Migration of small molecules to, and across the surface of polymer matrices is a little-studied problem with important industrial applications. PVAc films are of industrial significance as the material of choice for the manufacture of latex paints, glue, food coatings. It is important to understand how additives present in the films can segregate to interfaces as these factors can severely affect the desired properties of the films. We have used surface tension experiments to underpin understanding of the drying process, and have identified the phase separation occurring during the solution casting of plasticized films containing second migrants. We wish now to obtain a greater understanding of how the distribution of additives evolves during the solution casting of the films and how it is influenced by molecular weight, polarity and compatibility of the components.