.20 2 1.10 2 1.20 2 1.10
CY pigment 0 0.00 15 8.22 0 0.00 15 8.22
DISPERBYK-145 0 0.00 1.5 0.82 0 0.00 1.5 0.82
BYK-UV 3500 2 1.20 2 1.10 2 1.20 2 1.10
Table 5
Formulations using DCPDMA or IBOA as a reactive diluent.
Components Name
REA-13 REA-14 REA-15 REA-16
phr wt% phr wt% phr wt% phr wt%
UVTA 100 60.24 100 54.79 100 60.24 100 54.79
DCPDMA 60 36.14 60 32.88 0 0.00 0 0.00
IBOA 0 0.00 0 0.00 60 36.14 60 32.88
IRGACURE 819 2 1.20 2 1.10 2 1.20 2 1.10
DAROCUR 1173 2 1.20 2 1.10 2 1.20 2 1.10
CY pigment 0 0.00 15 8.22 0 0.00 15 8.22
DISPERBYK-145 0 0.00 1.5 0.82 0 0.00 1.5 0.82
BYK-UV 3500 2 1.20 2 1.10 2 1.20 2 1.10
Table 6
Formulations using LA or IDMA as a reactive diluent.
Components Name
REA-17 REA-18 REA-19 REA-20
phr wt% phr wt% phr wt% phr wt%
UVTA 100 60.24 100 54.79 100 60.24 100 54.79
LA 60 36.14 60 32.88 0 0.00 0 0.00
IDMA 0 0.00 0 0.00 60 36.14 60 32.88
IRGACURE 819 2 1.20 2 1.10 2 1.20 2 1.10
DAROCUR 1173 2 1.20 2 1.10 2 1.20 2 1.10
CY pigment 0 0.00 15 8.22 0 0.00 15 8.22
DISPERBYK-145 0 0.00 1.5 0.82 0 0.00 1.5 0.82
BYK-UV 3500 2 1.20 2 1.10 2 1.20 2 1.10
2.7. Optimization of photoinitiator concentration
The concentration of surface cure and through cure photoini-
tiators was varied as shown in Table 7. The reactive diluent was
IDMA which was down selected from the other reactive diluents.
The pigment concentration was the other variable of note.
2.8. Degree of pigment dispersion
Degree of dispersion of pigment was observed by optical micro-
scope and scanning electron microscope (SEM). A coating to be
observedwithoptical microscopewas preparedbydilutingformula
REA-20 with formula REA-19. The samples were frozen with liquid
nitrogen, broken into desirable sizes and placed on SEM mounts
with a direction (1) parallel to the mounts surface for lms surface
observation or (2) vertical to the mounts surface for cross sectional
view.
3. Results and discussion
The UV-curable tung oil-based alkyd resin (UVTA) was prepared
as previously reported [8], except that the lead based transesteri-
cation catalyst lithage was replaced with lithiumhydroxide. The
NMR spectral data matches the previous report. In addition, GPC
(Gel PermeationChromatography) was performedfor boththe par-
ent alkyd and the UVTA. For the tung oil alkyd, the result showed
that the number average molecular weight (M
n
), the weight aver-
age molecular weight (M
w
), andpolydispersityindex(PDI) are 2290
and 17,530, and 7.66, respectively. As for UVTA, M
n
is 2413, M
w
is
68,740 and the polydispersity index (PDI) is 28.49. At room tem-
perature, the viscosity of tung oil alkyd and UVTA were measured
at be 29,000 and 88,500cP, respectively.
The UVTA was formulated with a number of reactive diluents,
photoinitiators andadditives. Additives were addedto aidwithdis-
persionof pigment particles and eliminate a cratering problemthat
occurred in some of the formulations. Photoinitiators were initially
screened by two criteria, pigment absorption and light source out-
put. The UV absorption data of the pigment is shown in Fig. 6. After
considerable screening [9], a mixture of Iracure 819 and Durocure
1173 were selected as the photoinitiators. Once reactive diluents
were narrowed down to a single candidate, optimization of pig-
ment concentration was determined.
An important aspect of pigmented coatings and especially UV-
curable coatings is the degree of dispersion of pigment particles.
The dispersion was checked for each coating formulation via per-
sonal observation and a rub-test. There are also numerous methods
398 P. Chittavanich et al. / Progress in Organic Coatings 73 (2012) 392400
Table 7
Formulations used for the optimization of photoinitiator concentration.
Components Name
PHO-I1 PHO-C2 PHO-C3 PHO-C4
phr wt% phr wt% phr wt% phr wt%
UVTA 100 57.47 100 55.59 100 52.69 100 50.08
IDMA 60 34.48 60 33.35 60 31.61 60 30.05
DAROCUR 1173 4 4.60 4 2.22 4 2.11 4 2.00
IRGACURE 819 4 2.30 4 2.22 4 2.11 4 2.00
CY pigment 0 0.00 9 5.00 18 9.48 27 13.52
DISPERBYK-145 0 0.00 0.9 0.50 1.8 0.95 2.7 1.35
BYK-UV 3500 2 1.15 2 1.11 2 1.05 2 1.00
Fig. 6. UV absorption curves under different concentrations of CY pigment.
Fig. 7. Representative optical image of pigment dispersion, REA-20.
that have been employed to quantify degree of dispersion [10], but
most of them are comparative rather than absolute and some of
them depend on other factors than dispersion, e.g., gloss [11]. To
validate the observation, the degree of dispersion was determined
by optical microscope and scanning electron microscope (SEM) as
shown in Figs. 7 and 8. It is observed in both micrographs that the
pigment is well dispersed.
Selection of the reactive diluent is a critical process in UV for-
mulation since the performance of any UV coating is determined
predominantly by the oligomers and the monomers incorporated
in the formulation. The reactive oligomers/monomers are usually
chosen based on desired properties such as adhesion, exibility,
hardness, scratchresistance, impact resistance and gloss. Function-
ality and viscosity, too, are important parameters when choosing
reactive diluents.
The resin in this work, UVTA, has a viscosity at 25

