coatings

Article
Stability of Aqueous Polymeric Dispersions for
Ultra-Thin Coating of Bi-Axially Oriented
Polyethylene Terephthalate Films
Petr Smolka 1,2, *, Lenka Musilová 1,2 , Aleš Mráček 1,2 ID
and Tomáš Sedláček 2
1 Department of Physics and Materials Engineering, Faculty of Technology, Tomas Bata University in Zlín,
76001 Zlín, Czech Republic; lmusilova@utb.cz (L.M.); mracek@utb.cz (A.M.)
2 Centre of Polymer Systems, Tomas Bata University in Zlín, 76001 Zlín, Czech Republic; sedlacek@cps.utb.cz
* Correspondence: smolka@utb.cz; Tel.: +420-576-035-102

Academic Editor: Stefano Farris

Received: 24 August 2017; Accepted: 12 December 2017; Published: 16 December 2017

Abstract: The stability of polyacrylate and polyester based aqueous dispersions designed for ultrathin
coating of extruded plastic films, especially bi-axially oriented polyethylene terephthalate (BOPET),
was studied. Also, the effect of the gemini surfactant based defoaming/wetting agent on the
properties of the dispersions was examined. The addition of the defoaming/wetting agent resulted
in reducing the surface free tension of the polyacrylate and polyester dispersion by 15% and 20%,
respectively and the initial foam height by 60% and 15%, respectively. At the same time, the agent
addition did not compromise the temperature and pH stability of the dispersions. Such modified
dispersion can be utilized for ultrathin coating of plastic film used for packaging, to improve their
processability, printability, and metallization.

Keywords: ultra-thin films; coating; polymeric dispersion; water based

1. Introduction
Plastics have long ago become common packaging materials. They are used to protect products
like food, pharmaceuticals, medical products, cosmetics, electronics, and many others [1]. Namely in
the food manufacturing process, packaging of the product is one of the most important steps, as it
maintains the quality of food for storage, transportation, and end use [2]. A single-layer plastic material
is usually not capable of fulfilling all the requirements of all the processes in the manufacturing chain,
thus multilayer flexible films are produced, mainly by in-line coating, lamination, coextrusion, etc. [3].
Coated plastic films provide many advantages over the standard material—e.g., resistance against
high temperatures—which in turn allows their usage in the pasteurization and sterilization processes.
Moreover, a coating can improve antibacterial and barrier properties (oxygen and vapor transmission
rates), lower the coefficient of friction, allow metallization of the film, etc. Another reason for
coating the substrate is bringing its surface free energy closer to the surface tension of printing inks
(reprographic, flexographic, photosensitive, . . . ), improving adhesion for lamination or making the
surface antistatic. Recently, many different chemical compositions have been used for coating extruded
plastic films. The film forming compound of such composition (polymeric dispersion) is usually
polyester, polyurethane, or polyacrylate resin and the dispersed phase is often chemically and/or
sterically stabilized. The thin film coating process can be substituted with corona treatment, to increase
the substrate surface free energy. Such an approach is demanding though, because of high initial cost
and process complications (possible electric interference with other equipment in the production line
and the maintenance cost). Besides, corona treated polymer surfaces are known to suffer from so called
“aging” of the treatment, a gradual reversal of the surface properties towards those of the untreated

Coatings 2017, 7, 234; doi:10.3390/coatings7120234 www.mdpi.com/journal/coatings

Coatings 2017, 7, 234 2 of 10

surface. Aging is known to be accelerated by elevated temperature and moisture and occurs with most
plasma treatment processes [4–10].
The coating process of typical polymeric foils (polyethylene, polypropylene, and even
polyethylene terephthalate) also meets with difficulties such as poor wetting of the substrate with the
dispersion (when the surface tension of the dispersion is relatively high with respect to the surface
free energy of the substrate to be coated). The dispersions themselves can perform well, however in
industrial conditions (gravure cylinder coating at high rate) their foaming can be a problem, as it can
compromise the surface properties of the final thin film on a substrate. Various additives can be used to
overcome such problems, though they should not compromise the properties of the initial dispersion,
namely its stability. This article gives information on modifying the properties of polymer dispersions
that can be used for ultra-thin coating of biaxially-oriented films and the effect of the additive on
the properties of the dispersions. Promoted adhesion of the substrate can significantly improve the
performance of further conversion steps (metallization, SiOx , and AlOx coating) and lamination with
other materials as BOPP, PE, aluminium foil, etc. and help in formulation of new advanced packaging
materials [1,11]. Namely in the case of BOPET, it is almost impossible to perform metallization of the
foil without proper pre-treatment with a suitable thin film.

