I have had great results with long exposures with Astia 100F, Velvia 50, even E100VS and Rollei 400IR films for long exposures. For color shots after sunset, my choice is Astia 100F (both MF and 135). I like how it works with the blues and purples of the setting sky.
For very long exposures and for general long expsosure use, I like Velvia 50. After 20m or so, it is a little more sensitive to blue but overall, the colors are pretty much together. I found that a shot that meters at 20mins will need another stop (40mins)
When you get an ND filter, realize they all do some sort of color shift. Better ones less so. This will be up to your preference...for me, the NDs I have, the shift is pleasing. But when you find one, do some research and see if it is okay with you.