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Thing is, even if you do it in the mould, ideally you still need to rough up the surface of the paint to ensure a good bond with the epoxy - some paints will bond without any prep, but not all do. Some will just peel straight off after you demould. It isn't something I would commit to without testing first.
Post painting is definitely the easiest way. Either mask up before scuffing the surface, or use a clear adhesion promoter. I've never tried an adhesion promoter personally, but the spray painters I know will use them. They prefer a mechanical key, but they say the adhesion promoters do a decent job when necessary.
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