If you have a normal system ( not a combi) you will probably have a 3 way valve or 2 divertor valves in your airing cupboard.This diverts your water so you can have either heating, hot water or both. There is a rubber ball inside this valve which can become worn, or if you have had your system flushed it could have some dirt on the seating allowing water to pass to your radiators,( when your water is heating up) even when they are turned off.Probably wants a new divertor valve.