2. Materials and Methods

2.1. Solution Preparation

Co-polyester polymer aqueous dispersion Eastek™ 1200 (Eastman, Kingsport, TN, USA),
referred to as Co-PES further in the text, and acrylic polymer aqueous dispersion PRIMALTM
AC-261 (Dow, Midland, MI, USA), referred to as ACR further in the text, were examined in the
means of particle size (z-average) temperature and pH dependence, zeta potential temperature and
pH dependence, surface free tension (SFT), foam forming, and stability. The testing solution was
prepared by mixing the concentrated polymeric dispersion with deionized water so that the total
solid content was approximately 6 wt.%, followed by homogenization with Teflon® coated magnetic
stirrer (VWR International, Randor, PA, USA) for 15 min. Fresh solution was prepared prior to each
measurement to avoid gel formation. Modified testing solutions were prepared by adding given
amount of the defoaming/wetting agent (2,4,7,9-tetramethyl-4,7-decanediol) (Air Products, Allentown,
PA, USA), designated as Agent 1 further in the text, followed by homogenization with a Teflon® coated
magnetic stirrer for 5 min.

2.2. Surface Tension Measurement

The critical aggregation concentration (CAC) and critical micellar concentration (CMC), of the
gemini surfactant in polymeric dispersion were determined from equilibrium surface tension
measurements as a function of surfactant concentration at 25 ◦ C. The surface tension of the solutions
was measured by the Wilhelmy plate method with the K100MK3 automatic tensiometer (Krüss GmbH,
Hamburg, Germany), with the platinum plate at 25 ◦ C. The tensiometer sample chamber was connected
to the thermostat (Termostat CC-308B Pilot Huber, Offenburg, Germany), to maintain the desired
temperature. Where appropriate (surface tension dynamics), the solution was stirred prior to each
measurement for 30 s with a clean glass rod and the measurement itself was initiated within the 30 s
period starting from the point when the stirring had finished. For each solution, at least three separate
measurements were performed.

2.3. Particle Size and Zeta Potential Measurement

The z-average (mean hydrodynamic diameter), zeta potential, and their temperature and pH
dependencies were measured by dynamic light scattering method (DLS) with the Zetasizer Nano ZS
(Malvern Instruments, Malvern, UK), coupled with the MPT-2 automatic titrator (Malvern Instruments,
Malvern, UK). The scattered light was observed at a 173◦ angle. The disposable folded capillary cell
Coatings 2017, 7, 234 3 of 10

(Malvern Instruments, Malvern, UK) was used for the z-average and zeta potential measurement.
Each presented value is the average of five measurements with different samples.

2.4. Foam Forming

The formation of foam was measured with polymeric dispersions prepared according to the
Section 2.1, modified with 0–0.517 wt.% of Agent 1. Then, 50 mL of modified solution was transferred
into the 250 mL graduated cylinder covered with Parafilm M® (Bemis Company, Inc., Oshkosh, WI,
USA), the cylinder was agitated with both hands for 30 s and the height of the generated foam was
recorded in time intervals 0, 5, and 30 min.

2.5. Thin Film Coating

The BOPET polymeric substrates (FATRA) with the thickness of 50 and 12 µm were used
for the laboratory and industrial scale testing, respectively. The coating of the BOPET polymeric
substrates with Co-PES and ACR dispersions was performed with an adjustable Baker Film applicator
3525 (Elcometer Ltd., Manchester, UK) on the laboratory scale and also in the industrial scale in
a professional production line with a gravure coating cyllinder (Brückner Group GmbH, Siegsdorf,
Germany) at the cooperating company (Fatra A. S., Napajedla, Czech Republic). In the laboratory
scale, the substrates were pre-treated with low temperature plasma, prior to dispersion coating.
The treatment was performed in the commercial Diener PICO plasma apparatus (Diener electronic,
Ebhausen, Germany), with capacitive radiofrequency coupling at the frequency 13.56 MHz and
pressure 0.4 mbar. The following procedure was utilized: The substrates were placed inside the
plasma chamber, then the vacuum pump was activated and after 5 min the chamber was purged
with pure air at 10 sccm for another 5 min to minimze the effect of contaminants possibly present
in the chamber. Subsequently, while the air flow was adjusted to 10 sccm, the glow discharge was
initiated. The forward power was set to 100 W and the reflected power was kept under 10%. In the
industrial process, the pre-treatment was performed with the corona discharge unit built directly in
the production line.

