Study of siloxane additives migration to the surface of polyester-(melamine)-polyurethane coatings: Aging effects after ethanol cleaning

This study determines the influences of siloxane flow agents’ migration on the outermost surface composition of clearcoats, before and after ethanol cleaning. This evaluation is undertaken to improve adhesion of pressure-sensitive adhesives (PSAs) on automotive paint systems. Most of the siloxane flow agents segregate from the bulk to the clearcoat outermost surface during curing. These additives can cover until 50% of the surface area but X-ray photoelectron spectroscopy (XPS) and time of flight-secondary ion mass spectrometry (ToF-SIMS) analyses indicate that they can be removed by ethanol cleaning. Composition of the cleaned clearcoats surfaces are similar as the composition of clearcoat formulated without siloxane additives: the polyester-(melamine)-polyurethane network is more detected than before cleaning. However, outermost surface analyses show that several aging weeks increase the siloxane additives segregation. This post-cleaning migration modifies the clearcoat surface composition and cancels the chemical modifications due to the ethanol cleaning. XPS analyses show that silicon concentrations after cleaning and aging are inversely proportional to the initial silicon concentrations measured after curing. It highlights that aging has to be controlled to improve adhesion of PSAs on clearcoats. A second ethanol cleaning on aged clearcoats is not effective to remove these new siloxane additives. Their formulation should be different from the flow agents and it could modify their solubility in ethanol. This result could also indicate that these new siloxane additives are not located on the last molecular layer of surface and they would not be soluble in ethanol.