No - I've not been using MS Print to PDF but I have an update...
I searched M-Files on that part number 'a11a477*' and it threw up three files all with the same name, all created at the same time, but one with a recent modification.
That file opened OK.
The others give the error message when I try to open them. I notice they do not show a preview and they have no 'relationships' or version history.
I think I'll risk deleting the two rogue files.