Boiler engineer I would say, Tooj.
With the CH off, rads shouldn't get any flow to them. It's a possibility that the boiler thermostat for the Hot Water, is faulty. It may not be switching off in time. This allows a build up of heat which is then being dissipated through the rad circuit.
Although .......... that shouldn't happen because you probably have a motorised valve in the airing cupboard that directs water to either CH or HW.
Perhaps the motorised valve is stuck halfway........ letting primary hot water (from boiler) into the rads.