I've tried paint + laser method, and after multiple attempts (laser power, focus, type of paint, feedrate) it can be done in principle.
In my case I've used my CNC 3020T with a 1W 445nm laser, high temperature black matt spray paint and modified FlatCAM slightly to generate isolation milling G-codes, but with IO on/off for the laser.
The problem is that this is awfully slow. 1W laser is not super-powerful and isolation milling takes a long time (but probably faster than actual milling with a conical bit - there feedrates have to be based on the tool and material).
Second issue is that even evaporated paint can leave transparent coating on the copper that is impenetrable to the etchant. Usually this requires some extra solvent (isopropanol), maybe ultrasonic bath and a lot of care to clean out places in between the tracks without destroying the remaining paint.
Another problem is quality, isolation milling doesn't produce nicest looking PCBs by its very nature, also I've tried multiple passes and that can leave some tiny bits of copper here and there.
Unfortunately, I don't have high power CO2 laser cutter. I've read some success stories there, if one disables air assist and vaporizes paint back to front (assuming the exhaust is on the top). Also, as someone mentioned, copper is a mirror for LWIR, so I would be worried about destroying the focusing lens.
Anyway, for now I'm back to doing toner transfer. It has issues (mostly registration and scale problems, CNC drilled holes don't often match the printed pattern very well on bigger boards - poor laser printer I suppose).
Here some photos of one of the first "successful" PCBs done with the laser + paint method: