I have 'B' bound to 'Select Category 7' (the blueprint hotbar category) and 'Shift-B' bound to 'Blueprint Library'. Pressing 'Shift-B' opens category 7 and does not open the blueprint library. (Pressing 'B' opens category 7 as normal)
tl;dr
Bindings
B - Open Category 7
Shift-B - Open Blueprint Library
Results
Pressing Shift-B opens category 7