Check your flow and return valves on boiler are fully open, and then check your rads for a by-pass route. Check that the thermistors are in the correct postion on the flow pipe.
If you can check with the manual and check the wiring of the room stat to the boiler. I think you still need to check that the pump runs after the room stat has been turned down thus cooling the boiler.
It could be overheating? But if you click off using the thermostat do you mean the stat on the boiler? If so then the pump should be over-running to cool the boiler. When you run the hot tap does this cool the boiler, so that it can be reset?
Do all of your rads have T.R.V.'s or is there a system by-pass, it sounds like there is no where for the water to circulate when the heating circuit shuts down. As mentioned by Stem.