Doesn't sound like PCB to me - the PCB doesn't know or care whether it is being called for heating or for hot water. Could well be the motorised valve on the central heating side jammed part way open.
The way it should work is the timer and room stat provide power to open the valve. When the valve is fully open it hits an internal micro-switch which in turn feeds power ("call") to the boiler requesting it to fire up. If the valve never opens fully, there will be no signal to the boiler to turn on. But when the boiler fires up for hot water, there will be accidental flow through the partially open CH valve.
You can test this theory by locating your central heating motorised valve and operating it manually using the skinny metal lever sticking out of the base of the valve head. The motorised valves will be somewhere near the main wiring box, and look like one of these

It is frequently the motor part of the unit that fails rather than the actual valve, in which case you can swap in a replacement motor unit without touching the actual plumbing, assuming you are electrically competent. Otherwise it will be a drain down to fit a complete new valve.
This assumes you have a separate two-port valve for CH and DHW ("S-plan").