Kraton polymers boost functional life of thermoplastic

road marking paints

Vincent Conserva and Martine Dupont, Kraton Polymers

ABSTRACT
Thermoplastic road marking paints with longer life and superior performance can be obtained
with the addition of Kraton polymers to the binder.

Styrenic block copolymers improve the mechanical properties of the binder which can increase
the performance life time of the road marking. Benefits of unsaturated and hydrogenated block
copolymers will be discussed. Both clearly reduce the paint erosion after numerous wheel
passages, improve the adhesion to glass beads and hence the retro-reflection properties.
Processing conditions will also be considered.

It will be shown that sprayable thermoplastic road markings with improved flexibility and
functional life can be produced by adding Kraton D1161PTM polymer to the composition.
Extrudable thermoplastic road markings with long functional life requirement in low traffic
density areas should be formulated with Kraton G1652MU polymer.

INTRODUCTION
A thermoplastic road marking material is a 100% solid, environmentally and user safe
compound. It fulfills current requirements on productivity, environmental protection and product
performance. Because the products are 100% solid, they do not require drying time and their
use keeps traffic disruption to a minimum. The absence of solvent and the easier handling of
waste reduce their impact on the environment. They can also be applied in thick layer (2-3 mm)
and ensure good coverage, which increases the service life of the marking product. Finally,
these materials show good adhesion on asphalt/bitumen roads and to glass bead.

However new regulations clearly strive to enhance driver safety and hence the level of
performance of road marking in terms of retro-reflection and erosion. These properties can be
further improved by the addition of a thermoplastic elastomer to the composition that would
boost the functional life of thermoplastic road markings by improving abrasion and crack
resistance. Better retro-reflection performance can also be achieved. This will be shown in this
paper.

THERMOPLASTIC ROAD MARKING PAINTS

Thermoplastic road marking paints (RMP) are a mixture of glass beads, pigment and filler held
together by a binder. As its names suggests, the composition becomes liquid when heat is
applied.

Binders of thermoplastic road markings consist of low molecular weight petroleum-based resins
or rosin derivatives optionally mixed with a plasticizer to reduce the brittle nature of the resin by
reducing the glass transition temperature (Tg) of the binder. They provide toughness, flexibility
and bond strength while holding all the components together. The low molecular weight of
these binder ingredients results in a relatively low abrasion resistance of the road marking. The
addition of a styrenic block copolymer (SBC) such a Kraton polymer improves the mechanical
properties of the binder, which increases the performance life time of the road marking. The use
of polymers to improve the quality of road marking paints will become more widespread as
regional regulations become more stringent in order to improve driver safety.

A typical thermoplastic road marking composition can be found in Table 1.

Table 1: Typical thermoplastic road marking paint composition

Range, weight % Material

8-15 Hydrocarbon resin
Binder 1-5 Plasticizer
(15-25%w) 0-5 Thermoplastic elastomer

5-10 Pigment (e.g. TiO2, ZnO)

Fillers 20-40 Extender (e.g. CaCO3)
(75-85 %w) 15-20 Glass Beads
20-40 Aggregates

WHAT ARE STYRENIC BLOCK COPOLYMERS?

Styrenic block copolymers are thermoplastic block copolymers consisting of polystyrene
domains in an elastomer-continuous phase. This provides elasticity to the system: the
polystyrene domains give cohesion to the system and act not only as physical cross-links in the
three-dimensional network, but also as reinforcing filler for the elastomeric matrix. The polymer
behaves like a cross-linked rubber at ambient temperature, but as these cross-links result from
physical interactions, they start to soften at temperatures close to the polystyrene Tg. This
allows them to flow under shear when heated, yet they recover their strength an elastomeric
properties on cooling. These characteristics make them suited for the formulation of hot melt or
extrusion applied coatings. They can also be milled into a fine powder and applied by various
melt spray processes. These polymers dissolve readily in resins used in thermoplastic road
markings at typical melting temperatures of 180°C to 220°C.

