One piece molds open to air are not a good idea for two reasons. One is the reason the OP mentioned- it is hard to pour the mold with exactly the right amount so that neither surface tension nor capillary tension do not make a curved edge.
The other reason is that the two-part urethane resin relies on heat generated by the chemical reaction to mixing in the hardener. If part of the actual part is in contact with the air, this area does not get heated as well as those surfaces not in contact with the air, and hence will not fully harden. I overpour just slightly when I make a one-piece mold, then place a block of particle board with a smooth surface on top of mold, with a weight on it to hold it in close contact with surface of mold. The mold must have been poured with the pattern on a smooth surface to begin with, so it represents a smooth surface around the cavity. This will give you a flat and fully cured back surface.