app.config is not what you want to use for user data, as it will be stored somewhere in Program Files (which the user should not have write permissions). Instead, the settings marked with a UserScopedSettingAttribute will go into the .config file with the user's area, somewhere in% LocalAppData%.
It seemed to me that the best way to find out what it is is to mess around with the "Settings" tab of Visual Studio (on the project properties pages), and then look at the code that it generates and look in% LocalAppData% to see the file, which it generates.
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