I've done exactly that, urethane resin backed up with fiberglass. I used Smooth-Cast Onyx, slush cast in a thin coat, then applied epoxy and glass mat. The epoxy bonds well with the resin and shows no sign of delaminating.
But the Onyx may be fine on it's own. I've slush cast parts about 1/16 to 3/32in thick, they are very tough but not brittle. But glass can be as hard or harder but a bit thinner if that's what you need.
I never use polyester, as Zombie Killer said it stinks, I can't stand the stuff. I use EpoxaMite medium from Smooth-On, very good tough stuff with no odor.
Edit to add: polyester and epoxy are both very tough on silicone molds. I've tried a number of solutions but I've found that urethane resin as a "gel coat" works best. The epoxy bonds to it well, and can't get through to the rubber.