Figure 1: Microstructure of styrenic block copolymers

Kraton polymers are based on different types of block copolymers, differing mainly by their
rubber type: styrene-butadiene-styrene (SBS) types, styrene-isoprene-styrene (SIS) types and
their saturated versions: styrene-ethylene/butylene-styrene (SEBS) and styrene-
ethylene/propylene-styrene (SEPS). They have an elastomer Tg of -60°C (SIS-SEBS) or -90°C
(SBS) and a PS Tg of +95°C.
 Figure 2: Styrenic block copolymer types

USBC polymers like SIS and SBS polymer show good cohesion and excellent flexibility at low
temperature. When superior resistance is required against UV, then HSBC might be required.
Because of the saturated nature of the rubber midblock, SEBS and SEPS polymers show
excellent weatherability, thermal stability and high tensile strength. Because of their higher
cohesion, they can be used in more diluted formulations and show excellent oil absorption
properties. These grades can also be functionalized to introduce reactive polar group for
improved adhesion to certain surfaces or for crosslinking reactions. Finally, as they exhibit
higher viscosities as USBC, they might be more suitable for extrudable than for sprayable RMP.

In this presentation we will concentrate on SIS and SEBS polymers.

STYRENIC BLOCK COPOLYMERS FOR THERMOPLASTIC

ROAD MARKINGS
Among suitable polymer additives for use in thermoplastic road markings, styrenic block
copolymers are the preferred materials of choice. Their unique structure of polystyrene blocks in
an elastomer continuous phase provides them specific visco-elastic properties, as can been
seen on Figure 3.

Figure 3: Elastic modulus G'

Their addition to the resin shifts the composition Tg to a lower value and significantly reduces
the elastic modulus. It can also be clearly seen that the mixture remains thermoplastic and
shows a strong elastic modulus decrease above a temperature, which is higher than the resin
melting point. Therefore, the use of styrenic block copolymers in the paint formulation can result
in binders with improved flexibility at lower temperatures, reduced brittleness, and higher
elasticity at higher temperatures compared to binders based on petroleum or rosin-derived
resins and modified with other polymers such as waxes.

Styrenic block copolymers are also fit for road marking paint processing techniques. Milled or
powdered Kraton polymers dissolve readily in resins used in thermoplastic road markings at
typical melting temperatures of 180°C to 220°C (patented technology EP 0 499 326 B1).

The use of polymers in road markings can however lead to a longer dissolution time and higher
hot melt viscosity compared to binders comprising only low molecular weight resins and
plasticizers. Therefore, the choice of type, morphology and amount of styrenic block copolymer
depends on the application technique (extrusion or spray), and on the ultimate road marking
performance desired.

Wear simulator

Figure 4: AETEC turntable detail: wheel on paint test panels

To highlight the benefits of styrenic block copolymers in thermoplastic road markings, we carried
out wear simulation tests according to norm EN13197. The wear simulator selected is described
in annex F of this norm. Detail of the turntable can be seen on the picture above.

In this study, one SIS polymer (Kraton D-1161PTM) and one SEBS polymer (Kraton G-1652MU
polymer) are compared to a binder without polymer additive.

Kraton D-1161PTM polymer has low polystyrene (15%) and di-block (17%) contents, which
allows formulating with a good balance between elasticity-flexibility and cohesion-erosion
resistance.
Kraton G-1652MU polymer has a saturated elastomeric block: it is harder and shows higher
cohesion and better stability.

Viscosity data

The type of polymer has an influence on the viscosity of the paint as can be shown in Table 2 .

Table 2: Viscosity data

Polymer Type Resin type Dissolution HMV 200°C HMV after

time at 200°C (cp) 4h at
(h) 200°C (cp)
Kraton D1161PTM SIS C5 HC resin 2 815 660
Kraton G1652MU SEBS Hydrogenated 2.5 1370 1340
C9 resin

In this table, viscosity data and dissolution times for the two polymers are given; all binders
consisted of 3 parts by weight of SBC and 14 parts by weight of resin. The SIS polymer resulted
in the lowest Brookfield hot melt viscosity (HMV) and showed only marginal degradation after
storage of the binder for 4 hours at 200°C. Polyisoprene degrades by chain scission which
results in a reduction of viscosity over time. HSBC polymers with a saturated elastomer mid-
block can demonstrate very good thermal stability resulting in almost no change in viscosity
over time. Their higher viscosity might however require an adaptation of the application
equipment. Their higher thermal stability could afford higher application temperatures, but those
could be detrimental to the other ingredients of the formulation.