C in the range
of 88,500cP which is tremendously viscous compared to other oil-
based alkyd resins [1214]. Therefore, mixing it with oligomers
is not considered here since most oligomers are too viscous to
be applied and need to be diluted by monomers. However, some
Fig. 8. SEMof pigment dispersion via cross-sectional view, REA-20.
oligomers today are designed to have lowviscosity and their incor-
poration in the formulations will be one of the future works.
In order to nd a suitable monomer for the UV-curable alkyd
paint, ten reactive monomers were chosen to be formulated with
UVTA at 0% pigment and 8.2% pigment (8.2% pigment is high-
est value in which wrinkle free lms could be obtained for all
monomers). The viscosity of each formula was controlled to be in
the range of 7001000cP. This range is in the application viscos-
ity of alkyd-based products [15,16]. Coating tests are presented in
Tables 8 and 9.
According to Burrel [17], Basu [18], Payne [19], Wicks and Chen
[20], wrinkles originate from the curing gradient of the lm, high
cure rate at the surface and lowcure rate at the bottom. Therefore,
anideal solutiontoeliminate wrinkles is todecrease the cure rate at
the surface and increase the cure rate at the deeper level; however,
it is difcult to separately control the cure rate of the two parts.
A fundamental approach is to adjust the cure speed of the whole
system by reducing or increasing the cure functionality as done
in this work. Results showed that lowering the cure speed of the
systems is a better way to minimize the curing gradient since all the
formulations with multi-functional monomers produce wrinkling
lms at pigment levels around 8.2% while those formulated with
the mono-functional monomers do not, and, consequently, it was
decided to exclude the multi-functional monomer from the later
work.
As predicted, formulation of UVTA with linear structure
monomers like LAand IDMAproduced better exibility and impact
resistant lms than lms produced with monomers having bulky
side groups such as DCPDMA and IBOA. Additionally, UVTA formu-
lations with LA and IDMA produced lms with properties that are
comparable with other alkyd resins [2224]. Use of the DCPDMA
P. Chittavanich et al. / Progress in Organic Coatings 73 (2012) 392400 399
Table 8
Coating properties: gloss, adhesion, and hardness.
Formula Monomer Pigment level Scratch hardness Cross cut adhesion test Gloss 60

