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its probably unrelated to your CSS and more to do with the PHP. I use frontpage XP and my first experience of PHP Was yesterday. Most files open in FP, but with PHP they open in notepad.
Check out the options in the software you use and it may have options for "default editors" in regards to file extensions
I could be wrong though, could be the CSS, as i say, im a PHP newbie :)
I have my Homesite settings set to use IE as the internal browser, and the page looks fine that way. It's when I click on the view external browser that the page displays fine in NN6, but in IE notepad opens showing the code instead. If I type the local file path/url into IE it works ok, although I could have sworn that last night even that didn't work. I'll just have to keep typing in the file name and click refresh to test changes as I'm working on it locally. When I uploaded a test copy to a server I didn't have any problems with it in either browser. And most importantly, the CSS worked the way I wanted it to - so far anyway!