I think that the part $(a)$ of proposition $2.4$ of [this paper ](https://arxiv.org/pdf/1506.08962.pdf) shows that for $n$ sufficiently large one can construct a unitary matrix $U=-I_{2}\oplus U'$, which can be decomposed as the product of three positive matrices. For such $U$ we have $\parallel U-I\parallel=2$.