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You will never miss a chance to create anything. Rifle Demons can appear in rank 30+ items in the Item World, or in the story, the only time one appears is right before the very last battle in the last episode. They can also appear in rank 15-29 items in a rare or legendary item on floors 41 and up, or in a rank 1-14 item in a legendary item on floors 81 and up.
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Yeah, enemies in MRs don't count towards unlocking them in the DA. I figured out the same way as you did.
If you want to wait or or not, it's your choice. Personally, I don't use monsters (even though I see a lot of potential in some of them), so it makes no difference to me, but just as aces4839 mentioned, Baciels only shows up very late in the main game.
That said, if you want to create a Baciel early, you'll probably have to go on some high level items to look for them (if you use the Hospital trick, it shouldn't take too long), though you'll have to defeat them, and I don't know if killing them with Thieves/Kunoichis' poison abuse counts towards unlocking them. If you're lucky and get Invincibility panels (might be a good idea to bring a Geomancer for a Geo Change, though it only works once per floor), it's feasible with a Samurai equipped with a weight. Samurai's ability only works if it can deal > 0 dmg, but if you use combos and the +dmg/combo multiplier from standing still, you'll kill it eventually.
I'm only speculating here, but you might be able to unlock them in the Dark World stages. None of them have Baciels (only the higher tiers), and while still beatable at low levels, again, I don't know if kills with sleep/poison works for that purpose. If you really want them, it's still worth the shot, I guess. According to Paradisio's FAQ: - Map 5-4 have a Malchidael (last tier/Rank 6 of Baciels), no Lv listed. - Map 8-4 have a Lv 180 Adnachiel (tier 3) - Map 13-1 have 18x Lv 260 Verchiel (tier 4), though at this point, it's better just to find them normally at 13-4 - Map 13-3 have a Lv 500 Malchidael. Again, it's better just to unlock them normally
DW 5-4 is an early and easy level (small level surrounded by Disperse dmg and a single enemy, the Malchidael) if you use sleep/poison. It's a little annoying to unlock the stage (you have to kill everything in the regular map using Tower attacks), though. If poison doesn't work for unlocking them, try your luck with a Samurai+weight (if you use multiples Kunoichis+weights to bring the combo up before dealing the final blow, doing >0 dmg is guaranteed), though it'll probably take some resets. Again, this is assuming kills in the DW counts towards unlocking (I don't see why not) and if killing a higher tier unlocks the basic form.