assuming you have a graphics card
TVPaint (great for freehand drawing)
then you should have at least one of these too
ImageProcessors
1) ArtEffect 4 (very good, especially with the addon plugins)
2) ImageFX 4.5 (nuf said)
additional Paint Programs
1) Photogenics 5 (very good, even if it is quite backwards IMO)
2) FxPaint 2.0 (don't know if this should be instead of TVPaint, but since I Consider TVPaint unmissable...)
3) PerfectPaint (well it is Free)
4) PPaint (well it is also free)