2.6. Thin Film Characterization

The surface of coated and uncoated substrates were analyzed with a scanning electron microscope
(SEM) Phenom Pro (Phenom-World B.V., Eidhoven, The Netherlands) in the environmental mode
(Phenom-World). The surface free energy of the coated and uncoated substrates was determined with
the non-toxic testing inks (Arcotest GmbH, Moensheim, Germany).

3. Results and Discussion

3.1. Surface Tension of Pure and Modified Dispersions

Surface tension of pure ACR and Co-PES dispersions was measured. The data in Figure 1 suggest
a similar trend for both pure dispersions—decent drop of the surface tension value over the 180 s period.
Pure ACR and Co-PES dispersion start at approx. 44 mN/m and 52 mN/m, respectively. Very similar
data were obtained for solutions aged for 24 h at 40 ◦ C. From the SFT point of view, both dispersions
remain stable enough over the typical processing period (preparation of dispersion—short-term
storage—coating), even at elevated temperatures.
In order to improve wetting properties, the ACR and Co-PES dispersions were modified with
the Agent 1. The dependencies of surface tension versus surface active agent concentration show
two breaks—at approx. 0.14 wt.% and 0.40 wt.%—which were attributed to the critical aggregation
concentration and critical micellar concentration, respectively, of Agent 1 (Figures 2 and 3). The trend
of curves seems to be unaffected by the chemical nature of dispersions and Agent 1 is highly efficient
already at low concentrations. The addition of 0.14 wt.% provides reduction of SFT value by 15% and
20% for ACR and Co-PES dispersion, respectively, which is favorable for the thin-film coating process.
Coatings 2017, 7, 234 4 of 10

Coatings 2017, 7, 234

The Agent 1 (as a representative of gemini surfactants) contains two hydrophilic and hydrophobic part
withinwithin
one single
Coatings 2017, 7, molecule,
234
one single thus
molecule, itsitssurface
thus surfaceactive properties(efficiency
active properties (efficiency and
and effectivity)
effectivity) are remarkably
are remarkably
betterbetter
than than
would wouldbe with their
be with single
their singlehydrophilic/hydrophobic analogues
hydrophilic/hydrophobic analogues [12–14].
[12–14].
within one single molecule, thus its surface active properties (efficiency and effectivity) are remarkably
better than would be with their single hydrophilic/hydrophobic analogues [12–14].

Figure 1. Surface tension time dependence of ACR and Co-PES dispersions; fresh and aged for 24 h at 40 °C.
Figure 1. Surface tension time dependence of ACR and Co-PES dispersions; fresh and aged for 24 h at
◦ C. 1. Surface tension time dependence of ACR and Co-PES dispersions; fresh and aged for 24 h at 40 °C.
40 Figure

Figure 2. Surface tension of ACR dispersion vs. surface active additive (Agent 1) concentration.

Figure 2. Surface
Figure tension
2. Surface of ACR
tension dispersion
of ACR dispersionvs.
vs. surface activeadditive
surface active additive (Agent
(Agent 1) concentration.
1) concentration.

Figure 3. Surface tension of Co-PES dispersion vs. surface active additive (Agent 1) concentration.

Figure 3. Surface tension of Co-PES dispersion vs. surface active additive (Agent 1) concentration.
Figure
3.2. 3. Surface
Particle Size andtension of Co-PES
Zeta Potential dispersion
of Pure vs. surface active additive (Agent 1) concentration.
Dispersions
3.2. Particle Size and Zetawith
The measurement Potential
pure of Pure Dispersions
dispersions at the temperature 25 °C revealed the z-average value
3.2. Particle
of (144 Size andand
± 4) nm Zetazeta
Potential of value
potential Pure Dispersions
of (−20.0 ± 0.6) mV for the ACR dispersion. With the Co-PES
The measurement with pure dispersions at the temperature 25 °C revealed the z-average value
The measurement ◦ C revealed the z-average value of
of (144 ± 4) nm and with pure dispersions
zeta potential at the± 0.6)
value of (−20.0 temperature
mV for the25
ACR dispersion. With the Co-PES
4
(144 ± 4) nm and zeta potential value of (−20.0 ± 0.6) mV for the ACR dispersion. With the Co-PES
the values were (15.0 ± 0.1) nm and (−39.0 ± 1.0) 4 mV, respectively. These numbers (namely the
Coatings 2017, 7, 234 5 of 10
Coatings 2017, 7, 234

