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An OnDemand scan may find viruses that OnAccess missed because it wasn't yet in the definitions at the time the computer was infected, or the file put on the computer.
We're more aggressive with the On-Demand scan since we run it every night on our client's machines. We decode mime files and scan down inside of zip files where with the on-access we're not as aggressive. This keeps their machines from being bogged down as much. Not matter how good the tech gets it's still a pretty nasty performance hit to a system.