Your question is tough to answer because of the variables. I choose Kydex, but for very specific reasons.
Generally Hybrid holsters are the most comfortable for continuous wear. On the down side, a big flat piece of leather doesn't breath very well, and is guaranteed to make you sweat. Cow hide will breath better than horse hide, and horse hide will also feel more oily. There is a hybrid available with a cow suede backing that will breath better than the others, and a new one coming out with a pig suede backing that will function even better than the cow suede.
There are many variations of Kydex holsters. A Kydex holster with a small footprint and rounded edges will not create as much sweat. Unfortunately mostKydex holsters have sharp or squared edges. There are a few that are very comfortable, but the vast majority will pinch, scratch, and poke you unmercifully.
Leather holsters can be comfortable if some forethought has been put into the design. Again as with Kydex, there are more uncomfortable IWB's than there are comfortable.
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