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You can mine for Union Ore and other rare Ores by going doing Quests which involve volcanic area.
Also,the best way is to get them in Pokke Farm.Get them in 2nd or 3rd Mining Point.
Lankey
Pokke Farm if your mining point is upgraded to +3
It can also be found in area 4 and 6 of the High-Rank Volcano or area 8 of the G-rank Great Forest.