Progress in Organic Coatings 51 (2004) 267272

Weathering study of epoxy paints

V.C. Malshe , Gulzar Waghoo
Paints and Polymer Division, University Institute of Chemical Technology, Matunga, Mumbai 400019, India
Received 26 March 2004; accepted 8 July 2004

Abstract
The weathering characteristics of TiO2 -based paints of diglycidyl ethers of bisphenol A (DGEBPA), bisphenol F (DGEBPF), bis-2,6-xylenol
F (DGEBXF), bis-2,6-xylenol S (DGEBXS) and bis-2,6-xylenol (DGEBX) with various curing agents have been studied by subjecting them
to accelerated and environmental weathering. Of all the epoxy resins, the paint using DGEBPA gave the best weathering characteristics with
better chalk resistance, optimum yellowing and good gloss retention when cured with amine terminated dimer fatty acid-based polyamide.
The methyl substitutions on aromatic ring and presence of methylene and sulfone groups between the phenolic moieties caused enhanced
degradation of epoxy resins as evidenced by their faster chalking on exposure. When cured with an aminosilane compound all the epoxy
paints showed excellent improvement in chalk resistance but were associated with poor initial gloss and more yellowing during exposure. The
relationship between the two types of weathering was found to be approximately two and a half hours exposure in accelerated ageing being
equal to 1 day in environmental weathering in Mumbai (India), thus leading to a nearly 10-fold acceleration of weathering.
2004 Published by Elsevier B.V.
Keywords: Epoxy resins; Curing agents; Paint; Accelerated weathering; Environmental weathering; Chalk resistance

1. Introduction
Epoxy resins have tremendous applications in the polymer
field because of their range of attainable properties and versatility [1]. However, due to the presence of aromatic moiety
generally they absorb at about 300 nm and degrade in the presence of UV light and humidity. Weathering of epoxy resins is
fairly good for castings and laminates but for thin films and
epoxy paints, it is generally regarded only as fair, because of
discoloration and chalking. This is the major cause of concern for the polymer chemists limiting the use of epoxies for
outdoor applications.
Kelleher and Gesner [2] have studied the degradation of
high molecular weight epoxy polymer of bisphenol A. They
found that there was a decrease in intrinsic viscosity as well
as gel formation, indicating that chain scission and crosslinking occurred simultaneously. The irradiation of bisphenol A
based polymers viz., polysulfone, polycarbonate and epoxy
resin led to chain scission as indicated by the reduction in

Corresponding author.
E-mail address: vcmalshe@hotmail.com (V.C. Malshe).

0300-9440/$ see front matter 2004 Published by Elsevier B.V.

doi:10.1016/j.porgcoat.2004.07.007

intrinsic viscosity. However, of the three, epoxy was the only

material that also showed gel formation along with chain scission. The singularity of this effect excluded the participation
of the bisphenol portion of the chain in the gel forming reaction. Furthermore, irradiation sufficient to cause a production
of 25% gel in the epoxy was ineffective in forming gel in a
completely acetylated polymer. This clearly showed that the
hydroxyl groups generated by the ring opening of epoxide
were responsible for the crosslinking reaction [3]. Riveton et
al. [4,5] also carried out the photo-oxidation of epoxy resin at
long and short wavelengths and found that the main reactions
involve the methylene groups in the -position to the ether
groups formed due to the dehydration of secondary hydroxyl
groups.
Silicone compounds are well known blocking agents
for the hydroxyl groups [6,7]. The effect of aminosilicone
compounds as curing agents for epoxy resins have been
reported and found to improve their water resistant properties
[8]. Ouyang et al. have also explored the effectiveness of
thin films of SiOx coatings in protecting polypropylene
and polyurethane polymers against photo-oxidation [9].
Also the direct photolysis of the Si O bond is rather

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V.C. Malshe, G. Waghoo / Progress in Organic Coatings 51 (2004) 267272

impossible because the dissociation energy of the Si O

bond is 185 kcal/mol [10].
In the present work, the chalking characteristics of the
paints made from the conventional liquid epoxy resin and
its chemically modified forms with different curing agents
are reported. The chemical structure of typical amine cured
diglycidyl ether of bisphenol A is

The possible weak links in the amine cured epoxy can be

hypothesized as indicated by dotted lines in the structure: (A)
isopropylidene group, (B) aromatic group, (C) alkyl hydroxy
group and (D) N-alkyl group.
To study the effect of individual group, five epoxy resins
namely, diglycidyl ether of bisphenol A (DGEBPA), diglycidyl ether of bisphenol F (DGEBPF), diglycidyl ether of
bis-2,6-xylenol F (DGEBXF), diglycidyl ether of bis-2,6xylenol S (DGEBXS) and diglycidyl ether of bis-2,6-xylenol
(DGEBX) were considered. DGEBPF, containing methylene
group between the two phenolic moieties was chosen for
the comparison with the isopropylidene group present in
DGEBPA. DGEBXF, having 2,6-dimethyl substituted aromatic ring was taken to check the effect of methyl substitution on the aromatic ring. DGEBXS having sulfone and
DGEBX without any group between the phenolic moieties
were also taken for the study. The role of secondary hydroxyl groups was evaluated by using an aminosilane curing agent of which amine part was responsible for curing of
epoxy while the alkoxy portion silylated the hydroxyl group
generated during the curing stage. The effect of N-alkyl portion was studied by using non-amine curing agents like phthalic anhydride, trimellitic anhydride and pyromellitic dianhydride. Simple TiO2 -based white paints were made from all
the epoxy resins and cured on aluminum panels with several
curing agents. These panels were then evaluated by subjecting them to accelerated and environmental weathering for the
chalking, gloss and yellowing properties.

(FPA), with amine value 200 by Uniform Paints and

-(aminoethyl)aminopropylmethyldimethoxysilane (AS) by
Reliance Silicones (India) Ltd. Epichlorohydrin, xylene,
butanol, triphenyl phosphine (TPP), triethylene tetramine
(TETA), dicyandiamide (DICY), phthalic anhydride (PA),
trimellitic anhydride (TMA), pyromellitic dianhydride

(PMDA), cyanuric acid (CA), sodium hydroxide, all of synthetic grade, were procured from Ranbaxy Fine Chemicals
Ltd.
2.2. Preparation
DGEBXF with EEW 195, DGEBXS with EEW 245 and
DGEBX with EEW 190 were synthesized using the standard method of epoxy preparation. In a typical method,
bisxylenols and epichlorohydrin were charged in 1:10 molar ratio in a four neck cylindrical glass vessel fitted with a
mechanical stirrer, addition funnel, condenser and thermometer. The mixture was heated to about 70 C and then 2.1 mol
of 40% aqueous sodium hydroxide solution was added drop
wise over a period of 1 h, the temperature being allowed to
rise to 110 C. The mixture was continued to reflux at 110 C
for 1 h, cooled and allowed to separate. The organic layer was
separated after washing with water and then filtered using a
sintered crucible. The filtrate was distilled to remove the excess epichlorohydrin to get a clear pale yellow viscous liquid
epoxy resin.
Simple solvent-based white paints using epoxy resin, TiO2
and xylenebutanol (1:1) solvent mixture were prepared in
ball mill by milling for 24 h. The curing agents FPA, TETA
and AS were added at the time of application whereas DICY,
CA, PA, TMA and PMDA were mixed during paint preparation in the ball mill. The pigment volume concentration
(PVC) of the paints including the curing agent was optimized
at 17% and the total solid content was 60%.

2. Experimental
2.3. Evaluation
2.1. Materials
DGEBPA (GY250) with epoxy equivalent weight (EEW)
180 was supplied by Ciba Speciality Chemicals, DGEBPF
(LAPOX XR40) with epoxy equivalent weight 185 by Atul
Ltd. Valsad, bis-2,6-xylenol F, bis-2,6-xylenol S, bis-2,6xylenol and rutile grade TiO2 by Filtra Catalysts & Chemicals Ltd., amine terminated dimer fatty acid based polyamide

The paints were applied on 1 mm thick aluminum panels

of size 75 mm 150 mm by flow coating method to have a
uniform coating thickness of about 5080 m. In the assessment of accelerated weatherability, the panels were exposed
to the weathering in QUV apparatus (Model QUV/Basic).
For this evaluation the panels were exposed to the cycle of
UV light and humidity. In a typical cycle, exposure to UV