the values were (15.0 ± 0.1) nm and (−39.0 ± 1.0) mV, respectively. These numbers (namely the zeta-
zeta-potential value)
Coatings 2017,
correspond with the practical experience, where the Co-PES dispersion remains
7, 234 correspond with the practical experience, where the Co-PES dispersion remains
potential value)
ratherrather
stable during storage and ultra-thin film coating, while the ACR dispersion shows the
stable during storage and ultra-thin film coating, while the ACR dispersion shows the
tendency towards
the values
tendency were
towardsgelation
(15.0 of the
± 0.1)
gelation nm
of stock
theand solution
(−39.0
stock ± 1.0)with
solution prolonged
mV, prolonged
with respectively.storage and/or
Theseand/or
storage numbers exposure
(namely
exposure to thetozeta-
elevated
elevated
potential
temperatures value)
in the correspond
coating with
process. the
In practical
the Figure experience,
4, the where
z-average the Co-PES
temperaturedispersion
temperatures in the coating process. In the Figure 4, the z-average temperature dependence of both remains
dependence of both
rather
systems stable during storage and ultra-thin film coating, while the ACR dispersion shows
systems is shown. The Co-PES dispersion exhibits similar stability in the observed temperature rangerange
is shown. The Co-PES dispersion exhibits similar stability in the observed temperature the
tendency
(except thetowards gelation
fluctuations of the
in the stockfrom
interval solutiontowith
10to prolonged
20 ◦°C), storage and/or exposure to elevated
(except the fluctuations in the interval from 10 20 C),as
asthe
theACR
ACR dispersion.
dispersion.
temperatures in the coating process. In the Figure 4, the z-average temperature dependence of both
systems is shown. The Co-PES dispersion exhibits similar stability in the observed temperature range
(except the fluctuations in the interval from 10 to 20 °C), as the ACR dispersion.

Figure4.4. z-average
Figure z-averagetemperature
temperature dependence
dependence of ACR of dispersion
ACR dispersion(squares)(squares)
and Co-PESanddispersion
Co-PES(triangles).
dispersion
(triangles).
The zeta potential temperature and pH dependencies of both systems are shown in the Figures 5 and 6,
Figure 4. z-average
respectively. As can temperature
be seen, the dependence of ACRdrops
zeta potential dispersion (squares) with
continuously and Co-PES dispersion
increasing (triangles).
temperature for
The
the ACR dispersion, though for the Co-PES dispersion it reaches a plateau at about 30 °C.shown
zeta potential temperature and pH dependencies of both systems are The totalin the
FigureschangeTheofzeta
5 and potential
6,zeta
respectively.
potentialtemperature
isAs canand
about bepH
12–15 dependencies
seen,
mVthe of both systems
zetainterval
in the potential °Care
5–50drops inshown in the Figures
continuously
both systems, with
though5 and 6,
increasing
the
respectively.
temperature
absolute for value As
theforcan
ACR be seen, the
the dispersion, zeta
Co-PES dispersion potential
though drops
for above
stays continuously
the Co-PES−30 mVdispersion with increasing
it reaches
at 50 °C (stable) temperature
whilea for
plateau
the ACR for
at about
the ACR dispersion, though−15 for
mVthe Co-PES dispersion it reaches a plateau at elevated
about ◦30temperatures
30 ◦ C.dispersion,
The totalitchange approaches of zeta at 50
potential °C.is The
aboutACR dispersion
12–15 mV in is the
less stable at
interval 5–50 C°C. The total
in both systems,
change ofshould
zeta potential is about the 12–15 mV in the interval 5–50example
°C in both systems, though the
though and this
the absolute be
value considered
for the in Co-PES coating process
dispersion setupabove
stays (for −30 mV at 50 ◦ Ccooling
additional (stable) ofwhile
the for
absolute
stock value
container, for
if the
the Co-PES
excess dispersion
dispersion fromstays
the above
gravure
◦
−30 mV
cylinder at 50 °C
refluxes(stable)
there). while
From for
the the
pH ACR
point
the ACR dispersion,
dispersion, it approaches
it approaches −15 −50
15°C.
mVThe at ACR
50 C. The ACR dispersion is less stable at elevated
of view, on the other hand, themVACR at dispersion keeps dispersion is less
its zeta potential stable
valueatdown
elevated temperatures
to pH 7 and then
temperatures and
and this should this should be considered in the coating process setup (for example additional
increases slowly be (IEP considered
about pH in 4) the coating
whereas theprocess
Co-PES setup (for example
dispersion additional
exhibits abrupt cooling
change of
already the
at
coolingstockof the stock
container, if container,
the excess if the
dispersion excess
from dispersion
the gravure from
cylinder the gravure
refluxes cylinder
there). From therefluxes
pH point there).
pH 8 and the IEP is approached around pH 7.
From of theview,
pH onpoint the of view,
other hand,on the
theACRotherdispersion
hand, thekeeps ACRitsdispersion
zeta potential keeps itsdown
value zeta potential
to pH 7 and value
thendown
to pHincreases
7 and then slowly (IEP about
increases pH 4)(IEP
slowly whereas
about thepHCo-PES dispersion
4) whereas the exhibits
Co-PESabrupt changeexhibits
dispersion already at abrupt
pH 8 and the IEP is approached around
change already at pH 8 and the IEP is approached around pH 7. pH 7.

