Preparation and properties of emulsifier-/solvent-free slightly crosslinked waterborne polyurethane-acrylic hybrid emulsions for footwear adhesives (III)–effect of trimethylol propane (TMP)/ethylene diamine (EDA) content

Stable emulsions of emulsifier-/solvent-free slightly crosslinked waterborne polyurethane-acrylic hybrids (WPU/AC-Ts) with a fixed acrylic monomer content (20 wt.%) and different trimethylol propane (TMP)/ethylene diamine (EDA) (0/0.20, 0.02/0.17, 0.04/0.14, 0.06/0.11, 0.08/0.08, the number indicated the mole% of TMP/EDA) for footwear adhesive materials were successfully prepared in this study. The as-polymerized hybrid emulsion containing 0.10/0.05 mole% of TMP/EDA content was found to be unstable, indicating that near 0.10/0.05 mole% of TMP/EDA content was beyond the limit value of crosslinkable TMP component for self-emulsifing. This study examined the effect of mole% of TMP/EDA on the stability and viscosity of hybrid emulsions, the tensile properties and dynamic mechanical thermal properties of hybrid film samples, and the adhesive strengths of formulated adhesives for footwear at both dry and wet states. As TMP content increased, the tensile strength/modulus/storage modulus/hardness of WPU/AC-Ts film samples increased, however, their elongation at break and water swelling% decreased significantly. The adhesive strength (peel strength) of formulated adhesives was found to be dependent upon the degree of drying, but almost not upon the TMP content in WPU/AC-Ts. The adhesive strength of footwear (EVA/leather) dried at room temperature for 24 h was higher than that of footwear dried for 30 min. However, the adhesive strength at wet state increased significantly with increasing TMP content. The optimum TMP/EDA contents were found to be 0.06/0.11 and 0.08/0.08 mole% to achieve the desired high performance adhesive properties such as high strength in wet state.