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The following answer assumes your working on a PC running XP or before.
As far as I recall, the folders are stored as hidden database files in hidden folders in the maze of folders under where your 'my documents' folder is stored. Sorry to be so vague but it's been some months since I moved to using Thunderbird (exports and backups are much easier)!
First step would be to change your windows view options to show hidden files and folders.
Then look for My Documents under your user on the hard drive (not the shortcut from the desktop but the _actual_ folder location). In the same directory will be folders labeled something like application data. Follow your nose through microsoft and outlook express to find a folder called 'identity{long string of alphanumerics}'. If you have more than one outlook express identity there will be more than one folder.
Back up that folder to back up your emails and OE folder structure.
Hope that helps,
Tess
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