I would want more than 5, all Hot Toys, but lets assume that each of the 5 I pick would represent a complete new line or indeed a continuation of an existing line:
1) Batman (1989)
2) Mike Harrigan (Danny glover, Predator 2)
3) Battle damaged T-800 - complete damage by end of film (T2)
4) T-800 - tech-noir scene (The Terminator)
5) Alien Queen
Let us also assume full likeness rights are acquired for each.
and figures/licenses that would make up my next 5....
6) Commissioner Gordon (gary oldman, I still hope)
7) Battle damaged Robocop (1st film, though peter weller doesn't allow his likeness used does he? If so then just accurate BD up to point before he removes helmet)
8) Spiderman (Tobey maguire)
9) Hulk (Ed norton's version more feasible I suppose)
10) Daredevil (Ben affleck - controversial choice, especially in light of who I'm omitting for it*, but it would make a good HT figure)
*coughchristopherreevesupermancough* - only because superman has kindasorta already been done, though I would definitely buy him if he happened to come along first