(I know this thread is a bit old but if anyone else wants to know)
Tldr: It seems to be multiplicative sadly.
I thought the rune might be OP with teemo since he can stack it up so fast, found that he could get shrooms down to 9.4s charge time, and have up to 35 shrooms on the map at once, but you can get it down to 12s with normal 40% cdr so its probably not worth...
Anyway the maths:
lvl3 teemo ult has 20s charge time normally
with 45% cdr + 15% from Ultimate hat was 9.4s
If it was additive:
20 * (1-0.6) = 8s cd
If it's multiplicative:
20 * [ (1 - 0.45)*(1 - 0.15) ] = 9.35s cd (which rounds to 9.4s)