It depends, I've often found that keys used during the leveling process are quite useful as they speed things up, particularly when you're on the first character. Furthermore, at max level, you're in the "end game" and you must farm unique items, the purples found with keys just don't cut it anymore.
I just use them randomly, if you follow Randy Pitchford on twitter you will get way too many codes to use when you hit max, I had 30 at one point in BL2.
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