What large caches of undigitized content exists? Surely, not everything has been digitized, but I can’t think it’s much in percentage terms.
The Vatican Library contains roughly 1.1 million printed books and around 75,000 codices, only a small percentage of which have been digitised.
The amount of private data that is locked up inside private internal databases is huge. This is especially true of regulated industries. There is a wealth of data - financial data showing how to budget for things, pricing data on various products that are B2B, standard operating procedures at mature companies that have gone through various revisions, designs for manufacturing plants so people don't keep reinventing and making the same mistakes again, and on and on.