V.C. Malshe, G. Waghoo / Progress in Organic Coatings 51 (2004) 267272

light was at 50 C for 4 h and exposure to humid conditions

was at 45 C for 4 h as per ASTM D4587. The panels were
subjected to ageing for different time intervals up to 1000 h.
The environmental weathering was done on the top of a three
storey building in UICT, Matunga, located in Central Mumbai (latitude 19 01.6 ) with annual rainfall of about 2200 mm,
relative humidity ranging from 61 to 87% the latter being the
highest in the monsoon period and mean daily temperature
ranging from 24 to 33 C. For the assessment of environmental weatherability, the panels were directly exposed to the
weathering in an unbacked rack inclined at 52 facing south.
The evaluations were done at intervals of 15 days for a period
of 12 months.
The gloss of the panels were measured at 60 angle of
incidence (ISO 2813) using BYK Glossometer. Yellowness
indices (ASTM D1925) of the panels were determined by
Gretag Macbeth make Spectrophotometer CE 7000A (Optiview propalette 2.0e). The measurements of gloss as well
as the yellowness index were done at three different portions of the panel and the average of the three readings was
taken. To evaluate the degree of chalking ASTM D4214 Test
Method BWet Finger Method was employed. The method
recommending one continuous rub on the surface with a wet
fingertip, however, was not suitable for materials with less
chalking. So the fingertip was revolved for 25 times over approximately 2 in. 2 in. of the exposed area with a medium
pressure. The medium pressure was quantified by placing the
finger on a balance and pressing downward until 2 kg pressure
was obtained.
In case of accelerated weatherability, the panels were also
weighed before and after the exposures on a Sauter AR 1014
balance with a capacity to measure up to 100 m to study the
loss of weight during the weathering.
The percentage weight loss was calculated using the formula:
xy
% weight loss =
100
x
where x is the weight in grams of paint before exposure and
y the weight in grams of paint after exposure, the value of x
being equal to the difference in weight between the coated
and the blank aluminum panel.

269

3. Results and discussions

3.1. Evaluation of chalking
Table 1 gives the chalking time of various epoxy paints
in hours and days exposed to accelerated and environmental weathering, respectively. The amount of curing agent is
expressed in parts per hundred parts of epoxy resin (phr)
and varied for different curing agents. For cyanuric acid as a
curing agent, TPP (0.25% based on epoxy resin) was added
during the paint making.
The order of chalking was found to be DGEBXS >
DGEBX > DGEBXF > DGEBPF > DGEBPA. Replacement of isopropylidene group (DGEBPA) with the methylene
group (DGEBPF) decreased the chalk resistance slightly. All
the three resins with methyl substitutions on the aromatic
group showed faster and more chalking than the ones without the substitutions. Presence of sulfone group (DGEBXS)
and absence of any group (DGEBX) between the phenolic
moieties further deteriorated the chalk resistance of epoxy
paint. Amongst the curing agent, use of FPA for DGEBPA
gave the best results with least chalking followed by TETA,
PA and CA but the films formed with CA as curing agent were
brittle and flaked off with longer exposure. The paints cured
with DICY, TMA and PMDA gave much faster chalking than
the remaining curing agents. When AS was used as a curing
agent, the chalk resistance of all the paint panels improved
remarkably. The improvement was more prominent for DGEBXF and DGEBX which showed chalk resistance of 400 h,
almost four times of that with FPA. DGEBPA showed the
maximum chalk resistance and showed chalking only after
800 h.
The results of the environmental weathering showed the
same trend as that of the accelerated weathering. The panel
coated with DGEBPA paint and cured with AS did not show
chalking even after 365 days. It was also interesting to note
that all the AS cured paints showed faint chalking even after the duration mentioned in accelerated as well as environmental weathering compared to samples cured with other
curing agents which showed severe chalking. The relationship between the two types of weathering was found to be
approximately two and a half hours exposure in accelerated

Table 1
Chalking characteristics of epoxy paints exposed to accelerated and environmental weathering
Curing agents

FPA (50 phr, 27 C)

TETA (13 phr, 27 C)
DICY (10 phr, 150 C)
PA (60 phr, 180 C)
TMA (32 phr, 180 C)
PMDA (30 phr, 180 C)
CA (25 phr, 150 C)
AS (30phr, 27 C)

Accelerated weathering (h)

Environmental weathering (days)

