Progress in Organic Coatings 77 (2014) 646656

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Progress in Organic Coatings

journal homepage: www.elsevier.com/locate/porgcoat

New printing inks with barrier performance for packaging

applications: Design and investigation
I.J. Zvonkina a, , P. Gkountara a,b , M. Hilt a , M. Franz b
a
b

Fraunhofer Institute for Manufacturing Engineering and Automation IPA, Allmandring 37, 70569 Stuttgart, Germany
Stuttgart Media University, Nobelstr. 10, 70569 Stuttgart, Germany

a r t i c l e

i n f o

Article history:
Received 15 April 2013
Received in revised form 2 December 2013
Accepted 5 December 2013
Available online 25 December 2013
Keywords:
Barrier coatings
Filled polymer coatings
Inks
Platelet llers
Permeability
Flexographic printing

a b s t r a c t
Barrier properties of packaging materials against moisture and oxygen penetration are of high relevance.
Enhanced protection of existing materials against weather conditions can be achieved by application of
printed coatings. To improve barrier performance of packaging materials, new inks for obtaining printed
coatings with a layered structure were developed and investigated. The proposed ink compositions for
exographic printing on paper substrates are based on an environmentally friendly acrylic binder and
contain inorganic llers with platelet particles incorporated in the polymer matrix. Coatings based on
the developed printing inks demonstrate signicantly decreased water vapour permeability compared
to traditional polymer inks. The effect of decreased permeability was investigated considering inks rheological behaviour, the coating structure, mechanical properties, surface energy and water uptake for
different ink formulations. The developed inks provide variable optical properties including coatings
with a relatively high transparency. The development of the functional barrier inks contributes to saving
natural resources by prolonging life performance of packaging materials and goods.
2013 Elsevier B.V. All rights reserved.

1. Introduction
The concept of improving the quality of paper packaging materials by enhancing their barrier performance is of high interest in
research, technology and application [15]. Enhancement of the
barrier properties of paper and board packaging materials is relevant for prolonging the life cycle of the materials and packed goods
thus bringing economic impact and contributing to saving natural resources. In addition to their barrier performance, packaging
materials are expected to be environmentally friendly, resistant to
mechanical impact, to be of a relatively low cost [1,2], and in several
cases to provide desired optical characteristics.
Examples of packaging materials with improved barrier performance include materials based on polymer lms, aluminium foils
and multi-layered polymer composite materials. Filled and unlled
polymer materials for packaging are usually based on polyvinyl
chloride, polystyrene, polypropylene, polyacrylonitrile and others
[3]. Inorganic llers with a platelet particle shape can be introduced in polymer materials for providing barrier effect against
water vapour and gases. The barrier effect is given by increasing
the tortuous path for water vapour and gas during their penetration
through the material [6]. Fillers with high aspect ratio and with a

Corresponding author.
E-mail address: irina.zvonkina@gmail.com (I.J. Zvonkina).
0300-9440/$ see front matter 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.porgcoat.2013.12.001

relatively high specic surface area contribute to an enhanced reinforcement effect [7]. Most commonly used inorganic llers with
platelet particles are layered clays, such as montmorillonite nanoclays and silicates in general, known for their barrier performance,
low cost and easy processability [3,7,8].
Paper and board materials have been widely used in packaging.
Traditionally used paper and board have, however, a disadvantage
of a relatively poor resistance to moisture and gases [9]. Application of polymer coatings with enhanced barrier performance
is one of the possibilities to improve the quality of paper packaging materials. Application of polymer materials for coatings by
printing has benets in technological and economic aspects. The
existing materials for printing providing the barrier effect against
moisture are based mainly on polymer compositions containing
waxes or other organic components for decreasing coating water
vapour permeability [10,11]. However, application of wax in a polymer composition in an amount sufcient for providing the barrier
effect of the coatings can be disadvantageous due to a possibility
for decreasing printability and the quality of the printed coatings.
This can be due to the drawbacks in the ink transfer and adhesion
leading to ink refusal, print mottle and smearing of water-borne
inks containing wax [12]. Decreasing permeability of water vapour
and gases through materials with polymer coatings still remains a
challenge.
Development of new polymer ink compositions for packaging
with enhanced barrier performance and other improved characteristics of the printed coatings, such as desired mechanical strength

