We have the same issue - the engineer told me that the water pressure is too low for the boiler to light when just using hot water - so you need to increase the boiler pressure up to about 1.5 bar - there will be a tap underneath the boiler - turn it on and you'll hear water running - look at the dial on the middle bottom of the boiler until it reaches 1.5, then switch off - now your hot water should work without the heating on ;-)
Howard Hughes, August 2008