Diglycidyl ether of

Diglycidyl ether of

BPA

BPF

BXF

BXS

BX

BPA

BPF

BXF

BXS

BX

250
250
100
150
100
100
150
800

200
150
100
100
100
100
100
600

100
50
100
100
100
100
100
400

100
50
100
100
100
100
100
300

100
50
100
100
100
100
100
400

150
120
60
60
45
45
90

90
45
45
30
30
30
60
270

45
30
45
30
30
30
60
210

45
15
45
30
30
30
60
120

45
45
45
45
30
30
45
180

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Fig. 1. Variation of yellowness index of various epoxy paints exposed to accelerated weathering.

environment being equal to 24 h in environmental weathering for the climatic conditions prevailing in Mumbai, thus
leading to a nearly 10-fold acceleration of weathering.
3.2. Evaluation of yellowness index
The variation of yellowness indices with the exposure time
for the paints cured with FPA and AS are the only ones being reported since the other curing agents led to much faster
chalking (Figs. 1 and 2). The yellowness index was more
or less the same for all the paints, the maximum being for
DGEBPF and DGEBX. All the AS cured samples showed
more yellowing than the FPA cured ones. For all the samples, the major yellowing occurred in the initial duration of
exposure, after which it showed a little change. This was due
to the fact that once chalking occurred, the chalked pigment
formed a protective layer on the surface preventing the further

degradation of paint polymer. In the accelerated tests, after

the initial increase in yellowness index there was a gradual
decrease in its value with more exposure as UV cycle was
followed by condensation cycle where the chalked pigment
got washed away exposing fresh surface to the top. This was
confirmed by the decrease in the weight of the paint panels
with more and more exposure.
3.3. Evaluation of weight loss
Fig. 3 give the percentage weight loss of the epoxy resin
paints cured with FPA and AS in the accelerated weathering.
The weight loss was more prominent after the QUV exposure
of over 200 h for FPA cured paints and over 500 h for the
AS cured paints. Also due to chalking there was up to 45%
weight loss with FPA curing agent whereas only 12% weight
loss was observed with AS. DGEBPA showed the minimum

Fig. 2. Variation of yellowness index of various epoxy paints exposed to environmental weathering.

V.C. Malshe, G. Waghoo / Progress in Organic Coatings 51 (2004) 267272

Fig. 3. % Weight loss of various epoxy paints exposed to accelerated weathering.

Fig. 4. Variation of % gloss of various epoxy paints cured with FPA exposed to accelerated weathering.

Fig. 5. Variation of % gloss of various epoxy paints cured with FPA exposed to environmental weathering.

271

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weight loss confirming least chalking while maximum weight

loss was observed for DGEBXS.
3.4. Evaluation of gloss
The effect of exposure on the gloss of only FPA cured
panels is shown in Figs. 4 and 5. In both the accelerated as
well environmental weathering, all the paint panels showed
marked decrease in gloss. It was found that the initial gloss
of all aromatic methyl substituted epoxy paints were very
high with DGEBX having the highest gloss. The gloss of
DGEBPA and DGEBPF comparatively were less and this
was also confirmed by taking a commercial white paint of
DGEBPA, which also showed poor initial gloss. It was interesting to note that though the loss of gloss as a percentage
was high for DGEBX, still its gloss after 150 h corresponded
to the 0 h gloss for DGEBPA in the accelerated ageing. A
gradual decrease for gloss of DGEBPA paint in environmental weathering was observed due to less chalking. The initial
gloss for all the AS cured paint samples were very low with
gloss values less than 10%. So their further evaluation of
gloss after exposure was not done.

4. Conclusions
The above study shows that of the weak links hypothesized:
(A) The aromatic moiety plays the major role in the degradation of epoxy resin. This is confirmed by the fact that
methyl substitution on aromatic part causes faster and
increased chalking of the paint as observed in the case
with DGEBXF, DGEBXS and DGEBX.
(B) The sulfone group in DGEBXS, followed by absence
of any group in DGEBX and the methylene bridge in

DGEBPF between the two phenolic moieties cause more

and faster chalking than the isopropylidene in DGEBPA.
(C) The secondary hydroxyl group is the next contributing
factor to the degradation of epoxy paints after the aromatic moiety as evidenced by the remarkable control of
chalking on silylation of the hydroxyl groups.
(D) Severe chalking with the anhydrides curing agent excludes any substantial role of the N-alkyl portion in
degradation.

Acknowledgement
The authors wish to thank Mr. T.N. Venkatesan, Managing
Director, Filtra Catalysts & Chemicals Ltd., for the support
to this project.

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