Applications I Labelling and Packaging
Waterborne Pressure
Sensitive Adhesives for Clear
Filmic Labels and Graphics
The label and packaging industry is constantly looking for innovative ways to improve the look
of a label and/or packaging. With ever stricter environmental standards and regulations, as well as
consumers’ increasing awareness of sustainability and environmental responsibility, the search for
green and environmentally friendly products is becoming a key task for the label and packaging
industry.
Olga Bernatova
The history of adhesives goes back a
long way. About 200,000 years ago, stone
tools were bound to wooden handles
with natural materials such as tar from
birch bark /1, 2/. Pressure-sensitive ad-
hesives (PSAs), however, were only dis-
covered and used by the surgeon Hor-
ace Day in 1845 /3/. He made the first
crude surgical adhesive tape and used it
in his practice.
While the history of label was dated from
17th century, the first label was simply a
hand-written parchment attached to a
wine bottle with string. Label with adhe-
sives became common in the 18th century
and was mainly used in the wine and food
trading industries. Natural materials such
as starch, natural rubber, casein etc. were
mainly used as adhesives for paper labels
on packaging boxes, bottles and cans. The
printing and labeling industry developed
significantly in the 19th century, expand-
ing its usage into postal service and phar-
maceutical.
Beginning of 20th century, PSAs became
commonly used as adhesives for produc-
tion of self-sticky labels. Such materials
perform well on different kind of sub-
strates (glass, paper, wood, metal and
later on also on plastics). Today the var-
ious labels based on various substrates
24 adhesion 4 I 18
printed with different technologies are quirements and customers’ expectation
available in the market and are no long- regarding the application performance
er just a piece of parchment paper carry- and usage. Some of the key parameters
ing product information, but are also part to focus on throughout the research are
of the aesthetic elements of a packaging. listed below.
The label and packaging industry is con- ● Well balanced adhesion – cohesion pa-
stantly searching for innovative ways to rameters
improve the look of a label and/or pack- – adhesion to variety of substrates in-
aging, “no-label” look being one of the cluding LSE
new trends. – high initial tack
Meanwhile, with the ever stricter envi- – optimized cohesion level in respect
ronmental standards and regulations, as to application usage and recycling
well as the increasing awareness of sus- ● Water-resistance
tainability and environmental responsibil- – non-whitening
ity from consumers, the search for green – adhesion retention after heat / hu-
and eco-friendly products becomes one midity exposure
of the key tasks for the label and packag- ● Clarity and UV stability
ing industries. As the packaging industry – non-yellowing
(mainly plastic materials) contributes sig- – “no-label” look
nificantly on high percentage of the world ● Durability
non-recyclable waste, trends are to move – temperature stable constructions
from traditional technologies to green- – chemical resistance
er solutions, such as biodegradable sub- – tear resistance
stances, sustainable/bio-based resources, – strength – sufficient bonding
re-useable/recycling products, waterborne ● Optimized rheology for wide range of
borne/low VOC materials and durable fin- coating processes
ish goods. ● Consistent label converting (cutting,
Synthomer therefore invested its re- slitting, etc.)
search and development resources into ● Good printability
waterborne PSA technologies to devel- ● Recyclability – “wash off”
op products which fulfill regulation re- performance.
© Synthomer
0 hr 1 hr
Monomer selection is key to
adhesion-cohesion balance
The key to formulate a good adhesive is
to understand application needs and trans-
late them to polymer design. A typical wa-
terborne polymer for PSA application is
polymerized with several acrylic mono-
mers, resulting in a polymer glass transi-
tion temperature in the range -60 to -30 °C.
Usually soft monomers are used togeth-
er with hard monomers or branching and
cross-linking co-monomers, to achieve the
desired adhesion-cohesion strength of the
polymer. Table 1 shows the influence of
soft and hard monomers and modifiers
to adhesion-cohesion performance. Poly-
mer A prepared mainly – based on soft
monomers like butyl-acrylate or 2-ethyl-
hexyl acrylate – is easy to peel off. Low
adhesion couples with very low cohesive
strength. Such a polymer usually leaves
adhesive residue on substrate. The incor-
poration of harder co-monomers (Polymer
B) enhance significantly the cohesion of
such a polymer. If monomers with x-link-
Soft / hard monomers ratio [%]
Mw modifier
Tack @ 20 gsm [N]
Adhesion @ 20 gsm [N/25 mm]
Cohesion @ 20 gsm [min.]
Table 1 > Adhesion-cohesion performance of polymers with different monomer compositions
3 hrs 24 hrs
ing functional groups are polymerized,
the cohesion is even higher. Polymers
with such a balance of adhesion and co-
hesion can be peeled off from various sub-
strates without leaving the residue. Such
polymers are used for formulation of re-
movable labels or adhesives for graphics
application where certain level of plasti-
cizer resistance is needed. Further mod-
ification of molecular weight make poly-
mer again softer. This high adhesion/high
cohesion products are suitable for perma-
nent label formulations.
To ensure good adhesion to variety of sub-
strates, specialty monomers with certain
functionality are used in small amount in
polymerization. These specialty mono-
mers ensure very good anchorage to ma-
jority of plastic substrates that are coat-
ed. They remain intact during usage and
when expose to common aging condition
such as high temperature, humidity or di-
rect contact with water. However in appli-
cation where recycling is part of the prod-
uct cycle, particularly for the bottle label-
ling industry, the adhesives should be eas-
Polymer A
95 / 5
no
4 6
7 8
1 > 200
Figure 1 > Water whitening of standard
polymer film after 1 hour, 3 hours and
24 hours water immersion
ily washed off in slightly alkaline caustic
soda solution (1.5 – 2 %) at temperatures
between 65 – 80 °C.
Surfactants – the double-edged
sword in polymerization
Surfactants or stabilizing colloids are one
of the key ingredients in waterborne po-
lymerization. They are is usually organ-
ic compounds containing a hydrophilic
head and hydrophobic tail, allowing it to
lower the surface tension of 2 immisci-
ble components and make them mixable.
At the beginning of waterborne polymer-
ization, the surfactant is used to form mi-
celle which allows polymerization to take
place. It also stabilizes the polymer parti-
cle in the final dispersion form, and con-
tribute to several polymer properties in-
cluding particle size and wetting. The hy-
drophilic head of the surfactant is howev-
er the main reason a polymer dispersion
is sensitive to water, causing a clear pol-
ymer film turns white when in contact
with water for a certain period of time
Polymer B Polymer C
82 / 18 82 / 18
no yes
20
28
> 200
© Synthomer
25
 Applications I Labelling and Packaging

Figure 2 > Water whitening of polymer

with traditional surfactant, blend of
traditional/co-polymerizable surfactant and
© Synthomer

Traditional surfactant Traditional surfactant Co-polymerizable co-polymerizable surfactant after 24 hours

+ Co-polymerizable surfactant water immersion
surfactant

water
evaporation
aqueous latex closest particle packing

particle
deformation
© Synthomer

film formation Figure 3 > Film formation mechanism

polymer film deformed particles of polymer

(Figure 1). This is especially severe when
free surfactants migrate to the surface of
the polymer film.
One of the possible approaches to over-
come the water whitening issue, is to
minimize the migration of surfactant to
the polymer surface by using a co-po-
lymerizable surfactant. Such surfactant
is grafted onto the polymer backbone,
hence restricting the surfactant from mi-
grating to the surface of the film but does
not alter the overall monomers compo-
sition and therefore maintaining the ad-
hesion-cohesion performance of the pol-
ymer. Figure 2 shows the water whiten-
ing resistance of polymer produced from
a conventional surfactant, a co-polymer-
izable surfactant and a mix of both. The
results show that the water whitening
resistance can be significantly improved
with a co-polymerizable surfactant.
Other factors influencing the water-sen-
sitivity are besides polymer composition,
the use of specialty monomers and sur-
factants also the film consistency, the
film formation (Figure 3) and of course
the particle size distribution. During
product development it was confirmed
that particle size and particle size dis-
tribution have a significant influence on
film formation.
Uniform particles usually give very con-
sistent film without micro-pores, which
minimizes water penetration through the
film. Polymer dispersion with unimod-
al particle size distribution was found
to give better water whitening resistance
(Figure 4), plus a more well-balanced ad-
hesion performance, compared to bimod-
al polymer system.
Aging performance of adhesives
is crucial for high performance
PSA label
While the resistance to white tarnishing is
an important property with regard to the
aesthetic impression, it is the functional-
ity of labels such as the maintenance of
adhesive strength after exposure to wa-
ter and heat that distinguishes a high-per-
formance adhesive label. Filmic labels are
very often used for labelling of beverages,
detergents, food which are stored at dif-
ferent temperatures for extensive period
of time. Furthermore these filmic labels
are usually exposed to humidity or water.
In this study the adhesive strength of 3 of
new developed Synthomer products and 2
market standards were tested after 1 and 3
days water immersion. Plextol (sample 1)

26 adhesion 4 I 18
 is the standard acrylic system with opti-
mized monomer composition. Samples 2
and 3 contain the co-polymerizable sur-
factant. As expected, both sample 2 and
3 shows outstanding peel adhesion reten-
tion after water immersion compared to
sample 1 and the two market benchmarks
(Figure 5).
For use as a label adhesive for recycling
bottles, a further modification of the pol-
ymer with a special x-linker that improves
wet adhesion is necessary. This modifica-
tion results in very good anchorage and
cohesive strength and ensures that the
adhesive can be removed from glass or
plastic bottles without leaving residues.
This simplifies the recycling process and
reduces energy consumption, making the
process more economical.
Due to the increasing demand for more
sustainable and environmentally friend-
ly products, the need for waterborne PSAs
to replace conventional solvent borne ad-
hesives will certainly increase in the fu-
ture. Synthomer is continuously investing
in product development to meet future leg-
islation and customer needs. //
© Synthomer

Figure 4 > Water whitening of polymer film with bi-modal (left) and unimodal (right) particle References
size distribution after 24 hours water immersion / 1 /Mazza, P., Martini, F., Sala, B., Magi, M., Co-
lombini, M., Giachi, G., Landucci, F., Lemorini, C.,
Modugno, F., Ribechini, E.: A new Palaeolithic
discovery: tar-hafted stone tools in a European
RETENTION OF PEEL 180° ADHESION Mid-Pleistocene bone-bearing bed. Journal of
30 Archaeological Science 33 (2006) [9] 1310
/ 2 /Kozowyk, P.R.B., Soressi, M., Pomstra, D.,
Langejans, G.H.J.: Experimental methods for
25 the Palaeolithic dry distillation of birch bark:
implications for the origin and development of
Neandertal adhesive technology. Scientific Re-
20 ports 7 (2017) [1]
/ 3 /Merrily A. Smith, Norvell M.M. Jones, Su-
san L. Page, Marian Peck Dirda in: Journal of the
15
American Institute for Conservation 23 (1984)
[2] 101-113
10

The Author
0
Competitive Product 1 Product 2 Product 3 Competitive
© Synthomer

Olga Bernatova
material A material B
(olga.bernatova@synthomer.com)
Ultimate Peel 180° Adhesion 1 day water immersion 3 days water immersion is working as a technical service manager with
Figure 5 > Retention of peel adhesion after Synthomer Germany.
1 day and 3 days water immersion

27