Enhanced migration of plasticizers from polyvinyl chloride consumer products through artificial sebum

In the present study, the migration of plasticizers from modeled and commercial polyvinyl chloride (mPVC and cPVC, respectively) to poly(dimethylsiloxane) via artificial sebum was assessed to mimic the dermal migration of plasticizers. In addition, the various factors affecting migration of phthalic acid esters (PAEs) from diverse PVC products were investigated. The migrated mass and migration ratio of PAEs increased but the migration rate decreased over time. The migration rate increased with sebum mass, contact time, and temperature but decreased under higher pressure. Low-molecular-weight PAEs (dimethyl phthalate and diethyl phthalate) migrated in higher amounts than high-molecular-weight PAEs (dicyclohexyl phthalate [DCHP] and diisononyl phthalate [DINP]). Diffusion of all PAEs in mPVC increased with temperature, with diffusion coefficients ranging from 10^-13 to 10^-15, 10^-12 to 10^-14, and 10^-10 to 10^-12 cm²·s^-1 at 25 °C, 40 °C, and 60 °C, respectively; the enthalpy of activation ranged between 127 and 194 kJ·mol^-1. Moreover, migration depended on total PAE content of the product, as the diffusion coefficient for DINP in cPVC (softer PVC) was approximately three orders of magnitude higher than that for DINP in mPVC (harder PVC); this may be due to the increase in free volume with increasing plasticizer content. Finally, the daily exposure doses of the plasticizers were estimated. These findings will be helpful for estimating dermal exposure risk.