I.J. Zvonkina et al. / Progress in Organic Coatings 77 (2014) 646656

and optical properties, is supposed to be benecial for different

packaging applications. Incorporation of inorganic llers with a
platelet particle shape was expected to enhance the barrier effect of
the printed coatings to water vapour and to provide other desired
functions to the coatings obtained by exographic printing.
Development of such materials for exographic printing is an
alternative approach to improve the quality of packaging materials.
Application of lled water-borne coatings with enhanced barrier
performance allows for creating new packaging materials based on
paper and board with benecial functional performance, sustainability and environmentally friendly nature.
The goal of the study was to develop new ink compositions
for exographic printing on paper with improved barrier effect
and other functional characteristics. The developed ink compositions were investigated with regard to their coating structure,
rheological behaviour, water vapour permeability performance,
mechanical properties, surface energy of the coatings, water uptake
by free lms and wetting of paper by the developed compositions.
The developed compositions were applied on the selected paper
substrate by exographic printing and water vapour permeability of the paper substrates covered by the printed coatings was
evaluated.

2. Materials and methods

A water-based acrylic dispersion (pH 7.9 at 23 C) used in
the study was provided by BASF SE. Three types of llers (aluminium, borosilicate glass and talc) with platelet particles were
selected. Aluminium ake paste and borosilicate glass powder were
provided by Eckart Effect Pigments GmbH and talc powder was
provided by Mondo Minerals B.V. To prevent foam formation during dispersion, an anti-foaming agent was used during preparation
of the printing ink compositions. A dispersion of the anti-foaming
agent was provided by BASF SE. Each of the llers was introduced in
acrylic polymer dispersion separately to obtain printing inks with
different ller volume contents (6 vol.%, 8 vol.%, 9 vol.% or 10 vol.%,
17 vol.% or 19 vol.% and 26 vol.%) to investigate the effect of type
and content of llers on the coating properties.
For incorporation of borosilicate glass and talc particles, aqueous
slurries of each of them were prepared using an ammonia based
dispersion agent provided by BASF SE and a pH buffer solution for
modifying pH during the preparation of the slurries. Dispersion was
performed using a high speed dissolver.
The prepared slurries were incorporated in the water-based
polymer dispersion containing an anti-foaming agent to obtain ink
compositions for each of the llers with different ller volume contents ranged from 810 vol.% to 26 vol.%. Critical pigment volume
concentration (CPVC) was calculated considering oil absorption
[13] and density of the llers [14]. Filler content in the prepared
compositions did not approach CPVC. Aluminium paste was introduced in the polymer binder composition as received using a high
speed dissolver to obtain ink compositions with different aluminium particle content ranged from 6 vol.% to 26 vol.%.
The prepared ink compositions were applied by a Doctor Blade
applicator to obtain coatings and by exographic printing. The coatings prepared using a Doctor Blade applicator served as a model for
investigation of the properties of exographic printed coatings.
In order to obtain the coatings, the prepared ink compositions were applied on glass, Tedlar polyvinyl uoride lm and
on selected paper substrates, and underwent drying at ambient
conditions. A white top coated Kraft liner paper was used as a substrate for the application of the developed compositions by a blade
applicator and by the laboratory exographic printing process. The
coatings on glass and paper substrates with thicknesses of 10 m
and 30 m were analysed as prepared.