Figure 5. Zeta potential temperature dependence of ACR dispersion (squares) and Co-PES dispersion (triangles).

5
Figure
Figure5. Zeta
5. Zeta potential
potential temperature
temperature dependence
dependence of ACR
of ACR dispersion dispersion
(squares) (squares)
and Co-PES dispersionand Co-PES
(triangles).
dispersion (triangles).
5
Coatings 2017, 7, 234

Coatings 2017, 7, 234 6 of 10

Coatings 2017, 7, 234

Figure 6.6.Zeta
Figure
Figure Zetapotential
6. Zeta pH
potential pH
potential dependence
pH dependenceof
dependence ofofACR
ACR dispersion
ACR dispersion (squares)
(squares)
dispersion (squares) and
and
and Co-PES
Co-PES
Co-PES dispersion
dispersion
dispersion (triangles).
(triangles).
(triangles).

3.3. Particle
3.3. Particle Size
3.3. Particle and
Size Size Zeta
and and Potential
ZetaZeta of ofModified
Potential
Potential of Modified Dispersions
ModifiedDispersions
Dispersions
The concentration
The concentration
concentration and andchemical
chemical structure
structure of used
used defoaming/wetting
of defoaming/wetting
defoaming/wetting agent can have have
agent a
The and chemical structure of used agent can have can
a significant a
significant
significant influence
influence on on particle
particle size
size and
and its
its distribution,
distribution, viscosity,
viscosity, dispersion
dispersion stability, or
stability, film
or film
influence on particle
formation. size and
Therefore, the its distribution,
particle size and viscosity,
zeta potential dispersion stability,
measurements or film
were formation.
performed. BasedTherefore,
on
formation.
the particle Therefore,
size and thepotential
zeta particle measurements
size and zeta potential
were measurements
performed. Based were
on the performed.
SFT Based on
measurements of
the SFT measurements of polymeric dispersions with various concentrations of surface active
the SFT
polymeric measurements
dispersions
additive, the optimal withof polymeric dispersions
various concentrations
concentration of Agent 1 was
with
of surface various
selectedactive
for the
concentrations
additive,
ACR and the of
optimal
Co-PES
surface active
concentration
dispersions
additive,
of Agent the
1 wasoptimal
modification, selectedconcentration
as describedforinthethe ACR of Agent
Sectionand 1 was
Co-PES
3.1. Based selected
dispersions
on those for modification,
the ACR
measurements, and Co-PES
the optimal dispersions
asconcentration
described in the
modification,
was as
defined described
as 0.14 wt.%in the
of Section
the Agent 3.1.
1. Based
Then, theon those
same measurements,
dependencies
Section 3.1. Based on those measurements, the optimal concentration was defined as 0.14 wt.% of as for the
pure optimal concentration
dispersions were
wasAgent
the defined 1. as
measured. 0.14z-average
The
Then, wt.%
the of the
same Agent 1.dependence
temperature
dependencies Then,as for thepure
same
(Figure dependencies
7) is similar
dispersions toas
were forofpure
that puredispersions
measured. dispersions,
The z-averagewere
exceptThe
measured. that z-average
there are notemperature
fluctuations atdependence
low temperatures, (Figure suggesting
7) is that the
similar to stability
that of of the dispersions,
