Helpful links, if you have bitmap without transparancy. But since you are using a png that is already transparant you don't have to go through all that.
I had no need to play silly games of matching the button color to the form transparancy key. Why do all that?
Set the button back color to transparant.
Set the button FlatStyle to flat.
Place the .png.
Done - get back to writing code.
You have to set the FlatStyle, because otherwise the O.S. theme of 3d style will cause it to do all the fancy glass and reflection effects when painted, thus overriding the transparency. It's one of those things that makes sense in hind-sight but will keep you guessing for a while the first time.