647

Free lms with thickness of 3540 m were obtained by pulling

off the coatings from Tedlar polyvinyl uoride lm substrates due
to a lower adhesion of the lled polymer lms to the Tedlar substrates. The prepared free lms served as a model of coatings to
investigate the effect of type and content of the llers on the structure and mechanical properties of the printed coatings.
The laboratory exographic printing was performed using a
exographic printing test machine Nissha (model S.15) equipped
with a Harper XLT-technology anilox roller with the 60 cell geometry, cell volume of 33.80 cm3 /m2 and a 70 L/cm line screen (Harper
Graphics GmbH). A full-tone printing plate Cyrel TDR 112 with
thickness of 2.84 mm and hardness of 38 Sh A used in the printing
tests was provided by DuPont GmbH.
The coatings prepared by a blade applicator and by exographic
printing as well as free lms were kept in a temperature and humidity controlled environment at standard conditions (23 C, 50% RH)
for at least 24 h before investigations.
Rheology analysis of the ink compositions was performed using
a Physica MCR 501 rheometer (Anton Paar GmbH) with cone-plate
geometry (1 angle) at a constant temperature of 23 C. The rheological behaviour was evaluated for at least 3 samples of each
composition to prove reproducibility of the measured tendencies.
Light transmittance of the coatings with the thickness of 30 m
applied on glass substrates was determined using Perkin-Elmer
UVvis spectrophotometer in the visible wavelength region of
400750 nm. The calibration of the spectrophotometer was performed using a glass substrate as a reference.
The structure of the coatings with the thickness of 10 m
on glass substrates was investigated by light and polarised light
microscopy using an upright and inverted light microscope (Carl
Zeiss AG) containing a digital camera to obtain images at different
magnications. The structure of a cryogenic fracture at a crosssection of free standing lms was evaluated using scanning electron
microscopy (SEM) (FEI Helios Nanolab).
Water vapour barrier performance of the coatings was evaluated by analysing the water vapour transmission rate (WVTR) of
free standing lms of similar thickness using a permeability tester
(Lyssy AG). The permeability at the steady stage was determined
by the following equation:
P=

W x
t A p

(1)

where W is the weight of the permeate passing through a lm

with the thickness x, mm, and area A, mm2 , during time t, s; p is
the differential partial pressure across the lm.
Water uptake ratio (WUR) of the prepared free lms was determined gravimetrically after their immersion in water at standard
conditions for specied time intervals. Water uptake ratio of each
lm was calculated as an average of the measurements for 3 samples. The WUR (%) was calculated as follows [15]:
WUR = 100

mt m0
m0

(2)

where mt and m0 correspond to the weight of samples before and

after their immersion in water during time intervals t.
Surface energy analysis was made at the standard conditions
by the sessile drop method using an OCA-series contact angle
device (DataPhysics Instruments GmbH) containing a digital camera. Four liquids (water, diiodomethane, thiodiglycol and ethylene
glycol) were used for the surface energy analysis. The surface
energy of the liquids used for the analysis is shown in Table 1
[1618]. The measurements were repeated at least 5 times for
each liquid. The relative standard deviation of each measurement
did not exceed 5%. The surface free energy was calculated by the
OwensWendtKaelble method [19,20].

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Table 1
Surface energy at 20 C of the liquids used for the surface energy analysis.

Water
Diiodomethane
Thiodiglycol
Ethylene glycol

Total surface
energy (mN/m)

Dispersive
component (mN/m)

Polar component
(mN/m)

72.1
50.0
54.0
48.0

19.9
47.4
39.2
29.0

52.2
2.6
14.8
19.0

Dynamic mechanical analysis (DMA) of free lms was performed using a Netzsch-DMA 242C device at the temperature range
from 60 C to 145 C at the heating rate of 2 K/min with preliminary cooling of the lms to 60 C at the cooling rate of 2 K/min.
Wetting of paper substrates by the inks was analysed by deposition of at least 5 drops of a similar size of each composition on the
surface of the selected paper substrates. Contact angle of the ink
drops on paper was determined afterwards using the device applied
for surface energy evaluation (see above). The tests were performed
at the standard conditions with equal time intervals after deposition. The compositions were diluted as required for printing process
to achieve similar viscosity for each type of the formulation prior to
the wetting tests. The drops were assumed to be symmetrical with
regard to the vertical axe.
Water vapour permeability of the substrates coated by exographic printing was determined gravimetrically after specied
time intervals of water evaporation through the coated substrates.
The tests were performed at the standard conditions according to
the modied method ASTM E96 as described in the study of Arabuli
et al. [21]. The partial water vapour pressure difference (p) at both
sides of the coated substrates was calculated as follows according
to [22]:
p = p