pure system
temperature dependence (Figure 7) is similar to that of pure dispersions, except that there are no
exceptcould
thateven
fluctuations there beare
at low
improved by modification
no fluctuations
temperatures, at lowwith
suggesting
the surface active
temperatures,
that the stability
agent. that the stability of the system
suggesting
of the system could even be improved
could From the
even be improved zeta potential
by point of
modification view, the situation is different,
with the surface active agent. as in Figure 8. The zeta potential
by modification with the surface active agent.
values of the ACR and Co-PES dispersions drop almost to zero at temperatures approaching 40 °C.
From the
From the zeta
zeta potential
potential pointpoint ofof view,
view, thethe situation
situation is is different,
different, as as in
in Figure
Figure 8.8. The
The zeta
zeta potential
The ACR dispersion keeps the −10 mV value by the temperature of about 30 °C, while with the potential
Co-
valuesPES
values of dispersion
of the ACR
the ACR and and Co-PES
Co-PES
a rapid drop of
dispersions
dispersions
zeta potential
drop
drop does
almost
almost to
to zero
not occur zero at temperatures
temperatures
untilatabout 37 °C. These
approaching
approaching 40 °C.
observations40 C.
◦
The ACR
The ACR dispersion
dispersion
should keeps
be kept keeps
in mind the
thewhen −10
−10 mV mV value
value by
designing by
an the the temperature
temperature
industrial of about
processofinvolving
about 30 such 30
◦ °C, while
C, while with
with the
dispersions withthe Co-
Co-PES
PES dispersion a
defoaming/wettingrapid drop
agent of
and zeta
proper potential
measures does
should notbe occur
applied until
(e.g.,
dispersion a rapid drop of zeta potential does not occur until about 37 C. These observations shouldabout
◦
cooling 37
the °C. These
stock observations
dispersion, as be
should be kept
mentioned in mind
above). The when
pH designing
stability at 25 °C, an
on industrial
the other process
hand, remains involving
kept in mind when designing an industrial process involving such dispersions with defoaming/wetting almost such
unchanged, dispersions
Figure 9. with
defoaming/wetting
agent agent and
and proper measures proper
should bemeasures
applied (e.g.,should be applied
cooling the stock(e.g., cooling the
dispersion, asstock dispersion,
mentioned as
above).
mentioned
The above).
pH stability at The pHon
25 ◦ C, stability
the otherat 25 °C, on
hand, the other
remains hand,
almost remains almost
unchanged, Figureunchanged,
9. Figure 9.

Figure 7. z-average temperature dependence of modified ACR dispersion (squares) and Co-PES dispersion (triangles).

6
FigureFigure 7. z-average
7. z-average temperature
temperature dependence
dependence of modifiedofACR
modified ACR
dispersion dispersion
(squares) (squares)
and Co-PES and Co-PES
dispersion (triangles).
dispersion (triangles).

6
Coatings 2017, 7, 234 7 of 10
Coatings 2017, 7, 234

Figure 8. Zeta
Figure 8. Zeta potential
potential temperature
temperature dependence
dependence of
of modified
modified ACR
ACR dispersion
dispersion (squares)
(squares) and
and Co-PES
Co-PES
dispersion (triangles).
dispersion (triangles).