Gouge hardness Pencil hardness

REA-1 TMPTMA 0% 6H 6H 1B 96.1
REA-3 POTMPTA 0% H F 4B 94.4
REA-5 HDMA 0% 3H H 4B 92.7
REA-7 TPGDA 0% 3H 2H 4B 97.2
REA-9 PONPGDA 0% 3H H 4B 98.1
REA-11 NPGDA 0% 4H 3H 3B 97.5
REA-13 DCPDMA 0% 5H 4H 2B 101.4
REA-15 IBOA 0% 3H 2H 4B 99.6
REA-17 LA 0% F HB 5B 84.1
REA-19 IDMA 0% F HB 5B 88.4
REA-2 TMPTMA 8.2% 6H 6H 1B 60.9
REA-4 POTMPTA 8.2% 2H H 4B 62.3
REA-6 HDMA 8.2% 3H H 4B 60.0
REA-8 TPGDA 8.2% 3H 2H 4B 61.4
REA-10 PONPGDA 8.2% 3H H 4B 63.5
REA-12 NPGDA 8.2% 4H 3H 3B 64.8
REA-14 DCPDMA 8.2% 5H 4H 2B 87.2
REA-16 IBOA 8.2% 3H 2H 4B 85.1
REA-18 LA 8.2% H F 5B 70.8
REA-20 IDMA 8.2% 2H F 5B 75.4
Table 9
Coatings properties: mandrel and impact resistance.
Formula Monomer Pigment level Conical mandrel test (% elongation) Impact resistance (lb/in.) Wrinkles
Direct Reverse
REA-1 TMPTMA 0% 3% 0.5 0.5 No
REA-3 POTMPTA 0% 28% 34 32
REA-5 HDMA 0% 24% 27 24
REA-7 TPGDA 0% 22% 24 22
REA-9 PONPGDA 0% 24% 29 29
REA-11 NPGDA 0% 14% 20 16
REA-13 DCPDMA 0% 7% 0.5 0.5
REA-15 IBOA 0% 22% 24 22
REA-17 LA 0% >32% >40 >40
REA-19 IDMA 0% >32% >40 >40
REA-2 TMPTMA 8.2% 3% 0.5 0.5 Yes
REA-4 POTMPTA 8.2% 26% 32 30
REA-6 HDMA 8.2% 22% 26 24
REA-8 TPGDA 8.2% 22% 24 22
REA-10 PONPGDA 8.2% 24% 28 27
REA-12 NPGDA 8.2% 14% 18 16
REA-14 DCPDMA 8.2% 9% 0.5 0.5 No
REA-16 IBOA 8.2% 22% 28 24
REA-18 LA 8.2% >32% >40 >40
REA-20 IDMA 8.2% >32% >40 >40
resulted in very brittle lms. The IBOA had better gloss and hard-
ness than IDMA, but there was no signicant difference in hardness
for the pigmented system.
Films from each formulation were also prepared for dynamic
mechanical thermal analysis (DMTA). Storage modulus and tan of
each systemwere measured. The glass transition temperature (T
g
)
was derived from the maximum -transition shown in the tan
data. The magnitude of storage modulus in the rubbery plateau
region was used to determine crosslink density of the material. The
linear relationship between crosslink density and rubbery plateau
modulus is [21]:

e
=
E

min
3RT
(1)
where
e
is thecrosslinkdensity, E

min
is theminimumstoragemod-
ulus (Pa) in the rubbery plateau, R is the gas constant (J/mol K) and
T is the temperature at minimum storage modulus (K). Table 10
provides the value of minimum modulus (E

