Selecting
the right SBCs for an adhesive formulation allows formulators to develop
specific solutions for various adhesive markets, optimizing cost and
productivity.

Table 1.
The main characteristic of styrene block copolymer (SBC) is
its thermoplastic property, which is provided by polystyrene blocks present in
the polymer molecule. Polystyrene blocks are able to build “physical links”
between neighboring molecules to form reinforced polymer webs. When the
temperature is raised to melt the polystyrene blocks or dissolve them in an
organic solvent, the physical links are softened and the polymer’s viscosity is
reduced in order to modify the original web structure and change the product’s
shape. When the polymer is dried or cooled, it recovers its elastomeric
properties and will maintain its new shape.
This thermoplastic characteristic provides several advantages for using SBCs in
adhesive formulations: compounds can be obtained with excellent physical
properties without vulcanization; adhesive compounds can be formulated by a
thermal processing technology (hot-melt adhesives); and adhesives can be
formulated by dissolving ingredients in organic solvents (solventborne
adhesives). SBCs synthesized using solvent-based technology also offer narrower
molecular weight distribution; this allows the polymers to dissolve directly
into organic solvents without a pre-mastication process, such as those employed
in the production of chloroprene rubber (CR), emulsion SBR, or natural rubber
(NR) based adhesives.
Dynasol produces several SBCs with different structures and compositions for
various market segment requirements (see Table 1).

Table 2.
SBCs in Solventborne Adhesives
Solventborne adhesive are mainly used in applications where
higher cohesive strength is required, such as those found in the building and
construction markets.
SBCs are widely used in solventborne adhesive formulations due to their
advantages over other elastomeric structures. They develop faster solubility
than other polymer bases, such as CR, NR, or emulsion SBR, without the need for
additional processes (such as pre-mastication) due to their narrow molecular
weight distributions. This, in turn, reduces operating costs and increases
productivity. SBCs also develop lower solution viscosities, allowing
formulators to increase the formulation’s solids content and reduce VOC
evaporation levels. This leads to a decrease in solvent volume, as well as
lower handling, transportation and storage costs.
Table 2 compares SBC-based solventborne formulations with a commercial
25%-solids CR-based adhesive. The first formula (F-01) was based on a radial
medium-molecular-weight copolymer. The second (F-02) used a blend of a
high-molecular-weight radial copolymer and a linear SBS containing 20% diblock.
The third formula (F-03) was a CR commercial adhesive. All were applied using
the same procedure and the same adhesive weight for the bond.

Figure 1. Comparative results of solventborne adhesive formulations. F-02 developed cohesive strength faster than F-01, and both developed higher cohesive strength than commercial reference.
As
shown in Figure 1, F-01 developed a faster cohesive strength than F-02; both
adhesives developed higher cohesive strength than commercial CR-based adhesive.
All three adhesives developed similar viscosity, while F-01 and F-02 had higher
solids content (35% solids vs. 25% solids content of F-03 commercial
reference).

Table 3.
SBCs in Hot-Melt Adhesives
The formulation and use of hot-melt adhesives offer a cost
benefit and environmentally friendly option to adhesive manufacturers; they
eliminate the drying process and, therefore, the equipment and energy
requirements of solvent- or water-borne adhesives. In addition, organic
solvents are not required, which reduces VOC emissions. Productivity is
improved by reducing cooling time. SBCs can be easily formulated as hot-melt
adhesives due to their thermoplastic nature, allowing them to melt by
increasing the process temperature in order to incorporate all of the
ingredients to obtain adhesive properties.
Table 3 shows a typical hot-melt adhesive formulation. An elastomeric base
(SBC) was used to absorb debonding energy as elastic deformation and develop
cohesive strength; a midblock tackifying resin was used to improve adhesion to
different substrates; an endblock tackifying resin was used to reinforce
styrenic domains cohesively; a plasticizer was used to modify polymer
viscosity, thus improving adhesive wetting; and a stabilizer was used to extend
the life of the ingredients.
Additives, such as viscosity modifiers and other non-reinforcing fillers, can
be incorporated into the adhesive formulation to reduce cost, as well as to
adjust rheological adhesive performance and other characteristics for improved
productivity.

Table 4.
Table 4 shows three hot-melt PSAs that can be used to
develop adhesives for tapes and label application. Based on blends of SBCs set
to perform at different application conditions, adhesives were formulated and
evaluated at Dynasol using standard analytical techniques in ambient controlled
conditions (50% relative humidity and 23°C). Adhesives were applied to 0.002”
PET film using stainless-steel panels as the substrate.

Figure 2. Adhesive characterization results for HMPSA formulated using different blends of SBCs with different structures (see Table 3).
Figure 2 shows comparative results for adhesive performance.
F-01, based on an SBS triblock polymer (C-500) and a SB/SBS polymer with 80% of
diblock (S-4318), developed the lower viscosity and Tg, and maintained
excellent adhesive performance. The softening point for this formula was 80°C.
F-02, based on the same C-500 blended with a low-viscosity radial copolymer
(C-405), developed 60% higher viscosity and cohesive strength than the first
formula, maintaining similar adhesive performance. The third formula developed
the highest viscosity and intermediate cohesive strength, and reached a
softening point of 110°C; this means that it can be used for some automotive
applications in the transport market.

Figure 3. Comparative characterization results for a hot-melt adhesive formulated using new multiarm SBCs and a commercial multiblock SBC.
New multi-arm polymers with lower styrene content (32-36%)
develop higher cohesive strength (tensile result) than commercial multi-block
polymers with 45% styrene content, and maintain similar adhesive viscosity. In
addition, the new polymers improve rolling ball tack evaluation. This means
that these adhesives can develop faster tack than those formulated using
multi-block copolymer, improving application speed and productivity in
application lines.

Table 5.
Figure 3 shows comparative characterization results for the
adhesives proposed in Table 5, which are based on three new multi-arm structure
polymers developed for adhesives, and use a commercial multiblock copolymer as
reference.

Table 6.
Table 6 shows the partial substitution of SIS using an S-SBR
in a PSA formula. An equal amount of SIS was substituted for S-SBR in the
formula; all other components were maintained according to the original formula
(Figure 1).

Figure 4. Adhesive characterization results for 20% and 35% SIS PSA formulation using S-SBR.
Figure
4 adhesive characterization results show that a 20% lower viscosity and an
improvement in holding power resistance is obtained for 20% and 35%
substitutions, while adhesive properties are consistent with the original
formula. Because S-SBR is less expensive than SIS polymers, formula costs can
be reduced.
Conclusion
- Thermoplastic characteristics allow SBCs to be
used in the formulation of either solventborne or hot-melt
adhesives.
- The availability of products with different structures and
compositions helps optimize performance according to the specific requirements
of each application.
- SBCs can be used at a higher solids content than other polymers, such
as CR and NR. They can achieve the same or better adhesive performance, thereby
reducing VOC emissions and cost related to solvents use.
- New multi-arm structure copolymers offer improved adhesive
performance over higher-styrene-content copolymers.
- S-SBR can be used as a substitute for SIS copolymer in adhesive
formulations, improving properties such as shear and adhesive viscosity, and reducing
formulation costs.
For more information on SBCs, contact Dynasol Elastomers at (877)
559-7568 or visit www.dynasolelastomers.com.Links