We present a possibility of tailoring the near-surface composition profiles of pressure sensitive adhesive (PSA) films by an exposure to atmospheres of different relative humidities (RHs). The statistical copolymer P(EHA-stat-20MMA) with a majority of ethylhexylacrylate (EHA) and a minority of methylmethacrylate (MMA), being cast from a toluene based solution, is chosen as a model system. The near-surface composition profile is probed with X-ray reflectivity. All probed samples show an enrichment of PMMA at the sample surface; however, the near-surface PMMA content strongly increases with increasing RH. The influence of the RH on the composition profile is present down to a depth of 50 nm. Therefore the surface tensions being derived from contact angle measurements do not show any measurable humidity dependence. In contrast, in a mechanical tack test with a smooth punch surface, a strong influence is probed. This observation can be explained by considering the integrated PMMA content over an appropriate near-surface region and the resulting impact on the cavitation process.

Ultrathin layers of the statistical copolymer P(nBA-stat-MA) with a majority of n-butyl acrylate (nBA) and a minority of methyl acrylate (MA) are characterized with respect to the film morphology and the mechanical response in a probe tack test. The probed copolymer can be regarded as a model system of a pressure sensitive adhesive (PSA). The films are prepared by spin-coating which enables an easy thickness control via the polymer concentration of the solution. The film thickness is determined with x-ray reflectivity (XRR) and white light interferometry (WLI). Grazing incidence small angle x-ray scattering (GISAXS) provides detailed and statistically significant information about the film morphology. Two types of lateral structures are identified and no strong correlation of these structures with the PSA film thickness is observed. In contrast, prominent parameters of the probe tack test, such as the stress maximum and the tack energy, exhibit an exponential dependence on the film thickness.