 RH

100

RH2
100

(3)

where p is water vapour pressure equal to 23.756 mm Hg, RH1 and

RH2 correspond to the relative humidity inside (100) and outside
(50) of the cup, respectively.
3. Results and discussion
To provide improved barrier performance to the printing inks,
a layered structure of the printed coatings was designed. Different inorganic llers with platelet particles were incorporated in
acrylic polymer composition to achieve an enhanced water vapour
barrier effect of the printed coatings and other benecial coating properties. The selection of the llers was made considering a
goal of obtaining different mechanical and optical properties of the
printed coatings in addition to the barrier effect, including designing printed barrier coatings with a relatively high transparency.
Aluminium akes incorporated in the polymer dispersion composition were supposed to provide coatings with a silver shade and
a gloss effect. Talc was expected to be used for the development of
transparent coatings considering a close proximity in the values of
the refractive index of talc to that of the polymer. Glass akes covered by a thin silica coating were applied to achieve a relatively high
transparency with a slight silver gloss due to the light refraction and
multiple light scattering inside the platelet glass particles.
Fig. 1 demonstrates the transmittance of polymer coatings lled
with glass and talc platelets with coating thickness of 30 m
applied on glass substrates as a model of coatings printed on paper.
With increasing ller content, transmittance of the coatings lled
with glass platelets slightly decreases, whereas for talc lled coatings no signicant difference was observed (Fig. 1a and b). The llers
applied in the developed inks have diverse mechanical properties
thus providing different contribution to mechanical strength and
to the barrier effect of the printed coatings.

Fig. 1. Light transmittance of polymer coatings lled with glass and talc platelets
with the ller content of 1719 vol.% (a) and 26 vol.% (b) applied on glass substrates.

3.1. Rheology evaluation

Evaluation of the rheological behaviour of the lled polymer
compositions is of high relevance in development and characterisation of barrier printing inks. The developed printing inks
are supposed to demonstrate thixotropic behaviour that would
contribute to satisfactory levelling during a printing process. A
decrease in viscosity with increasing shear rate is supposed to yield
in viscosity values sufcient for the ink composition to ow and
to occupy heterogeneities on the paper surface. This is especially
important for providing enhanced barrier performance of the coatings to avoid or to decrease coating defects such as pin holes.
The developed ink compositions were analysed with regard
to their ow behaviour using a cone-plate viscometer Physica MCR 501 (Anton Paar GmbH) in the shear rate interval of
0.0110 000 s1 that corresponds to the interval, in which printing inks are usually exposed to shearing during a typical printing
process [23]. Each measurement was repeated at least 3 times to
prove reproducibility of the measured results. The obtained results
demonstrate a pseudo-plastic and, in most cases, a tendency of a
thixotropic behaviour of the developed compositions (Fig. 2), which
is favourable in printing and generally in polymer coatings applications.
For talc lled compositions, the obtained curves exhibit
reversible structure changes after increasing and decreasing shear
rate in the analysed interval, demonstrating thixotropic behaviour,
that is of relevance during levelling, draining and pumping [23].
The poorest ability to rebuild the structure after removing shear at
the applied shear conditions is observed for aluminium lled compositions (Fig. 2). Such rheological behaviour can be presumably

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649

Table 2
Water vapour permeability and relative standard error for free lms based on the
developed ink compositions.
Composition

WVPC
(g/m 24 h Pa)

WVPC, barrer

Relative standard
error (%)

Polymer binder
Aluminium, 9 vol.%
Aluminium, 19 vol.%
Aluminium, 26 vol.%
Talc, 8 vol.%
Talc, 17 vol.%
Talc, 26 vol.%
Glass, 10 vol.%
Glass, 19 vol.%
Glass, 26 vol.%

20.2 106
5.75 106
2.34 106
1.57 106
15 106
12.4 106
6.25 106
8.62 106
4.73 106
4.51 106

23.3
6.62
2.70
1.81
17.3
14.3
7.2
9.93
5.45
5.20

1.85
2.35
1.00
0.9
4.26
0.57
0.27
2.96
4.16
2.66

Fig. 2. Viscosity curves with increasing and decreasing shear rate for the developed
ink compositions and unlled polymer dispersion.

