Progress in Organic Coatings 53 (2005) 239–245

Development of a heat resistant UV-curable epoxy coating

Madhu Bajpai ∗ , Vipin Shukla, Firdous Habib
H.B. Technological Institute, Oil and Paint Technology Department, Kanpur 208002, India

Received 19 April 2004; received in revised form 27 October 2004; accepted 23 December 2004

Abstract

Epoxy novolac resin possesses good heat resistant property as compared to other conventional epoxy resins. A thermally stable UV-curable
epoxy coating has been developed by using functional amino silanes, viz., N-[3-(trimethoxysily1) propyl] ethylenediamine and a copolymer
of aminopropylmethyl dimethyl siloxane in definite ratio. It has been observed that the use of silicon compounds invariably enhances the
thermal stability, chemical resistance and corrosion resistance of the epoxy coating. It has also been observed that silane bearing trimethoxy
group gave better adhesion properties whereas silicon gave better thermal stability.
© 2005 Published by Elsevier B.V.

Keywords: Novolac epoxy; Cresol epoxy; Acrylation; Organo silicon compound; Photo-initiator; UV-curing

1. Introduction containing compounds. Recently, heat-resistant UV-curable

coatings have enjoyed considerable growth due to environ-
Structural materials have limitations for use at high tem- mental awareness and increased productivity compared to
peratures due to oxidation, chemical reaction and erosion. To traditional method of curing [5,6].
provide improved reliability at high operating temperatures, Novolac epoxy acrylates provide a higher aromatic con-
high heat- and corrosion-resistant protective coatings are tent and more crosslink sites in the pendent positions along
used. Heat-induced degradation may proceed more rapidly the backbone of molecules than conventional DGEBA epoxy.
than light-induced degradation at high temperature. Most or- This gives a high heat resistance coating [7] and makes such
ganic coatings degradate in few minutes [1,2]. Conventional epoxy acrylates desirable for imparting this characteristic.
organic protective coatings fail due to carbonization and evo-
lution of aggressive gases. Such films age rapidly at elevated
2. Experimental
temperature (>100 ◦ C) and exhibit loss of flexibility, elastic-
ity, adhesion and protective value. 2.1. Materials
In general, physical properties of highly desirable heat
resistant coatings are: a high glass transition temperature Phenol novolac epoxide Synthesised in laboratory
(>250 ◦ C); a high decomposition temperature (>400 ◦ C) as Cresol novolac epoxide Synthesised in laboratory
determined by differential thermal analysis; and a high re- Diglycidyl ether of bisphenol-A Ciba Giegy, Bombay
sistance to weight loss as measured by thermogravimetric Epichlorohydrin E. Merck
analysis (TGA) [3,4]. Acrylic acid E. Merck
Triethyl amine E. Merck
In the past, heat resistant epoxy coatings have been Trimethylol propane triacrylate Aldrich
developed by conventional curing using different silicon- Pentaerythritol tetracrylate Aldrich
1,6-Hexanediol diacrylate Flucka
␥-Amino propylmethyl siloxane Synthesized in laboratory
∗ Corresponding author. N-[3-(Trimethoxysilyl)-propyl] Aldrich
E-mail addresses: madhubajpai 6@rediffmail.com ethylene diamine
(M. Bajpai), vipin1222@rediffmail.com (V. Shukla), 2,2-Diethoxy acetophenone Flucka
Firdaushabibkhan786@yahoomail.com (F. Habib).

0300-9440/$ – see front matter © 2005 Published by Elsevier B.V.

