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Introduction
Can coatings are widely used in the production of
metallic food containers. These coatings are used to
protect metal substrates against corrosion and to avoid
contact between the metal and the foodstuffs. Epoxyphenolic can coatings are usually used on tin-plate
substrates, and have been so used and developed since
the 1950s.1,2
As an organic coating, epoxy-phenolic can coatings
are generally produced from reactive thermosetting
resin precursors, namely epoxy resin precursors and
phenolic resin precursors, which are deposited onto a
metal substrate. During curing, the polymer flows to
form a smooth film and, simultaneously, a crosslinking reaction takes place to create a continuous
network.1,2 Therefore, the ability to predict the curing
behavior of such can coatings is of great importance to
the coating applications.
In recent years, migration of epoxy resin components
into food from epoxy-based can coatings including
epoxy-phenolic can coatings has received considerable
attention. The initial concern mainly surrounded organosols and types of epoxy-based can coatings that in
some cases exceeded the specific migration limit (SML)
for bisphenol A-diglycidyl ether (BADGE), current at
the time. This standard has been revised and is the
subject of epoxy regulation (EC) No 1895/2005. The
extent of any migration between the internal can
coating and the food content has been recognized as
being within the recommendations of food contact
legislation.1,3,4
99
Bisphenol A (BPA), also known as 2,2,-bis(4-hydroxyphenyl) propane, is an important monomer that is used in
the manufacture of epoxy resins for can coatings that are
intended to be in contact with foods and beverages.5 In
recent years, there has been increasing public concern
regarding BPA migration into canned food. Low-level
migration of BPA has been studied in canned vegetables,68 in infant formula,9 in canned alcoholic drinks,10
and in canned fish and meat products.7
BADGE, also known as 2,2-bis(4-hydroxyphenyl)
propane bis(2,3-epoxypropyl) ether, is employed as an
intermediate in the manufacture of epoxy-based can
coatings.4 For over 10 years, published data in several
European countries (UK, Switzerland, Germany, The
Netherlands, Austria, Italy, Denmark) have been
available on BADGE-derivatives and their migration
from can coatings into foods and food simulants across
a range of canned foods.4,8,1017
In order to address these migration issues, several
food contact factors have been addressed. The wetting
resistance of the internal can coating films and the
possibility of the interactions between the internal can
coating films and the food content in the can have been
studied. One hypothesis is that if the food content in
the can does not swell and penetrate the surface of the
coating films, migration into and out of the food
content will be less likely to occur.18,19
Among the factors of relevance to the behavior of
the coating surface are the slip agents in the formulations of the can coatings. These have been modified
with the goal of achieving optimal properties (e.g.,
abrasion and rub resistance, optimal friction).1,2,20,21
There are several theories (including the Bloom
theory, the Ball theory, the Cone theory, and so
on)20 to explain how the slip agents that are present at
the film surface of the can coating might have a
significant influence on the migration resistance and
related properties of the coating film.
Slip agents, both natural and synthetic, are commonly
used in surface coatings to improve surface lubricity and
to impart abrasion or scratch resistance.1,2 These slip
agents are sometimes referred to as internal lubricants
since they are added to the wet coating formulation and
rely on migration to the surface of the coating, on
curing.1,2,4,20,21 Examples include the poly(ethylene)
and polyamide wax types that are usually used in small
amounts to achieve the desired performance characteristics, e.g., lubrication, hardness, and flexibility.2,20,21
This article examines specifically the effects of the
use of three selected slip agents in coating formulations
on several properties of an internal can coating.
