I believe the first carbon fiber production frame was a Graftek, made by Exxon. I think it came out in 1983 or so. Greg LeMond rode a carbon fiber Look frame (rebadged from time to time) in most of his tours.
It's funny how all the new high-end alu frames now have...carbon stays????
OK...it Graftek came out in the 70s'...here is a link...
http://www.classicrendezvous.com/USA/Graftek.htm