min
), glass transition
temperature (T
g
) and crosslink density (
e
) of each system.
Considering the clear coat systems, it was observed that
crosslink density of monofunctional monomer is lower than mul-
tifunctional monomer. The formulation containing TMPTMA has
the highest crosslink density and T
g
. Not surprisingly, the T
g
of the
formulations that have bulky pendant group such as DCPDMA and
IBOA are much higher than the formulations that contain linear
structure (e.g. LAandIDMA). The short-chainmonomer like NPGDA
also has higher T
g
and higher crosslink density than PONPGDA,
whose structure is similar to NPGDA, but has a longer backbone.
This can be explained by the reduced segmental motion of the
polymer backbone. The high crosslink density of the formulation
containing TMPTMA and NPGDA is in agreement with the mandrel
exibility test, which shows that the samples are brittle.
Although the presence of a second phase (pigment particles)
makes the crosslink density semi-quantitative, it gives the same
trend as the unpigmented systems. It was also observed that the T
g
of the formulations with long side chain acrylic monomers such
as LA and IDMA increased with the presence of pigment. This
is expected since the interaction between the particles and the
polymer reduce the mobility of the polymer chain, resulting in
400 P. Chittavanich et al. / Progress in Organic Coatings 73 (2012) 392400
Table 10
Viscoelastic properties of formula REA-1 through REA-20.
Formula Reactive diluent Pigment level Tg (

