The invention relates to a transdermal therapeutic system which comprises a back layer that is impermeable to the active substance, and a peelable protective layer that is impermeable to the active substance and at least one matrix layer consisting of polysiloxanes and/or polysiloxane derivatives and containing micro-reservoirs. Said micro-reservoirs contain at least one ion pair from a pharmacologically active substance and an additive and either the active substance is nucleophilic and the additive is electrophilic or the active substance is electrophilic and the additive is nucleophilic.