caused by a non-uniform corn-ake shape of the particles and their

length/thickness aspect ratio that makes it more difcult for the
particles to adjust their orientation along the ow during shearing.
Incorporation of platelet particles enhances a pseudo-plastic
behaviour of the printing ink compositions during shearing compared to that of non-lled polymer dispersions at low shear rates,
presumably due to the effect of the orientation in the ow during
shearing (Fig. 2). A decrease in viscosity at higher shear rates is
expected to satisfy the desired ow behaviour of the inks during
their application. The achieved viscosity of the developed compositions is supposed to contribute to sufcient adhesion of the
coatings after their application on paper substrates that contributes
to enhanced barrier performance of the printed coatings.
3.2. Structure of coatings
To investigate the structure of the printed coatings prepared
from the developed ink compositions, coatings were applied on
glass substrates by a blade applicator. The coatings applied on glass
served as a model of the coatings obtained by exographic printing
from the developed inks. The thickness of the dry coatings was close
to 10 m that corresponds to the thickness of exographic printed
coatings using the selected combination of an anilox and a printing plate. The obtained coatings were analysed by light microscopy
using conventional and polarised light.
The light microscopy images for polymer coatings containing aluminium akes with different ller content (Fig. 3a and b)
demonstrate a relatively uniform distribution of inorganic particles
inside a polymer matrix. With increasing ller content, particles
tend to locate closer to each other and an overlapping of the
particles increases, thus providing a denser structure. The space
between ller particles, which is occupied by polymer matrix,
decreases (Fig. 3a and b).
Similar tendency was observed for coatings lled with glass
akes and talc. A gradual change in the structure is observed with
increasing ller content for both llers (Figs. 4 and 5). The glass
particles seem to be located closer to the surface demonstrating a
tendency of the coatings to be self-stratied due to a presumably
higher hydrophobicity of the glass akes surface (Fig. 4a and c). Talc
particles are likely to be distributed more uniformly in the coatings
(Fig. 5a and c). The application of polarised light microscopy for
analysis of talc containing polymer coatings provides a possibility
to detect more detailed information regarding the structure of the
coatings due to the anisotropic character of the optical properties
of talc.
To investigate the layered structure of the printed coatings
at the cross-section, a cryogenic fracture surface of free lms at
the cross-section was evaluated with the application of scanning
electron microscopy (SEM). Filled polymer free lms with a similar

thickness of 35 m containing different amount of llers were used

as a model of printed coatings. The structure at the cross-section
of aluminium lled polymer lms is demonstrated in Fig. 6.
Filler particle distribution and the interface between the ller
and the polymer as well as nature of the llers and the polymer
are some of the main factors to consider when designing barrier
functional coatings. The SEM images demonstrate that the platelets
are mostly aligned along the free surface of the lms (Fig. 6). With
increasing ller content, the number of the layers built up by the
ller particles increases. The structure of the layers changes and
becomes more continuous at a higher ller content compared to
lms with a lower ller content (6 vol.%). Layers in the lms with
lower aluminium akes content consist of platelets separated by
polymer (Fig. 6a and b). The distances between the layers are likely
to be similar to each other (Fig. 6c).
The interface between the ller and the polymer (Fig. 6d)
demonstrates a relatively good compatibility of the ller with the
polymer matrix. A strong interface between the ller and the polymer is one of the essential features for barrier performance of
printed coatings. A weak interface would lead to the presence of
microscopic voids in a coating that would cause diffusion of water
molecules through the coatings [24] due to capillary forces.
3.3. Water vapour permeability
Design of a layered structure inside the coatings was expected to
lead to a decrease in water vapour permeability due to formation of
a tortuous path for diffusing molecules inside the polymer matrix
that agrees with [6]. For evaluation of the barrier performance of
the developed printing inks, free lms prepared from the developed
compositions were used as a model of printed coatings, assuming
the same thickness of all the analysed lms. The relative standard
deviation of the experimentally determined values did not exceed
5% (Table 2).
As it was expected, water vapour permeability of the free lms
based on the developed compositions decreased with incorporation of llers in the polymer matrix (Fig. 7). The strongest barrier
effect was observed for the compositions containing aluminium
particles, followed by glass and talc containing printing inks correspondingly. A signicant decrease in water vapour permeability
compared to non-lled polymer lms was observed even at a lower
ller content below 10 vol.% for all the llers. The highest decrease
was observed for aluminium akes containing lms and glass lled
lms (more than 50%), whereas for talc containing compositions
permeability of the lms was reduced for about 20% (Fig. 7).
The effect of the incorporation of llers and of increasing their
content in the ink compositions on barrier performance of the free
lms is demonstrated by relative permeability calculated as a ratio
of permeability for lled polymer lms to that for unlled polymer
lms according to [6,24,25] (Fig. 8).

