Event log and Application log are the golden places to start. I've seen similar and it was due to the scheduled backup starting. Setting an exception to not backup the spooler directory (why would you anyway??) fixed it on that instance.
I had reviewd the logs and could not find correlations between events and the occurrence. Seems like the issue got resolved on its own and the employee can print around 5:08 pm with out the print spoolers crashing on the network printers. Thanks for your suggestions.