Figure 9. Zeta
Figure 9. potential pH dependence
Zeta potential of modifiedof
pH dependence ACR dispersion
modified ACR(squares) and Co-PES
dispersion dispersion
(squares) (triangles).
and Co-PES
dispersion (triangles).
3.4. Foam Forming
3.4. Foam
FoamingForming
of both polymeric dispersions was determined as a function of defoaming/wetting
agentFoaming
concentration
of both and time. Thedispersions
polymeric results for ACR dispersion (Figure
was determined 10a) show
as a function higher value of the
of defoaming/wetting
foam height of pure ACR dispersion, compared to pure Co-PES
agent concentration and time. The results for ACR dispersion (Figure 10a) show higher dispersion (Figure 10b).of The
value the
foaminess of ACR is 2.6 times higher than for Co-PES. The foam height of
foam height of pure ACR dispersion, compared to pure Co-PES dispersion (Figure 10b). The foaminesspure ACR dispersion was
around
of ACR (108.0
is 2.6 ±times
4.0) mm.
higherThethan
first addition
for Co-PES.of Agent 1 caused
The foam lowering
height of pureof foam
ACR height to (40.0
dispersion ± 0.5)
was mm,
around
i.e., more than 60%. As can be seen in the Figure 10a, the foaming of ACR
(108.0 ± 4.0) mm. The first addition of Agent 1 caused lowering of foam height to (40.0 ± 0.5) mm, i.e.,decreases markedly
between
more than0.02
60%.andAs 0.08
can be wt.%
seenconcentration
in the Figure 10a,of thetheAgent
foaming1 (close
of ACR todecreases
the CACmarkedly
value). Whenbetweenthe
concentration of Agent 1 is close to the CMC, the foam height reaches a plateau.
0.02 and 0.08 wt.% concentration of the Agent 1 (close to the CAC value). When the concentration of
AgentSimilar results
1 is close to thewere
CMC,observed
the foam for Co-PES,
height reachesFigure 10b. The foam height of pure Co-PES
a plateau.
dispersion
Similarwas around
results were(41.0 ± 3.0) for
observed mm. The first
Co-PES, addition
Figure of Agent
10b. The foam1height
caused oflowering of foam
pure Co-PES height
dispersion
to (35.0 ± 0.1) mm, i.e., about 15%. When the concentration of Agent
was around (41.0 ± 3.0) mm. The first addition of Agent 1 caused lowering of foam height 1 exceeded the Agent 1 CACto
(0.14 wt.%), again the plateau was reached.
(35.0 ± 0.1) mm, i.e., about 15%. When the concentration of Agent 1 exceeded the Agent 1 CAC
(0.14 These
wt.%),results
again theindicate
plateauthatwas
Agent 1 can work as defoamer for both ACR and Co-PES dispersions,
reached.
thoughThese results indicate that Agent 1profound
the direct impact will be more can workin asthe acrylic for
defoamer dispersion.
both ACR and Co-PES dispersions,
though the direct impact will be more profound in the acrylic dispersion.

7
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Coatings 2017, 7, 234 8 of 10
Coatings 2017, 7, 234

Figure 10. Foam height time dependence of the ACR dispersion (a), and Co-PES dispersion (b) with
Foam height time
Figure 10.concentrations
different of thedependence
Agent 1. of the ACR dispersion (a), and Co-PES dispersion (b) with
Figure 10. Foam height time dependence of the ACR dispersion (a), and Co-PES dispersion (b) with
different concentrations of the Agent 1.
different concentrations of the Agent 1.
3.5. Thin Film Coating and Characterization
3.5. Thin Film Coating and Characterization
3.5. Thin
The Film Coating
coating in theandlaboratory
Characterization
scale was performed solely for the purpose of determination
The the
whether coating in the laboratory scalesubstrate
was performed solely for be
thesuitable
purposeforof determination whether
The coating in the laboratory scale was and
dispersions will wet the thus
performed would
solely for the purpose the industrial process.
of determination
the dispersions
Figure 11the will
displays wet the
the surface substrate
of the
virginand thus would
and ACR be suitable for the industrial process. Figure 11
whether dispersions will wet substrate and dispersion
thus wouldcoated substrates.
be suitable for theAs can be seen,
industrial the
process.
displays the surface
manual of virgin a and ACR dispersion coated substrates.layer.
As can
In be
theseen, the manual coating
Figure 11coating
displaysprovides
the surface relatively
of virginthick
and (up
ACRtodispersion
10 microns) coated substrates. case
As of
can thebeindustrial
seen, the
provides the
process, a relatively
layer is thick
so (up (partly
thin to 10 microns)
becauselayer.
of In the
the thincase of the
liquid industrial
layer depositedprocess,
with the
thelayer is so
gravure
manual coating provides a relatively thick (up to 10 microns) layer. In the case of the industrial
thin (partly
cyllinder because
andlayer
also dueof the thin liquid layer deposited with the gravure cyllinder and also due to the
process, the is sotothinthe (partly
biaxial because
stretching—the
of the thin dispersion
liquid is deposited
layer deposited before
withthethetransverse
gravure
biaxial stretching—the
direction orientation dispersion
takes place), isitdeposited
can before
hardly the transverse
be analyzed with direction
any otherorientation
methodthe takessurface
than place),
cyllinder and also due to the biaxial stretching—the dispersion is deposited before transverse
it can
tension hardly be
measurementanalyzed with
(eitherplace),any other
inks oritsessile method than
drop method). surface
Testingtension
theany measurement
substrate (either
with ink than inks
revealed or
the
direction orientation takes can hardly be analyzed with other method surface
sessile drop energy
surface method). of Testing the
42,substrate with
mJ·ink revealed the surfaceACRfree energy of approx. 42,Co-
40,
tension free approx.inks 40,sessile
and 62 m for virgin BOPET, coated
withBOPET, and
−2
measurement (either or drop method). Testing the substrate
−2 for virgin BOPET, ACR coated BOPET, and Co-PES coated BOPET, respectively.
ink revealed the
PES 62 mJ·m
and coated BOPET, respectively.
surface free energy of approx. 42, 40, and 62 mJ·m−2 for virgin BOPET, ACR coated BOPET, and Co-
PES coated BOPET, respectively.