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Fig. 3. Light microscopy images of polymer coatings lled with aluminium akes at 9 vol.% (a) and 26 vol.% (b) serving as a model for printed coatings.

Fig. 4. Light microscopy images of polymer coatings lled with glass particles at 10 vol.% (a), 19 vol.% (b) and 26 vol.% (c) serving as a model for printed coatings.

As it follows from Fig. 8, water vapour permeability decreases

abruptly with incorporation of aluminium and glass particles in
polymer matrix. This is demonstrated by a sharp decrease in
relative permeability for compositions with changing their ller
content from 0 vol.% to 910 vol.%. Further increase of the ller
content leads to a smoother decrease in permeability. An increase
of the ller content higher than 19 vol.% (up to 26 vol.%) does not
enhance signicantly the barrier effect of aluminium and glass lled
lms. Incorporation of talc results in a gradual decrease of relative
permeability up to a higher ller content of 26 vol.% (Fig. 8).
3.4. Mechanical properties
Improvement in the barrier performance of free lms made
from the developed compositions was correlated with an enhancement of the mechanical properties of the lms. The DMA curves
of free lms demonstrate an increase in storage modulus at the
rubbery plateau with incorporation of llers and with increasing
their content for all types of the applied llers (Fig. 9ac). The glass

transition temperature of the polymer binder is 38 C which is

below the operating temperatures. It slightly changes with incorporation of llers remaining, however, in the negative temperature
region.
Incorporation of the platelet particles in a polymer matrix presumably decreases the degree of freedom of polymer chains that
results in increased modulus at the rubbery plateau (Fig. 9). An
increase in storage modulus at the rubbery plateau is likely to be
associated with a lower mobility of polymer chains and decreased
free volume of the polymer [26]. A decrease in the mobility of polymer chains and a decreased elasticity of the coatings are supposed
to enhance the barrier effect of the coatings. Thus, enhancement
in the mechanical strength of printed coatings is supposed to contribute to the improved barrier properties of the coatings.
Layers of platelet particles tend presumably to suspend a crack
development during formation of a fracture surface, thus contributing to enhanced mechanical strength of the coatings. This
is demonstrated by the structure of lines ending at the locations corresponding to the ller layers at the SEM images of the

Fig. 5. Polarised light microscopy images of polymer coatings lled with talc at 8 vol.% (a), 17 vol.% (b) and 26 vol.% (c) serving as a model for printed coatings.

I.J. Zvonkina et al. / Progress in Organic Coatings 77 (2014) 646656

651

Fig. 6. SEM images of polymer coatings lled with aluminium akes at 6 vol.%, different magnication (a and b), 12 vol.% (c) and interface between aluminium and polymer
(d).

cryogenic fracture cross-section (Fig. 6b). An increased resistance

to mechanical impact improves expectedly the barrier performance
of the printed coatings.
3.5. Surface energy analysis
Surface energy characteristics are expected to affect the barrier
performance of printed coatings. A decrease in hydrophilicity of the

coating surface is supposed to diminish afnity to humidity, thus

it is expected to lead to an enhanced barrier effect.
Surface energy analysis of coatings was performed by measuring
the contact angle of water on the coating surface using the sessile
drop method and its evaluation based on the Owens, Wendt and
Kaeble approach [19,20]. Surface energy analysis was performed
for coatings applied from the ink compositions with different ller
volume content of the llers prepared as described in Section 2.

