Progress in Organic Coatings 51 (2004) 172180

Chalk resistant epoxy resins

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 diglycidyl ethers of bisphenol A (DGEBPA), bisphenol F(DGEBPF) and bis 2,6-xylenol F(DGEBXF) were partially modied with
various linear and aromatic dibasic acids. The paints prepared using these resins and cured with amine terminated dimer fatty acid based
polyamide (FPA) were evaluated for their weathering characteristics by subjecting them to accelerated and environmental weathering. The
chalk resistance and the gloss increased with the increase in the carbon length of the linear acids. The paint prepared with DGEBPA modied
with sebacic acid and cured with FPA gave the best weathering characteristics with remarkable improvement in chalk resistance, optimum
yellowing and good gloss retention. The aromatic modications on the contrary enhanced the degradation of epoxy resins as evidenced by
their faster chalking on exposure.
2004 Elsevier B.V. All rights reserved.
Keywords: Epoxy resins; Dibasic acids; Accelerated weathering; Environmental weathering; Chalk resistance
1. Introduction
Epoxy resins are being extensively employed world wide
for industrial castings, high strength adhesives, durable lam-
inates, cold solders, potting compounds for all varieties of
electrical and electronic apparatus [1]. Depending on the
chemical structure of the curing agents and the curing con-
ditions, it is possible to obtain toughness, chemical resis-
tance, mechanical properties ranging fromextreme exibility
to high strength and hardness, good heat resistance and high
electrical resistance. However, the most important technical
factor which has prevented their outdoor use is their tendency
to surface breakdown by crazing when exposed to UV light
and humidity.
Due to the presence of aromatic moiety, epoxy resins gen-
erally absorb at about 300 nm causing simultaneous random
chain scission and crosslinking [2]. The degradation is further
enhanced if it contains pigments which also absorb in the UV
region leading to chalking. Chalking is dened as the forma-

Corresponding author. Tel.: +91 22 24145616x462;

fax: +91 22 24145614.
E-mail addresses: vcmalshe@hotmail.com, vcmalshe@rediffmail.com
(V.C. Malshe).
tion of a friable powder on a pigmented coating evolved from
the lm itself at or just beneath the surface. Various methods
are mentioned in the literature to quantify chalking [3].
Although several studies have been carried out on the
degradation of epoxy resins [46], work reported to improve
their stability is limited. The oldest development in improv-
ing the weathering resistance of epoxy resins was the use of
trihydrated alumina as a ller which is found to be transparent
to UV light [7]. The other works in this area include the use
of alicyclic [8] and hydrogenated bisphenol A [910] epoxy
resins. Trihydrated alumina limits the use of pigments, ali-
cyclic epoxy resins do not give all the desired properties of the
conventional epoxies and hydrogenation of bisphenol Amoi-
ety adds to the process and cost making them uneconomical.
The present work deals with a simple approach of im-
proving the chalk resistance of epoxy resins namely, digly-
cidyl ether of bisphenol A (DGEBPA), diglycidyl ether of
bisphenol F (DGEBPF) and diglycidyl ether of bis xylenol
F (DGEBXF) by modifying them with various linear or aro-
matic dibasic acids in 2:1 molar ratio to get terminal epoxy
groups as shown in Scheme 1.
Simple white paints based on rutile grade TiO
2
were made
from all the resins. The rutile grade TiO
2
is known to act as
catalyst for degradation of epoxy resin. No special additives
0300-9440/$ see front matter 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.porgcoat.2004.07.018
V.C. Malshe, G. Waghoo / Progress in Organic Coatings 51 (2004) 172180 173
Scheme 1.
to improve the UV stability and other weathering character-
istics were added in all the paints. The aim was to study the
weathering of epoxy resins so that their paints which lasted
as much as 1 year with the modied epoxy could have still
better life with pigments and additives that have protective
properties. The paints were cured on aluminum panels with
an amine terminated dimer fatty acid based polyamide (FPA).
These panels were thenevaluatedbysubjectingthemtoaccel-
erated and environmental weathering for the chalking, gloss
and yellowing properties.
2. Experimental
2.1. Materials
DGEBPA(GY250) with epoxy equivalent weight 180 was
supplied by Ciba Speciality Chemicals, DGEBPF (LAPOX
XR40) with epoxy equivalent weight 185 by Atul Ltd. Val-
sad, bis 2,6-xylenol F and rutile grade TiO
2
by Filtra Cat-
alysts & Chemicals Ltd. Thane and FPA (amine value =
200) by Uniform Paints, Vapi. Epichlorohydrin, xylene, bu-
tanol, triphenyl phosphine, malonic acid, succinic acid, adipic
acid, azelaic acid, sebacic acid, isophthalic acid, orthoph-
thalic acid, terephthalic acid sodium hydroxide, all of syn-
thetic grade, were procured from Ranbaxy Fine Chemicals
Ltd.
2.2. Preparation
DGEBXF was synthesized using the standard method of
epoxy preparation. Bis 2,6-xylenol F and epichlorohydrin
were charged in 1:10 molar ratio in a four neck cylindrical
glass vessel tted with a mechanical stirrer, addition funnel,
condenser and thermometer. The mixture was heated to about
70

C and then 2.1 moles of 40% aqueous sodium hydroxide

solution was added drop wise over a period of one hour, the
temperature being allowed to rise to 110

C. The mixture was

continued to reux at 110

Cfor one hour, cooled and allowed

to separate. The organic layer was separated after washing
with water and then ltered using a sintered crucible. The
ltrate was distilled to remove the excess epichlorohydrin to
get a clear pale yellow viscous liquid epoxy resin with an
epoxy equivalent weight 195.
The reactions of epoxy resins with the acids were car-
ried out in a four neck cylindrical glass vessel tted with a
mechanical stirrer, condenser, thermometer and an inlet for
purging nitrogen. In a typical method, epoxy resin and the
dibasic acid in 2:0.95 molar ratio were charged into the ves-
sel and heated to 60

C when triphenyl phosphine (0.25% by

weight of epoxy resin) was added. The reaction was carried
out at 90

C in a nitrogen atmosphere and was monitored by

the decrease in acid value.
All the acid modied resins with acid value less than 5
were formed in 4 h and were tacky solid in nature with soft-
ening range of 4050

C. Solvent based white paints compris-

ing epoxy resin, TiO
2
and xylene-butanol(1:1) solvent were
prepared in ball mill by milling for 24 h. The curing agent
FPA was added at the time of application. The pigment vol-
ume concentration (PVC) of the paints including the curing
agent was optimized at 17% and the total solid content was
60%.
2.3. Evaluation
The paints were appliedon1 mmthickaluminumpanels of
size 75 mm 150 mm by ow coating method to have a uni-
form coating thickness of about 5080 microns and air-dried
for 48 h. In the assessment of accelerated weatherability, the
panels were exposed to the weathering in QUV accelerated
weathering tester (Model QUV/Basic). For this evaluation
the panels were exposed to the cycle of UV light and humid-
ity. In a typical cycle, exposure to UV light was at 50

C for
4 h and exposure to humid conditions was at 45

C for 4 h as
174 V.C. Malshe, G. Waghoo / Progress in Organic Coatings 51 (2004) 172180
per ASTM D4587. The panels were subjected to ageing for
different time periods up to 700 h. The environmental weath-
ering 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 pan-
els 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 was 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 (Op-
tiview 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 by ASTM D4214, Test
Method BWet Finger Method was employed. The method
recommending one continuous rub on the surface with a wet
ngertip, however, was not suitable for materials with less
chalking. So the ngertip was revolved for 25 times over ap-
proximately 50 50 mm
2
of the exposed area with a medium
pressure. The mediumpressure was quantied by placing the
nger 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 g to study the
loss of weight during the weathering.
The percentage weight loss was calculated using the for-
mula
%Weight loss =
x y
x
100
where x = weight in grams of paint before exposure, y =
weight in grams of paint after exposure and the value of x
was equal to the difference in weight between the coated and
the blank aluminum panel.
Table 1
Chalking characteristics of epoxy paints exposed to accelerated and environmental weathering
Weathering Accelerated (hours) Environmental (days)
Modied with Epoxy resins Epoxy resins
DGEBPA DGEBXF DGEBPF DGEBPA DGEBXF DGEBPF
250 100 200 150 45 90
Terephthalic acid 150 150 150 60 60 60
Isophthalic acid 150 150 150 75 75 75
Orthophthalic acid 100 100 100 45 45 45
Malonic acid 250 100 200 90 30 90
Succinic acid 350 150 250 120 30 120
Adipic acid 450 200 300 240 45 120
Azelaic acid 600 250 350 60 150
Sebacic acid 650 250 350 60 150
3. Results and discussions
3.1. Evaluation of chalking
The data on accelerated and environmental exposure is
reported in Table 1. It can be seen that among the three ba-
sic resins the order of chalking was DGEBXF > DGEBPF
> DGEBPA. DGEBXF which had methyl substitutions on
aromatic ring showed the maximum chalking. The modica-
tion of all the epoxy resins with aromatic acids decreased the
chalk resistance due to incorporation of more aromatic moi-
ety. With linear dibasic acids there was rst decrease in chalk
resistance with malonic acid but with succinic acid and higher
homologues it increased with the increase in carbon length.
The chalk resistance of DGEBPA when modied with adipic
acid was almost doubled and with azelaic acid and sebacic
acid it increased to over 600 h in the accelerated weathering
test. Also no chalking was observed for 1 year for DGEBPA
modied with azelaic and sebacic acids in the environmental
weathering tests. It was interesting to note that azelaic and
sebacic acid modied DGEBPA showed very faint chalking,
even after the duration mentioned whereas severe chalking
was observed for the similar modications of DGEBPF and
DGEBXF in accelerated as well as in environmental weath-
ering. The relationship between the two types of weathering
was found to be approximately two and a half hours expo-
sure in accelerated environment being equal to 24 h in envi-
ronmental weathering for the climatic conditions prevailing
in Mumbai, thus leading to a nearly 10-fold acceleration of
weathering.
3.2. Evaluation of yellowness index
Figs. 13 give the variation of yellowness index exposed
to accelerated weathering and Figs. 46 are that of environ-
mental weathering for the paints cured with FPA. The yel-
lowness index of the acid modied resin paints was found
to increase more than that of the corresponding basic resin
paints. The aromatic acidmodiedepoxypaints showedmore
yellowing than the linear modications in the environmental
V.C. Malshe, G. Waghoo / Progress in Organic Coatings 51 (2004) 172180 175
Fig. 1. Variation of yellowness indices of DGEBPA epoxy paints exposed to accelerated weathering.
Fig. 2. Variation of yellowness indices of DGEBXF epoxy paints exposed to accelerated weathering.
Fig. 3. Variation of yellowness indices of DGEBPF epoxy paints exposed to accelerated weathering.
176 V.C. Malshe, G. Waghoo / Progress in Organic Coatings 51 (2004) 172180
Fig. 4. Variation of yellowness indices of DGEBPA epoxy paints exposed to environmental weathering.
Fig. 5. Variation of yellowness indices of DGEBXF epoxy paints exposed to environmental weathering.
Fig. 6. Variation of yellowness indices of DGEBPF epoxy paints exposed to environmental weathering.
V.C. Malshe, G. Waghoo / Progress in Organic Coatings 51 (2004) 172180 177
Fig. 7. % Weight loss of DGEBPA epoxy paints exposed to accelerated weathering.
Fig. 8. % Weight loss of DGEBXF epoxy paints exposed to accelerated weathering.
Fig. 9. % Weight loss of DGEBPF epoxy paints exposed to accelerated weathering.
178 V.C. Malshe, G. Waghoo / Progress in Organic Coatings 51 (2004) 172180
Fig. 10. Variation of % gloss of DGEBPA epoxy paints exposed to accelerated weathering.
Fig. 11. Variation of % gloss of DGEBXF epoxy paints exposed to accelerated weathering.
Fig. 12. Variation of % gloss of DGEBPF epoxy paints exposed to accelerated weathering.
V.C. Malshe, G. Waghoo / Progress in Organic Coatings 51 (2004) 172180 179
Fig. 13. Variation of % gloss of DGEBPA epoxy paints exposed to environmental weathering.
Fig. 14. Variation of % gloss of DGEBXF epoxy paints exposed to environmental weathering.
Fig. 15. Variation of % gloss of DGEBPF epoxy paints exposed to environmental weathering.
180 V.C. Malshe, G. Waghoo / Progress in Organic Coatings 51 (2004) 172180
weathering. The yellowness index varied in the range of
3040 for linear modications and 4050 for aromatic modi-
cations of the DGEBPAand DGEBXF, the maximumbeing
for DGEBPF and its modied forms ranging from 5060. In
the accelerated ageing, after the initial increase in yellow-
ness index there was a gradual decrease in its value with the
exposure as UV cycle was followed by condensation cycle
where the chalked pigment got washed away exposing fresh
surface to the top. The less yellowing for all aromatic mod-
ications in accelerated weathering can also be attributed to
the fact that the aromatic modied paints showed more and
faster chalking. This was conrmed by the decrease in the
weight of the paint panels with more and more exposure.
3.3. Evaluation of weight loss
Figs. 79 give the percentage weight loss of the epoxy
paints cured with FPA in the accelerated weathering. The
weight loss was more prominent only after the QUV expo-
sure of over 200 h. It was observed that the percentage weight
loss for all the epoxy paints initially increased when modi-
ed with malonic acid but then decreased as the carbon length
increased. DGEBPAmodied with sebacic acid showed min-
imum weight loss conrming least chalking while maximum
weight loss of 14.8% was observed for DGEBXF modied
with malonic acid. The aromatic acid modication showed
about 57% weight loss.
3.4. Evaluation of gloss
As can be seen from the Figs. 1015, the initial gloss of
the epoxy paints increased with the carbon length with gloss
being maximum for the sebacic acid modied paints. All the
aromatic acid modied epoxy paints showed drastic drop in
the gloss in less than 100 h of accelerated and 60 days of en-
vironmental exposures. For linear acid modications, DGE-
BXF showed high initial gloss as compared to DGEBPA and
DGEBPF, however, due to excessive chalking there was re-
markable drop in their gloss in both the accelerated as well as
the environmental weathering. DGEBPFalso showed consid-
erable drop for all its forms while DGEBPA and its modied
forms comparatively showed better gloss retention.
4. Conclusions
The above study shows that a simple modication of the
basic liquid epoxy resin with linear long chain dibasic acids
considerably increases its chalk resistance with good gloss
retention. DGEBPA as such and with the modication using
linear dibasic acids gave better chalk resistance as compared
to DGEBPF and DGEBXF. It is important to note that the
entire study was carried out by using only a basic paint for-
mulation comprising resin, curing agent, TiO
2
and solvent.
The paints with good weathering characteristics can be ob-
tained if these modied epoxy resins are formulated with
pigments, extenders, additives and UV/light stabilizers.
Acknowledgement
The authors wish to thank Mr. T. N. Venkatesan, Managing
Director, Filtra Catalysts & Chemicals Ltd., for the support
of this project.
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