doi:10.1016/j.porgcoat.2004.12.010
240 M. Bajpai et al. / Progress in Organic Coatings 53 (2005) 239–245
2.2. Method
2.2.1. Synthesis of novolac resin
Novolac resin was prepared by condensation reaction be-
tween phenol/cresol and formaldehyde in acidic condition.
Initially phenol/cresol (1 mole) with some quantity of water
was taken in three-neck flask. The pH was adjusted to 0.5 with
sulphuric acid (used as catalyst) and the contents heated to
80 ◦ C with constant stirring. The required amount (0.5 mole)
of formaldehyde (37% formaline solution) was added over
a period of 3 h through a dropping funnel, and stirring was
continued for an additional 30 min, water was then removed
under vacuum.
2.2.2. Synthesis of novolac epoxy resin
Laboratory prepared novolac/cresol novolac (1 mole) was
reacted with epichlorohydrin (10 mole) at 102–105 ◦ C and
40% sodium hydroxide solution was added gradually to the
reactants over a period of 3 h through a dropping funnel. After
completion of reaction, salt (NaCl) was removed by washing
with hot water and then water was removed through vacuum
distillation.
2.2.3. Synthesis of epoxy acrylate resins
Acrylation of above prepared epoxy resins was carried
out by using 1:09 molar ratio of epoxide and acrylic acid
in presence of triethyl amine as catalyst (1phr) and hydro-
quinone (200 ppm) as inhibitor. The reaction was carried out
at 90 ± 2 ◦ C in nitrogen atmosphere, and completion of re-
action was determined by calculating the acid value [8] at
definiten time intervals.
2.2.4. Synthesis of γ-amino propyl methyl siloxane
2.2.4.1. Synthesis of methyl dichlorocyanoethyl silicon.
Methyl dichloro silane, directly reacts with acrylonitrile at
110 ◦ C in presence of speier’s catalyst for 5 h. The prepared
methyl dichlorocyanoethyl silicon was distilled off.
2.2.4.2. Cohydrolysis of methyl dichlorocyanoethyl sil-
icon. Methyl dichlorocyanoethyl silicon (10%) and
dichloromethyl silane (90%) were dropped in water at
room temperature for cohydrolysis purpose and water
was removed under vacuum and the prepared compound
was characterized by I.R. ( C N, 2156 cm−1 ; Si O Si,
1040–1060 cm−1 ; Si Me, 1261 cm−1 ) as shown in Fig. 1.
2.2.4.3. Reduction of cyano ethyl methyl polysiloxane. The
above-prepared product was submitted for reduction by dis-
solving in tetrahydrofuran (THF) using lithium aluminium
hydride (LiAIH4 ) at 66 ◦ C for 4–5 h. The prepared ␥-
amino propyl methyl silicon was characterised by I.R. (v-
NH2 , 3400–3500 cm−1 ; Si O Si, 1040–1060 cm−1 ; Si Me,
1261 cm−1 ) [9] as shown in Fig. 2.
2.2.5. Preparation of test samples
All prepared acrylated epoxides were mixed with the ap-
propriate quantity of reactive diluents, i.e., TMPTA, PETA
and HDDA, organosilicon compound and photo-initiator. The
panels were coated with a film applicator of approximate 15-
␮m film and then exposed to a UV-lamp of 80 W/cm for
curing. The panels were evaluated for various film character-
istics.
2.2.6. Thermogravimetric analysis
Thermogravimetric analysis of the samples was carried
out (on TGA V5.1A DuPont 2100 by heating at the rate of
20 ◦ C/min) to study the thermal behaviour of the coatings.
3. Results and discussion
Table 1 shows the coding and characteristics of the vari-
ous epoxy resins. The novolac epoxy resin (E1 ) has epoxide
equivalent weight 225, highly viscous and pale yellow in
colour. Cresol novolac epoxy resin (E2 ) has epoxide equiva-
lent weight 200, highly viscous and slightly yellow in colour.
Diglycidyl ether of bisphenol-A resin (E3 ) having epoxide
equivalent weight 180, is highly viscous slightly less than E1
and E2 and water white in colour.
Table 2 shows the change in acid value of different epoxide
acrylate resins with reaction time. It is apparent from the table
that the acid value decreases with the reaction time. The time
required for product having desired acid value (≤6.0 KOH/g
solid) was 210, 273 and 300 min for AE3 , AE2 , AE1 , respec-
tively.
Fig. 3 illustrates the change in acid value with reaction
time for all the samples. It is apparent from the plot that
the decrease in acid value in the initial stages of reaction
is not linear. This is due to higher concentration of reactive
sites and greater possibility of association of acid and epox-
ide groups. The linearity of the plot in higher conversion
region, 70% and above (taking the decrease in acid value
from the initial value as a measure of conversion) reveals that
the reactivity of functional group is independent of molec-
ular size, which is characteristic of such an esterification
reaction.
 M. Bajpai et al. / Progress in Organic Coatings 53 (2005) 239–245 241

Fig. 1. I.R. spectrum of cyano ethyl methyl polysiloxane.

Fig. 2. I.R. spectrum of ␥-aminopropyl methyl polysiloxane.

