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What you are describing sounds as if the "button-over" image doesn't exist (or the path to it has not been found).
If you are using your method you need to export your button using the option Export HTML and Images.
Then, in Dreamweaver, use the Insert Fireworks HTML button and navigate to the HTML with the correct name (not the images).
NB. Just rereading your post and what might be happening is that by pressing the Home button in the preview you are transferring from the temporary preview in Explorer to the "real page" in your files, where the button (or button path) doesn't exist in that state.
Just rereading your post and what might be happening is that by pressing the Home button in the preview you are transferring from the temporary preview in Explorer to the "real page" in your files…
I could bet that is the problem. Maybe you haven’t saved the page yet; or maybe is something with the path to your files, try to use relative paths with the dot syntax to locate files inside your site.
Hope it helps.
I take it you have created a rollover?
If this is the case then I usually use the insert interactive images option in Dreamweaver to insert rollover images. Create two button of your different colours and use this option in Dreamweaver once you have exported them to your hard drive. I find it much easier. The wizard is very easy to use. You browse for your two buttons, give it an alt tag, and also the link for the button, in your case index.htm.
I hope this helps.