If you want a really top quality surface finish i would rule out any ideas of joining 2 mold halves, you will get a line even if you can machine each half perfectly. It's amazine how a misalignment of even a fraction of a thou will make visible lines and ridges that you can feel with a fingertip.
My suggestion would be to make the master as a positive, finish it with some high gloss (or whatever) clear coat to give you absolute control over the surface finish and then make the mold in silicone. People making statue heads etc regularly do this high gloss finish molding, you could check the art forums for resin casting statue techniques or check some of the resin suppliers have online tutorials on making high quality molds and casts.


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