Fig. 7. Water vapour permeability of unlled and lled polymer free lms serving as a model for printed coatings.

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Fig. 8. Relative permeability of free lms prepared from the developed lled polymer inks.

With incorporation of llers and with increasing their content,

the contact angle of water on the coating surface in most cases
slightly increases, exceeding in all the cases 90 , which is typical
for hydrophobic coatings (Table 3).
Fig. 10 demonstrates polarity of the coating surface calculated as
a ratio between the polar component and the total surface energy
according to [27]. With incorporation of a smaller amount of the
llers (below 10 vol.%), surface polarity slightly increases in case of
talc lled coatings presumably due to a decrease in the coating total
surface energy. For other llers polarity does not change signicantly at lower ller content. With increasing further ller content
higher than 910 vol.%, polarity of the surface mostly decreases in a
more pronounced way (Fig. 10). An exception is given by aluminium
lled coatings with the ller content changing from 19 vol.% to
26 vol.% showing a relatively similar polarity.
3.6. Water uptake
Water vapour permeability of coatings is expected to be related
to the processes of water uptake and swelling of coatings in water.
To evaluate this effect, water uptake tests of free lms were performed. Due to similar thickness of the free lm samples, they can
serve as a model of the respective printed coatings. The amount of
water taken up by free lms made from the developed ink compositions was monitored after specied time intervals as described

Table 3
Free surface energy and water contact angle of coatings applied form the developed
ink compositions.
Composition

Surface energy
(mN/m)

Water contact
angle ( )

Polymer binder
Aluminium, 9 vol.%
Aluminium, 19 vol.%
Aluminium, 26 vol.%
Talc, 8 vol.%
Talc, 17 vol.%
Talc, 26 vol.%
Glass, 10 vol.%
Glass, 19 vol.%
Glass, 26 vol.%

20.85
20.58
21.87
20.59
20.46
20.81
20.71
20.99
21.15
21.01

90.6
91.2
91.4
92.5
91.5
90.6
93
91.3
91.4
93

above (see Section 2). The water uptake results for non-lled polymer lms and for samples with an intermediate ller content of
each type of the lled polymer compositions as a function of the
total immersion time in distilled water are shown in Fig. 11.
The water absorption capability of free lms changes with time
of their immersion in water. An average tendency for water uptake
is shown in Fig. 11. The results demonstrate two stages of water
uptake. At the beginning, the amount of absorbed water increases
abruptly with increasing ller content. At this stage occupation of
pores in the lm by water molecules is supposed to take place that
is driven mainly by micro-capillary forces and by the afnity of
hydrophilic components of the lms to water (Fig. 11). After a sharp
increase, water uptake values come to a plateau corresponding to
the second stage with a slower increase of the amount of absorbed
water. Unlled polymer lms have the highest water uptake; the
compositions lled with aluminium akes have the lowest water
uptake values. The lms based on talc and glass lled compositions are located in between in a decreasing of water uptake order
(Fig. 11).
The process of water uptake by lled and non-lled polymer
lms is supposed to be related to polymer swelling [28]. This can
decrease the lm porosity at the interfaces of the polymer and llers
or in the polymer. The increased due to this pressure at the interface
can lead to expelling of water molecules from the lled polymer
lms. Therefore, water uptake increases sharply at the beginning
of immersion in water and after a certain time interval it can slightly
decrease (Fig. 11). The speed of water uptake is not uniform during
the time of immersion of the lms in water as well, as it follows
from Fig. 11.

3.7. Application of coatings by printing and evaluation of the

printed samples
Based on the evaluation of the properties of the coatings prepared prior to printing, the formulations with the ller content of
19 vol.% for aluminium containing compositions and 26 vol.% for
glass and for talc containing coatings were recommended for printing inks. The selection of the compositions was made considering a
combination of the barrier performance and the mechanical properties. A higher ller content of aluminium (26 vol.%) results in

I.J. Zvonkina et al. / Progress in Organic Coatings 77 (2014) 646656

653

Fig. 9. DMA plots of free lms based on lled and unlled polymer printing ink compositions containing aluminium (a), glass (b) and talc (c) platelets with different ller
content.

a more brittle behaviour as demonstrated by DMA as the value

of the ller content presumably gets closer to CPVC, while it
does not affect signicantly the barrier performance of the lled
coatings. For glass and talc lled coatings the best performance

was achieved using ink compositions with 26 vol.% ller content.

