Complete the following tasks to unlock the corresponding effect. Characters that are unlocked by playing Time Attack it doesn't matter if you play Single or Group and the time is not a factor. You can also use continues.

Unlock Ishida Quincy Final Stage:
Clear Story Mission #6

Unlock Hitsugaya Bankai:
Clear Story Mission #9

Unlock Renji Bankai:
Clear Story Mission #12

Unlock Byakuya Bankai:
Clear Story Mission #17

Unlock Ulquiorra:
Beat Karakura Heroes Mach

Unlock Rukia Shinigami:
Clear Time Attack with Kuchiki Rukia

Unlock Hisagi Shuuhei:
Clear Time Attack with Komamura Sajin

Unlock Kusajishi Yachiru:
Clear Time Attack with Zaraki Kenpachi

Unlock Ise Nanao:
Clear Time Attack with Kyouraku Shunsui

Unlock Kurotsuchi Nemu:
Clear Time Attack with Kurotsuchi Mayuri

Unlock Kyouraku Shunsui:
Clear Time Attack with Ukitake Jyuushirou

Unlock Komamura Sajin:
Clear Time Attack with Yamamoto Genryuusai Shigekuni