C) fromDMTA E

min
(MPa) e (mol/m
3
)
REA-1 TMPTMA 0% 110 89.8 8511
REA-3 POTMPTA 0% 34 18.1 2032
REA-5 HDMA 0% 44 20.4 2069
REA-7 TPGDA 0% 52 20.9 2105
REA-9 PONPGDA 0% 44 20.0 2055
REA-11 NPGDA 0% 84 22.2 2287
REA-13 DCPDMA 0% 89 4.0 401
REA-15 IBOA 0% 55 3.6 387
REA-17 LA 0% 19 1.9 210
REA-19 IDMA 0% 21 2.3 239
REA-2 TMPTMA 8.2% 74 20.8 2183
REA-4 POTMPTA 8.2% 38 4.8 532
REA-6 HDMA 8.2% 41 4.9 543
REA-8 TPGDA 8.2% 45 5.3 562
REA-10 PONPGDA 8.2% 40 4.6 513
REA-12 NPGDA 8.2% 48 6.1 665
REA-14 DCPDMA 8.2% 52 3.9 417
REA-16 IBOA 8.2% 39 3.4 377
REA-18 LA 8.2% 33 2.9 321
REA-20 IDMA 8.2% 35 3.2 359
PHO-I1 IDMA 0% 20 1.93 213
PHO-C2 IDMA 2.9% 35 3.88 404
PHO-C3 IDMA 9.48% 38 4.20 439
PHO-C4 IDMA 13.52% 41 5.94 623
an increase in modulus and T
g
. However, a different trend was
observed for the formulations with branched structured multi-
functional monomers where the T
g
decreased with the presence
of pigment. The pigments universally affected the cure of the sys-
tem, but did not have as strong of an interaction with the branched
monomers. Since branched monomers create a highly crosslinked
system, interactions between the polymer and pigment will not
greatly affect the lmproperties; a high crosslink density will con-
tribute more to the lm properties than the presence of pigment.
However, the lowering of the T
g
upon addition of pigment to the
branched monomers is most likely due to the pigment disrupting
the branched monomer fromforming a fully crosslinked network.
4. Conclusion
The synthesis of the UV-curable coating material based on tung
oil was successfully prepared using a relatively benign catalyst
as compared the lead catalyst lithage. The UVTA was formulated
with a mixture of pigments, reactive diluents, photoinitiators,
dispersing additive and silicone additive to create a UV-curable
alkyd-based pigmented coating. Through cure limited the maxi-
mum pigment level informulations to14wt%. Highqualitypigment
dispersions were obtained. A mono-functional monomer, isode-
cyl methacrylate (IDMA), was found to impart excellent exibility,
impact resistanceandadhesiontothemetal substrate. Usingacom-
bination of initiators, IRGACURE 819 at 2% and DAROCUR 1173 at
24%, with UVTA and IDMA, a pigmented coating with a good
balance of lmproperties could be prepared.
References
[1] R. Golden, Low-emissiontechnologies: apathtogreener industry, RadTechRep.
19 (3) (2005) 1418.
[2] R. Mehnert, A. Pincus, I. Janorsky, R. Stowe, A. Berejka, UV & EB Curing Tech-
nology & Equipment, John Wiley and Sons Inc., NewYork, 1998.
[3] M.Y. Cheong, T.L. Ooi, S. Ahmad, W.Md.Z.W. Yunus, D. Kuang, Synthesis and
characterization of palm-based resin for UV coating, J. Appl. Polym. Sci. 111 (5)
(2009) 23532361.
[4] J. Chen, M.D. Soucek, W.J. Simonsick, R.W. Celikay, Synthesis and photopoly-
merization of norbornyl epoxidized linseed oil, Polymer 43 (20) (2002)
53795389.
[5] H. Pelletier, A. Gandini, Preparation of acrylated and urethanated triacylglyc-
erols, Eur. J. Lipid Sci. Technol. 108 (5) (2006) 411420.
[6] K. Zou, M.D. Soucek, UV-curable organicinorganic hybrid lmcoatings based
on epoxidized cyclohexene derivatized linseed oil, Macromol. Chem. Phys. 205
(15) (2004) 20322039.
[7] G. Teng, M.D. Soucek, Epoxidized soybean oil-based creamer coatings, J. Am.
Oil Chem. Soc. 77 (4) (2000) 381.
[8] N. Thanamongkollit, M.D. Soucek, Synthesis of UV-curable tung oil and UV-
curable tung oil based alkyds, Prog. Org. Coat. 73 (2012) 425434.
[9] P. Chittavanich, Pigmented UV-curable alkyd, M.S. Thesis, University of Akron,
December 2009.
[10] T. Van Sang, V. Velamakanni Bhaskar, R. Adkins Ronald, Comparison of
methods to assess pigment dispersion, J. Coat. Technol. 73 (923) (2007)
6170.
[11] L.A. Simpson, Factors controlling gloss of paint lms, Prog. Org. Coat. 6 (1978)
130.
[12] P. Uschanov, N. Heiskanen, P. Mononen, S. Liisa Maunu, S. Koshimies, Synthesis
andcharacterizationof tall oil fatty acids-basedalkydresins andalkyd-acrylate
copolymers, Prog. Org. Coat. 63 (2008) 9299.
[13] R. Mikami et al., U.S. Patent 4,069,178 (1978).
[14] A.M. Issam, C.Y. Cheun, A study of the effect of palmoil on the properties of a
newalkyd resin, Malays. Polym. J. 4 (1) (2009) 4249.
[15] http://www.dow.com/PublishedLiterature/dh 004e/0901b8038004e32d.pdf
(accessed 12.03.09).
[16] http://www.fspma.com/PDFs/Paint/SPEC MP-5.pdf (accessed 12.03.09).
[17] H. Burrell, Ind. Eng. Chem. 46 (10) (1954) 2233.
[18] Basu, K. Soumendra, L.E. Scriven, L.F. Francis, A.V. McCormick, Mechanism of
wrinkle formation in curing coatings, Prog. Org. Coat. 53 (2005) 116.
[19] J.A. Payne, L.F. Francis, A.V. McCormick, J. Appl. Polym. Sci. 66 (1997)
1267.
[20] Z.W. Wicks Jr., G.-F. Chen, J. Coat. Technol. 50 (638) (1978) 39.
[21] L.W. Hill, Prog. Org. Coat. 31 (1997) 235.
[22] R.A. Sailer, M.D. Soucek, Oxidizing alkyd creamers, Prog. Org. Coat. 33 (1998)
3643.
[23] J. Dziczkowski, M.D. Soucek, A newclass of acrylated alkyds, J. Coat. Technol. 7
(5) (2010) 587602.
[24] K. Wutticharoenwong, J. Dziczkowski, M.D. Soucek, Tung based reactive dilu-
ents for alkyd systems: lmproperties, submitted for publication.