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To get other characters apart from Rukia, Ichigo, Ishida, Orihime and Chad which you get by defauly you have to complete missions in Mission mode. Get the following amount of points which are displayed at the top-right corner of the screen to unlock the corresponding characters.
Unlock Abarai Renji - 03 Points
Unlock Madarame Ikkaku - 06 Points
Unlock Hinamori Momo - 09 Points
Unlock Matsumoto Rangiku 12 Points
Unlock Hitsugaya Toushiro - 15 Points
Unlock Sajin Komamura - 18 Points
Unlock Zaraki Kenpachi - 21 Points
Unlock Urahara Kisuke - 24 Points
Unlock Shihouin Yoruichi - 27 Points
Unlock Soifon - 30 Points
Unlock Kurotsuchi Mayuri - 35 Points
Unlock Kaname Tousen - 40 Points
Unlock Ichimaru Gin - 45 Points
Unlock Kuchiki Byakuya - 50 Points
Unlock Tsumugiya Ururu - 55 Points
Unlock Kurosaki Ichigo (Hollow) - 60 Points
Unlock Kon - 65 Points
Unlock Aizen Sousuke - 70 Points