No, you don't need to kill the boss to get PSG to drop but bosses have overall higher chance to drop than common mobs and you need a minimum of an A rank against the boss to have a chance at PSG. Map S rank has the highest overall chances of dropping PSG.
"The Aegis (armored humanoid) squads and the 4402 CE Guards as well as Ouroboros have a chance to drop ASh-12.7, PSG-1, Z-62, ARX-160"
Taken from the Cube guide.
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