Experimental
Materials
A generic model BPA-based epoxy-phenolic formulation and the relevant raw materials (including three
100
Slip 1 (g)
Carnauba
wax + lanolin wax
Slip 2 (g)
Lanolin
wax
Slip 3 (g)
Polyamide
wax
EPHS1
EPHS2
EPHS3
EPHS12
EPHS13
EPHS23
EPHS123
EPHNS
2.5
0
0
2.5
2.5
0
2.5
0
0
0.5
0
0.5
0
0.5
0.5
0
0
0
0.5
0
0.5
0.5
0.5
0
101
0.5
1.0
160.88C
1.5
2.0
89.30C
2.5
0
100
200
300
400
500
Temperature (c)
100
0.0
0.5
Weight (%)
80
60
120.99C 51.64%
40
360.19C 34.30%
1.0
187.72C
1.5
148.35C
2.0
108.39C
20
Residue:
7.966%
(1.840 mg)
2.5
131.65C
3.0
100
200
300
400
500
Temperature (c)
100
200
300
400
500
Temperature (c)
102
Rapid solvent(s)
evaporation (C)
Film network
development (C)
Decomposition of
formed film
30100
30100
100210
100210
210370
210375
Onsets at 370C
Onsets at 375C
30100
30100
100210
100215
210390
215400
Onsets at 390C
Onsets at 400C
0.5
1.0
1.5
2.0
147.76C
107.19C
2.5
119.72C
3.0
0
100
200
300
400
500
Temperature (c)
1
1
0.8
cos q
0.5
0.0
0.6
2.4 m
0.4
6.4 m
0.5
438.86C
14.2 m
0.2
1.0
0
0
1.5
10
20
LV
30
40
50
Surface tension (mN/m)
60
70
115.55C
2.0
100
200
300
400
500
Temperature (c)
103
Coating
2.4
EPHNS
EPHS2
EPHS3
EPHS23
EPHS1
EPHS12
EPHS13
EPHS123
31.6
33.2
31.6
33.0
21.5
24.3
22.2
23.2
4.6
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
31.9
32.4
31.8
32.5
22.2
24.7
23.4
23.6
14.2
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
32.0
32.8
31.4
32.4
22.7
24.3
23.0
23.3
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
0.0300
EPHNS
0.0250
EPHS1
0.8
EPHS2
EPHS3
0.6
cos q
EPHS12
EPHS13
0.4
EPHS1
EPHS2
0.0200
EPHS3
0.0150
EPHS12
EPHS13
0.0100
EPHS23
EPHS123
EPHS123
EPHNS
0
0
10
20
LV
c 30
40
50
Surface tension (mN/m)
0.0000
60
70
104
EPHS23
0.0050
0.2
50
100
150
200
250
Number of rotations
Fig. 9: Weight loss under abrasion for the cured epoxyphenolic coatings containing different combinations of the
slip agents (load of 280 g)
0.0350
280 g
0.0300
480 g
0.0250
0.0200
680 g
0.0150
880 g
0.0100
1080 g
0.0050
0.0000
0
50
100
150
200
250
Number of rotations
Fig. 10: Weight loss under abrasion for the cured epoxyphenolic coatings containing Slip system 1 under different
loads
0.0350
280 g
0.0300
480 g
0.0250
0.0200
680 g
0.0150
880 g
0.0100
1080 g
0.0050
0.0000
0
50
100
150
200
250
Number of rotations
Fig. 11: Weight loss under abrasion for the cured epoxyphenolic coatings containing Slip system 2 under different
loads
0.0350
280 g
0.0300
480 g
0.0250
0.0200
680 g
0.0150
880 g
0.0100
1080 g
0.0050
0.0000
50
100
150
200
250
Number of rotations
Fig. 12: Weight loss under abrasion for the cured epoxyphenolic coatings containing Slip system 3 under different
loads
Conclusions
Slip agents are commonly used in commercial epoxyphenolic can coatings for different purposes. The slip
combination of carnauba wax and lanolin wax enhances the hardness of such coating formulations.
Lanolin wax can play a lubricant role in the manufacture of cans. Polyamide waxes give improvement of
coating wear from coating tools (e.g., roll coating). The
results from this study show that these three slip agents
also influence other characteristics and properties of
epoxy-phenolic can coatings.
It is clear that all of the three slip agents have an
impact on the thermal properties of coatings. The TGA
results show differences in the decomposition caused
by the different slip agents. The polyamide wax has the
greatest influence on the decomposition of the coating.
The three slip agents also affected the solvent(s)
evaporation, the film formation, film network development, and formed film decomposition processes for
the curing coatings. The use of the slip agents delays
solvent evaporation.
The use of the carnauba-lanolin mixtures, in the
epoxy-phenolic coating formulation, improves the
surface appearance after curing. Lanolin wax and
polyamide wax cause the development of a poor
surface appearance for the same coating formulation.
The use of the carnauba-lanolin mixtures in the
coatings reduces the wetting ability of cured coating
surface and would provide less opportunity for the
cured coating film to interact with fluid materials. This
combination plays an important role in protecting the
cured coating surface from wetting by foodstuffs.
These results provide some justification for the
employment of the carnauba-lanolin combination in
the manufacture of the cans and can components
coated with epoxy-phenolic can coatings.
Acknowledgments The work was carried out as a
part of a Defra LINK project FQS45 New technologies
and chemistries for food can coatings. Funding by
105
12.
13.
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