Table 1
Characteristics of epoxy resins
S. no. Sample resin Code Epoxide equivalent weight (EEW) Texture appearance
1 Novolac epoxy resin E1 225 Highly viscous, pale yellow in colour
2 Cresol novolac epoxy resin E2 200 Highly viscous, very slight yellow in colour
3 Diglycidyl ether of bisphenol-A E3 180 Highly viscous, water white in colour
242 M. Bajpai et al. / Progress in Organic Coatings 53 (2005) 239–245

Table 2
Acid value and reaction time of different epoxy acrylate resins
S. no. Reaction Acid value (mg KOH/g solid)
time (min)
AE1 AE2 AE3
1 0 120.0 120.0 120.0
2 30 92.0 84.0 74.0
3 60 78.0 66.0 49.0
4 90 65.0 50.0 34.0
5 120 53.0 38.0 21.0
6 150 44.0 28.0 14.0
7 180 35.0 21.0 9.5
8 210 28.0 14.0 6.0
9 240 22.0 9.0 –
10 270 16.0 6.0 –
11 300 6.0 – –
Where AE1 , novolac epoxy acrylate; AE2 , cresol novolac epoxy acrylate;
AE3 , bisphenol-A epoxy acrylate.

Figs. 4–9 show the I.R. spectra of the different epoxy resins
and acrylated epoxy resins.

3.1. I.R. spectra of epoxy resin and epoxy acrylated

resins

Figs. 4–6 shows the I.R. spectra of novolac epoxy resin,

cresol novolac epoxy resin and bisphenol-A epoxy resin,
Figs. 4–6. I.R. spectrum of novolac epoxy resin (E1 ) (Fig. 4), cresol novolac
E1 , E2 and E3 , respectively. A prominent band is observed
epoxy resin (E2 ) (Fig. 5) and bisphenol-A epoxy resin (E3 ) (Fig. 6).
at 940, 933 cm−1 in E1 , E2 and E3 , respectively, which
shows the presence of oxirane rings in all epoxy resins.
The I.R. spectrum of epoxy acrylates shown in Figs. 7–9

Fig. 3. Drop in acid value with time.

 M. Bajpai et al. / Progress in Organic Coatings 53 (2005) 239–245 243

Fig. 10. Thermogravimetric graph.

Table 3 shows the coating composition of different

epoxy acrylate resins with varying of organo silicon com-
pounds having same photo-initiator (2,2-diethoxy acetophe-
none) and same reactive diluents. All films are cured within
20 s.

Figs. 7–9. I.R. spectrum of novolac epoxy acrylate (AE1 ) (Fig. 7), cresol
novolac epoxy acrylate (AE2 ) (Fig. 8) and bisphenol-A epoxy acrylate (AE3 )
(Fig. 9).
of AE1 , AE2 , AE3 , respectively, exhibit bands in the re-
gion of 1735, 1775 and 1750 cm−1 , which confirms the pres-
ence of ester linkages. The epoxy bands are not so promi-
nent in these spectra due to the opening of the oxirane ring
during the process of acrylation. Bands corresponding to
acrylol double bond appeared at 1607, 1610 and 1615 cm−1
for acrylated resin AE1 , AE2 and AE3 , respectively, and
a broad band near 3454 cm−1 shows the presence of –OH
group.
3.2. Tests
The coated tin, mild steel and glass panels were subjected
to following performance tests according to BIS-101 speci-
fications.
3.2.1. Flexibility
Flexibility test was carried out on 1/4 mandrel. Films
of all samples were flexible enough to pass through the
mandrel as shown in Table 4. Specially sample no. III, VI,
IX, XV, XVIII show highest flexibility because they contain
higher percentage of silicon compounds as compared to other
samples.

Table 3
Formulations (of heat resistant coating with different amounts of silicon compounds
S. no. Ingredients Samples no.

I II III IV V VI VII VIII IX X Xl XlI XIII XlV XV XVI XVII XVIII XVIII
1 AE1 45 45 45 45 45 45 – – – – – – – – – – – – –
2 AE2 – – – – – – 45 45 45 45 45 45 – – – – – – l–
3 AE3 – – – – – – – – – – – – 45 45 45 45 45 45 45
4 TMPT A 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10
5 HDDA 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15
6 PETA 19.5 19 18.5 19.5 19 18.5 19.5 19 18.5 19.5 19 18.5 19.5 19 18.5 19.5 19 18.5 18.5
7 DEAP 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4
8 APMS 0.5 1.0 1.5 – – – 0.5 1.0 1.5 – – – 0.5 1.0 1.5 – – – –
9 TSPEDA – – – 0.5 1:0 1.5 – – – 1.5 1.0 1.5 – – – 0.5 1.0 1.5 1.5
AE1 , novolac epoxy acrylate resin; AE2 , cresol novolac epoxy acrylate resin; AE3 , bisphenol-A epoxy acrylate resin; TMPTA, trimethylol propane triacrylate;
HDDA, 1,6-hexanediol diacrylate; PET A, pentaerythritol tetracrylate; DEAP, 2,2-diethoxy acetophenone; AMPS, ␥-aminopropyl methyl siloxane; TSPEDA,
N-{3-(trimethoxysilyl)propyl} ethylene diamine.
244 M. Bajpai et al. / Progress in Organic Coatings 53 (2005) 239–245

