It may have come from the movie "The Core," when Delroy Lindo is describing the ship needed to go to the Earth's core, which can only theoretically be built. When someone asks him what it would be made of, he said, "The real name has 37 syllables, but I just call it... unobtanium."
The use of the word "blue" to refer to sexually explicit content was first recorded in Scotland in 1824. "Blue" meant "lewd" because prostitutes dressed in blue gowns.