If you do not use your immersion there are a couple of reasons why this might happen 1) do you have any mixer showers/taps fed on the hot side by tank and cold side by cold main as if a mixer is letting cold through it can backfill the hot water cylinder causing overflow or 2) the coil in your cylinder is allowing central heating water to backfill the hot water system. Do you have a pressurised heating system and is it losing pressure or is the heating f&e tank higher than your overflowing cold water tank?
SE gasman
March 2009