Viscoelastic Behavior, Thermodynamic Compatibility, and Phase Equilibria in Block Copolymer-Based Pressure-Sensitive Adhesives

The viscoelastic behavior, thermodynamic compatibility, and phase equilibria in block copolymer-based pressure-sensitive adhesives were investigated. The block copolymers investigated were: (1) polystyrene-block-polybutadiene-block-polystyrene (SBS) copolymer (KRATON® D-1102, Shell Development Company) and (2) polystyrene-block-polyisoprene-block-polystyrene (SIS) copolymer (KRATON® D-1107, Shell Development Company). The tackifying resins investigated were: (1) WINGTACK® 86 (Goodyear Tire & Rubber Company) and (2) PICCOTAC® 95BHT (Hercules Inc.). Samples of various compositions were prepared by a solution-casting method with toluene as solvent. Measurements of dynamic storage modulus (G'), dynamic loss modulus (G'), and loss tangent (tan δ) were taken, using a Rheometrics Mechanical Spectrometer. It was found that: (1) both WINGTACK 86 and PICCOTAC 95BHT were equally effective in decreasing the plateau modulus (G^O_N), and increasing the glass transition temperature (T_g) of the polyisoprene midblock of KRATON 1107; and (2) WINGTACK 86 was very effective in decreasing the G^O_N and increasing the T_g of the polybutadiene midblock of KRATON 1102, whereas PICCOTAC 95BHT was not. The observed difference between WINGTACK 86 and PICCOTAC 95BHT in decreasing the G^O_N and increasing the T_g of the polybutadiene midblock of KRATON 1102, whereas PICCOTAC 95BHT was not. The observed difference between WINGTACK 86 and PICCOTAC 95BHT in decreasing the G^O_N and increasing the T_g of the polybutadiene midblock of KRATON 1102 (perhaps to SBS block copolymers in general) is explained by the values of the interaction parameter for WINGTACK 86 and KRATON 1102, and for PICCOTAC 95BHT and KRATON 1102. The interaction parameter was determined, using the piezoelectric quartz sorption method. Phase diagrams were constructed for the four block copolymer/tackifying resin systems investigated, using information obtained from both dynamic viscoelastic measurements and optical microscopy. It was found that when mixed with KRATON 1102, PICCOTAC 95BHT formed separate domains whereas WINGTACK 86 did not over the range of concentrations and temperatures investigated. This confirms the evidence obtained from two other independent experimental techniques, namely, dynamic viscoelastic measurements and the piezo-electric sorption method. We have concluded from the present study that PICCOTAC 95BHT is not as an effective tackifying resin as WINGTACK 86, when each is mixed with KRATON 1102. It is pointed out further that information on the order-disorder transition temperature T_r, which was determined from a rheological technique proposed by us, is valuable in determining optimal processing conditions for block copolymer-based pressure-sensitive adhesives.