If the vessel had lost its charge, too much charge or failed altogether, or the pressure reducing valve had failed or not present then the expansion relief valve SHOULD drip first as its pressure setting is usually 1 bar lower than the combined pressure and temperature relief valve. The only time I would expect the combined pressure and temperature relief valve to activate due to excess pressure is if there's a problem with one of the above and the expansion relief valve had failed.
Edit: If there was a problem with a mixer unit letting by then any cold mains pressure not balanced and at higher pressure than supply to cylinder can also cause this problem.