Paint application and composition

A typical Central European paint formulation was chosen. The paints were produced in
Germany. Kraton Polymers in cooperation with Sovitec - Group R&D applied the paints via
spray on flat test substrates, according to EN13197 (Figure 5).

Figure 5: test plate

The paint composition is given in Table 3.

 Table 3: paint composition

formulation composition (%) ref KD1161 KG1652

SIS SEBS
C5 resin 15 15 15
oil 2 2 2
rosin resin 1 - -
PE wax 2 2 2
styrenic block copolymer 2 2
TiO2 10 10 10
fillers 30 29 29
premix glass bead, 1000-125 mm 40 40 40
g/m² applied paint 3300 3000 3000

drop on beads, g/m², 3F coated, 600-125 mm 300 300 300

Superior erosion resistance

Figure 6 demonstrates the effect of the addition of styrenic block copolymers to the binder of
road marking paints.

Figure 6: erosion resistance

 6
The thermoplastic reference paint without Kraton polymer failed the test after 1.5*10 wheel
passages. Adding Kraton Polymer to the binder enables excellent erosion resistance up to
6
4*10 wheel passages.

Kraton G1652MU polymer exhibits superior erosion resistance due to its 30% polystyrene
content in combination with the hydrogenated elastomer phase. The paint surface is hardly
6
eroded after 4*10 wheel passages.

Kraton D1161PTM polymer erodes to a higher extend due to the presence of diblocks and its
low polystyrene content.

Figure 7, showing the paint percentage retained after wear test, confirms the improved erosion
resistance for the Kraton polymer containing paints.

120
wheel passages, MM passages

100

80

60 reference
Kraton D1161PTM
40
Kraton G1652
20

0
0 1 2 3 4 5
erosion retained, %

Figure 7: erosion retained in function of wheel passages

Superior retro-reflection

Regulations clearly strive to enhance the level of performance of road markings in terms of
retro-reflection and luminance. The coefficient of retro-reflected luminance (RL), which is an
indication of night time visibility, was measured after the wear simulator test. Its evolution as a
function of the number of wheel passages can be seen on Figure 8.

This graph confirms improved RL for the styrenic block copolymers containing paints. The
6
thermoplastic reference paint without Kraton polymers failed the test after 1*10 wheel
6
passages. Adding Kraton polymer to the binder enables excellent RL over 4*10 wheel
passages. After elimination of the drop on beads, the premix beads are exposed to the paint
surface. The premix beads are retained thanks to Kraton polymer‘s elastic properties, leading to
improved RL.
 Figure 8: Evolution of the retro-reflection coefficient with number of wheel passages

Kraton D-1161PTM exhibits excellent RL, due to its SIS nature, polymer structure and balance
of flexibility and cohesion. The erosion of the surface and exposure of the premix glass beads
leads to a clean paint surface. So, its lower erosion resistance compared to Kraton G1652
polymers appears here to lead to improved retro-reflection performance.

Kraton G1652MU polymer results in lower RL values, due to its SEBS nature and high cohesive
polymer structure. The erosion process is slowed down, leading to less exposure of the premix
glass beads and to dirt pick up. This grade is therefore better suitable for road markings with
long functional life requirements in low traffic density areas.

CONCLUSION
Thermoplastic road marking paints with longer life and superior performance can be obtained
with the addition of Kraton polymers to the binder.

Styrenic block copolymers improve the mechanical properties of the binder which can increase
the performance life time of the road marking. Both unsaturated and hydrogenated block
copolymers clearly reduce the paint erosion after numerous wheel passages, improve the
adhesion to glass beads significantly and, as a result, establish better retro-reflection
performance in the medium and long term. Furthermore, styrenic block copolymers can exhibit
high extendibility and can increase the durability of the thermoplastic road marking even at a
SBC addition level as low as 2%.

Sprayable thermoplastic road markings with increased flexibility and functional life will benefit
from the addition of Kraton D-1161PTM polymer in the binder.

Kraton G-1652MU polymer is recommended in the binder of extrudable thermoplastic road

markings with long functional life requirements in low traffic density areas.
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