In the present study a methodology for TOF-S-SIMS measurements is developed to gain information on the distribution of molecules on and in polymer coatings (thickness similar to 100 mu m). Experiments were carried out on model systems consisting of one or more additive-containing polyvinylbutyral coatings. Several organic additives were selected: carbocyanine dyes, basonyl blue and the pharmaceutical risperidone. The additives have been measured as pure compounds on a Si substrate to obtain good reference spectra. After optimisation of the sample preparation method, the coatings were embedded in epoxy resin and stored in an oven (60 degrees C) for 24 h. Cross-sections were made by means of a microtome. S-SIMS spectra were taken on the prepared cross-sections before and after An was deposited on the sample surface. Compared to the untreated samples, the An covered samples give rise to more intense secondary ion signals. Generally, signals of the intact cations were more intense than those of the fragment ions. Apart from mass spectra, images of the additive distribution in the coatings could also be acquired by recording structural ion signals. It was possible to make secondary ion images of the additive molecule ions with a (sub)-micrometer lateral resolution. (c) 2006 Elsevier B.V. All rights reserved.