Since most old tubs are porcelain, painting the outside of the tub wouldn't soak through to the inside...or am I missing something. Do a google search for paint that don't emit toxins, there's a lot out there.
If it is an old cast iron tub with porcelain then the only reason you would need to paint it at all is if you simply want to paint it for a specific color look. There are epoxy paints available to recoat the inside of the tub so it acts like the porcelain. If there are chips on the porcelain inside or out you will end up with rust from the iron underneath the chip. (I haven't looked closely at a porcelain tub lately--I assumed that was a dipping process and the ceramic is on both sides. If your tub isn't that way then maybe a Rustoleum paint would be best).
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