There are two main sets of enzymes within malt responsible for converting starch to various sugars.
Alpha amylase converts starch to longish chain sugars that are less fermentable and therefore add to body and mouthfeel. It is optimised by temperatures in the high 60s and low 70s and when optimised, it works quite quickly.
The other enzyme, beta-amylase is able to break starch and longer chain sugars down to very short chain sugars which are almost entirely fermented by yeast and add little to body or mouthfeel. This is optimised by temperatures in the very high 50s all the way to mid 60-ish. It takes longer to do its business than alpha.
These optimal temp ranges are just that - ranges. Therefore while alpha might work great at 68, it will still be (less) active at 64. Beta will still be (less) active at 69.
However as things get towards the hotter end of their range, they will denature. This takes time -it's not instant although the hotter it gets, the quicker the denaturing takes.
Take all those bell curves and summarise - at 66 both alpha and beta are active. The longer you're there, the more shorter chain, fermentable sugars will result (within reason) so longer mash* within range = more fermentable wort.
*until all the available enzymes have denatured