Look when Harry and Lloyd are in the van and they are talking about what Lloyd sold to the kid. When the camera is based on Lloyd's face, Harry's hair will be blowing around, and when it's on Harry's face the window will be up.
I do, in fact, own a 1990 Ford Econoline 350* Van and they do have vents that and the intakes are set up so that LOTS of air comes in, especially if you have it on vent. Another thing, what about an air conditioner? And another, if the other window is open the air does circulate around the van, and if they're going about 75 mph + it could move your hair.. err... not that I went over the speed limit, because that's against the law.
Nachomac is right. It does happen throughout their van trip. But it is really noticeable right when Lloyd asks Harry to pull over so he can go to the bathroom. When Harry says "we can't stop now", his hair is really all over the place.