(a) (b)

Figure (a) (b) substrates.

Figure 11.
11. SEM
SEM images
images of
of the
the virgin
virgin (a)
(a) and
and laboratory
laboratory ACR
ACR coated
coated (b)
(b) substrates.
Figure 11. SEM images of the virgin (a) and laboratory ACR coated (b) substrates.
4. Conclusions
4. Conclusions
4. Conclusions
The effect of the gemini surfactant based defoaming/wetting agent on the properties of aqueous
The effect of the gemini surfactant based defoaming/wetting agent on the properties of aqueous
acrylic
Theand polyester
effect dispersions
of the gemini was studied.
surfactant The dispersions were
based defoaming/wetting examined
agent from the perspective
on the properties of aqueous
acrylic and polyester dispersions was studied. The dispersions were examined from the perspective
of surface
acrylic tension,
andtension, particle
polyester size,
dispersions zeta-potential, and
was studied. The foaming. Pure ACR and Co-PES dispersion were
of surface particle size, zeta-potential, and dispersions were
foaming. Pure examined
ACR fromdispersion
and Co-PES the perspective
were
of surface tension, particle size, zeta-potential, and foaming. Pure ACR and Co-PES dispersion were
8
8
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found to have the SFT about 44 mN/m and 52 mN/m, respectively and kept this value relatively well
when aged for 24 h at both 25 ◦ C and 40 ◦ C. The addition of 0.14 wt.% of Agent 1 reduces the SFT value
by 15% and 20% for ACR and Co-PES dispersion, respectively, which is favorable for the thin-film
coating process. Taking the above-mentioned into account, the modified dispersions will provide
better wetting of a substrate without the need for its surface treatment and will withstand short-term
storing even at mildly elevated temperatures. On the other hand, according to the data obtained
from the z-average and zeta-potential measurements, prolonged storage and/or exposure to elevated
temperatures in the coating process can possibly bring problems with gelation in the case of ACR
dispersion. The Co-PES dispersion is expected to perform better in such conditions. Besides better
wetting, the addition of the Agent 1 is defoaming the dispersions significantly, though its effect is
more obvious in the ACR dispersion than in the Co-PES dispersion (initial foam reduction 60% and
15%, respectively). Such modified dispersion can be utilized for Co-PES ultrathin coating of plastic
film (especially BOPET) used for packaging, to improve their processability, printability, metallization,
and barrier properties.

Acknowledgments: This article was written with the support of the Operational Program Research and
Development for Innovations co-funded by the European Regional Development Fund (ERDF) and the national
budget of the Czech Republic, within the framework of the project Center of Polymer Systems (reg. number:
CZ.1.05/2.1.00/03.0111). This work was also supported by the Ministry of Education, Youth and Sports of the Czech
Republic—Program NPU I (LO1504), the European Regional Development Fund (Grant No. CZ.1.05/2.1.00/19.0409).
The research was performed in collaboration with the industrial partner Fatra, a. s., Czech Republic.
Author Contributions: Petr Smolka conceived and designed the experiments and wrote the paper;
Lenka Musilová performed the experiments and performed data evaluation; Aleš Mráček performed data
evaluation and literature research; Tomáš Sedláček contributed the materials and analytical apparatus.
Conflicts of Interest: The authors declare no conflict of interest. The founding sponsors had no role in the design
of the study; in the collection, analyses, or interpretation of data; in the writing of the manuscript, or in the
decision to publish the results.

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