Additives are an essential part of polymer formulations because they decisively influence the chemical behavior of daily polymer products. Whereas many analytical techniques exist to analyze additives in the polymer bulk, only a few techniques are able to obtain chemical information on the polymer surface, among these Time-of-Flight Secondary Ion Mass Spectrometry. Many studies have proven the general usefulness of TOF-SIMS analysis for the characterization of polymer materials and polymer additives. However, systematic investigations on the optimum analytical conditions for a sensitive detection of additives from polymer surfaces are still sparse. We therefore investigated the influence of the primary ion bombardment parameters on the emission behavior of model samples. The samples were prepared by spin coating the antioxidant Irganox 1010 in different concentrations onto additive free LDPE substrates. The secondary ion parameters yield, disappearance cross-section and secondary ion emission efficiency (yield per damaged area) were determined for primary ion bombardment with Ga@super +@, Cs@super +@, and SF@sub 5@@super +@. The primary ion energies were varied between 4 and 10 keV for SF@sub 5@@super +@ and Cs@super +@ and between 5 and 25 keV for Ga@super +@ bombardment. From these experiments optimum analytical conditions for the analysis of thin additive coatings on polymer materials were deduced. The results will be applied to real world polymer surfaces with respect to additive quantification and additive degradation processes.