I think this is the same thing that happened to my boiler as it had the same symptoms. It turned out to be a flow valve that was worn out and so would only fire if the flow was high e.g. when the heating is on. Luckily we have a maintenance contract so it was fixed by an engineer.
i had the same problem a few months back and it turned out to be a holed or weak diaphram.i am a handyman not a plumber and easily fixed the problem. cost �16.00
my father is a british gas trained heating engineer with 40 yrs experience and is know self employed, he gave the answer above with the prices so make sure you don't get ripped off, a lot of people out there are glorified plumbers who will charge whatever they can get away with.