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SL was designed prior to published app technology and when SL is set up as a published app, it will begin by re-directing the local printers and initializing them. This appears to be set to a fixed amount of time rather than when the task is done. So users with many printers can sometimes run into a situation where SL has not yet completed parsing through the list of printers but moves on to the next task during login/start up. When this happens, SL may not recognize the printer that the user is trying to use and will default to the first one in the list/local printer/something other than what the user wants.
Starting in SL 2011 (no service pack required), you can use a solomon.ini setting to build in a delay that you can customize to allow adequate time to redirect all printers:
[miscellaneous]RemoteAppDelay = <value between 0 and 99 seconds>
So for instance, if I thought a 7 second delay would do the trick, I would add the following to my solomon.ini file:
[miscellaneous]RemoteAppDelay = 7
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