Table 4
Properties of cured films
S. no. Sample Scratch hardness Pencil Flexibility (1/4 ) Gloss (%) Distilled water 5% H2 SO4 5% NaOH
no. (in gIn) hardness resistance resistance resistance
1 I 1800 4H Passed 95–97 V.G. V.G. F
2 II 1950 4H Passed 95–96 V.G. V.G. G
3 III 2000 5H Passed 95–97 V.G. V.G. F
4 IV 1800 4H Passed 95–95 E V.G. V.G.
5 V 1950 4H Passed 95–98 E E V.G.
6 VI 2000 5H Passed 95–92 E E V.G.
7 VII 1900 4H Passed 98 V.G. V.G. G
8 VIII 2000 4H Passed 97 V.G. E G
9 IX 2050 5H Passed 98 V.G. E V.G.
10 X 1900 4H Passed 199 E E G
11 XI 2000 4H Passed 100 E E V.G.
12 XII 2100 5H Passed 92 E E V.G.
13 XIII 1600 3H Passed 85 G F P
14 XIV 1700 3H Passed 87 G F P
15 XV 1800 4H Passed 85 V.G. E F
16 XVI 1600 3H Passed 85 V.G. V.G. P
17 XVII 1700 3H Passed 88 V.G. V.G. F
18 XVIII 1800 4H Passed 82 V.G. V.G. V.G.
E, excellent; F, fair; P, poor; V.G., very good.

3.2.2. Scratch hardness
Load bearing capacity of the films was checked by au-
tomatic scratch hardness tester. Scratch hardness of various
samples is shown in Table 4. Results show that scratch hard-
ness of sample no. III, VI, IX, XII, XV and XVIII with higher
percentage of silicon compound was higher.
3.2.3. Pencil hardness
In the test sample, strip is drawn under a pencil (for ex-
ample, one with changeable 0.5 mm flattened leads) until a
hardness grade is reached which will scratch the surface. The
coating is then assigned a hardness value such as H, 2H,
3H, etc., signifying the hardness grade. We use different pen-
cils of different grades and found that samples III, VI, IX,
XII, XV and XVIII passes maximum extent of hardness (see
Table 4).
3.2.4. Gloss
After watching the sample from different angles, it had
been observed that samples of cresol novolac epoxy had ex-
cellent gloss (100%) as compared to the other samples (see
Table 4).

Fig. 11. Thermogravimetric graph. Fig. 12. Thermogravimetric graph.

 M. Bajpai et al. / Progress in Organic Coatings 53 (2005) 239–245 245

Table 5 cured epoxy has been evaluated from the dynamic thermo-
Activation energy of samples grams. The fractional decomposition (α) for the respective
S. no. Sample no. Activation energy (J/mole) temperature has been calculated from TGA graphs. Higher
1 I 18.2 value of activation energy (see Table 5) may be due to the
2 II 20.1 presence of polynuclearity in the resin (presence of silicon in
3 III 22.6 the resin). High activation energy for the decomposition of
4 IV 21.8
5 V 22.7
the system leads to better thermal stability of the compound
6 VI 24.2 [10–12].
7 VII 20.9
8 VIII 23.7
9 IX 26.1 4. Conclusion
10 X 22.4
11 XI 24.5
12 XII 26.0 The thermal stability of the epoxy resin increases to about
13 XIII 16.2 420 ◦ C with the higher content of silanes (1.5%). The in-
14 XIV 22.2 creased activation energy with respect to increase in silicon
15 XV 25.9 compound upto a certain level indicates a more thermally
16 XVI 21.2
17 XVII 22.1
stable cresol novolac epoxy resin system. Chemical and cor-
18 XVIII 24.8 rosion resistance of the composition have also shown an im-
provement while scratch hardness and flexibility have given
satisfactory results.
3.2.5. Resistance against distilled water
Samples exhibited good to excellent resistance when they
are exposed to distilled water. Samples, which have high per-
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