The selected developed printing inks were applied on paper substrates by exographic printing. The procedure, devices and type

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Fig. 10. Polarity of the surface of coatings based on different ink compositions.

of paper substrates in printing application were the same for all

the selected compositions. Viscosity and pH evaluation as well as
the foaming test, described elsewhere [29], were made prior to
printing. Flexographic printing was performed using a printing test
machine Nissha (model S.15) equipped with the selected combination of an anilox roller and a printing plate (see Section 2)
The selection of the anilox roller and printing plate was made
considering the goal to achieve a relatively high thickness and a
uniform surface, which are necessary to achieve improved barrier
performance of the printed coatings.
The developed ink compositions recommended for printing
applications are characterised by improved wetting behaviour on
the selected paper substrates compared to the unlled polymer
composition. Wetting behaviour of the selected paper by the developed inks was evaluated by a contact angle of ink droplets on the

Table 4
Wetting contact angle of the polymer binder and of the developed ink compositions.
Composition

Wetting contact
angle ( )

Relative standard
error (%)

Polymer binder
Aluminium, 19 vol.%
Talc, 26 vol.%
Glass, 26 vol.%

86
79.1
64.9
59.4

1.3
3.3
5.4
4.2

selected paper substrates (see Table 4). Improving wetting is essential to enhance adhesion of the printed coatings to paper and to
avoid or to decrease pinhole formation during exographic printing. This is especially relevant for improving barrier performance
of the printed coatings.

Fig. 11. Water uptake ratio for unlled and lled polymer lms.

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655

Fig. 12. Water vapour permeability of uncoated paper substrates and developed ink compositions containing aluminium, talc and glass llers.

The substrates covered by exographic printed coatings were

analysed with regard to their permeability by water vapour at
the standard conditions. With incorporation of llers the barrier
performance of coatings improved for at least 70% for aluminium
containing printed coatings (19 vol.% of aluminium) and for 60%
for talc and glass containing printed coatings (26 vol.% of llers)
compared to uncoated paper (Fig. 12).
The results obtained in the tests agree with the tendency
observed for decreasing water vapour permeability for unlled and
lled polymer free lms prepared from the developed ink compositions (Figs. 7 and 8). Both tests demonstrate an improvement
in the barrier performance of polymer lms with incorporation of
the selected llers. The best barrier performance was achieved for
aluminium lled inks.
Evaluation of thickness of the paper substrates coated by the
printed inks demonstrated that a relatively high volume of the
applied compositions was transferred using the selected anilox
roller and the printing plate. The proposed combination of the
anilox roller and the printing plate provided a possibility to
obtain relatively even coatings with thickness exceeding 20 m for
2236% by exographic printing.

4. Conclusions
New exographic inks were developed based on acrylic polymer dispersion with incorporation of inorganic llers consisting of
platelet particles. The different types of llers introduced in the
polymer matrix provide an enhanced barrier effect to the printed
coatings and contribute to different mechanical, optical and other
properties of the coatings. The design of the developed materials
provides a layered structure of the coatings with a relatively good
distribution of particles in the polymer matrix.
Water vapour permeability of free lms serving as a model of
coatings decreased signicantly with incorporation of llers and
with increasing their content in the polymer matrix. An increased
barrier effect of the coatings is associated with an enhanced
mechanical strength, a slightly decreased polarity of the coating
surface at certain ller content and with other physicalmechanical
properties of the coatings applied from the developed inks.

The developed inks were applied on the selected paper substrates by laboratory exographic printing. Incorporation of llers
in the polymer binder at certain content led to a slightly improved
wetting of the paper substrates that is of relevance in a printing
process. The substrates covered by printed coatings demonstrated
a decreased permeability of water vapour at standard conditions.
The proposed new environmentally friendly inks contribute to
the development of packaging materials with improved barrier
performance, achieved by application of the developed printed
coatings with decreased water vapour permeability.
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