You can modify Judge assignments at any time- before, during, and after your competition. 

RocketJudge signature auto-assignment algorithm kicks in when you click "Check In" next to a Judge's name (or when they click "Check In" themselves for Judge self-check in), so unless you do manual assignments, there will not be assignments to modify before the competition begins/check in starts. 

We do not recommend modifying Judge assignments after the Competition ends, because you might accidentally delete Judge evaluations. Deletions are permanent.  
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Learn how to change judge assignments here.