Thank you all so very much, guys. You have confirmed my suspicions.
What actually happens is that in HW only mode, Rad 4 heats up quickly and all the other upstairs rads follow. Not what we intended!
The first oddity was that Rad 4 was getting its heat from the RETURN (or what would normally be its return). DP has it in one - reverse circulation. It seems that water is being pushed back up Rad 4 because of the close proximity of the return connections from the HW cylinder and Rad 4.
Once the water starts moving, there's no stopping it. It comes back from Rad 4 via its "flow" and then, when it joins the 22mm, acts as a feed to all the other rads, further helped by convection. The circuit is complete.
Oilman, as always, has the fix. If we reconnect the HW return to a point BEFORE it splits into upstairs/downstairs, i.e. closest to the boiler, then balance should be restored. Any backflow will meet with a wall of water with nowhere to go.
Does this theory hold good? There's a lot at stake here. With the help of coathangers, torches and mirrors I think we found where the problem lies. Your observations have confirmed this and I thank you most sincerely. If it's a question of re-routing the HW return to the boiler port, that will be relatively painless.
None of this helps a condition in one of the bedrooms where the rad gets hot as soon as you fire up the HW, with no obvious effects elsewhere. I guess it has, quite simply, been plumbed into the HW circuit - and I ain't going to bark any more knuckles over that!
The builder has gone out of business.
Paul