That is the Call far instruction, it takes an absolute address that has a value both for the code segment and instruction pointer.
Ref: http://x86.renejeschke.de/html/file_module_x86_id_26.html
9A = Call far instruction
45 00 = Value for code segment (0045)
5F 9C 45 00 = Value for instruction pointer (00459C5F)