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@Smallfurry
If you are talking outer layers:-
Probably down to breathability. Gore-tex is one of the most waterproof membranes on the market. Event is one of the most breathable, could try that.
If you are talking base layers:-
Once you overload the wicking function of a synthetic baselayer it will tend to feel cold (ie. you feel the wetness). Merino wool on the other hand will still feel warm depite being wet.
This does not take into account the fact that man made fibers simply irritate some peoples skin. Especially when wet.