His duties will be taken on by chief executive Gerd Finkbeiner.
Dr Rall has been with the company since 1995, and was appointed to the board in 2005, and the company said he left "of his own accord".
Manroland supervisory board chairman Hanno Feidler thanked Rall for "his commitment and excellent cooperation over many years ... also for the trustworthy cooperation and wish him all the best for the future".
Rall will leave at the end of this month.
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"This is a repeat of what happened to 1066 Capital t/a Crystal a year ago. They also never put this company in administration.
We are all still left unable to claim the redundancy and notice pay owed..."
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