Ali, I can only say what works for me, and I use slow-sync a lot for social events where a bit of movement coupled to some ambient light in the background is nice. Expressions and gestures are very quick, spontaneous and fleeting, and I find the best way to capture them is absolutely as soon as possible, ie first curtain sync. If any part of the ambient light image "seems to lie on top" of the flash exposure, the only way to reduce this is to use a shorter ambient exposure time, to darken the background; first or second curtain sync will not affect it.
Dalex, I understand what you're saying now, sorry, my mistake. Yes, if the exposure is long enough for the subject to have reopened their eyes after whatever made them blink in the first place, and then the flash fires completely unannounced, you've got 'em!