First appearance (Usagi): Act 2
First appearance (Ami): Act 3
First appearance (Rei): N/A (although she definitely has one)
First appearance (Makoto): N/A (although she definitely has one)

Usagi and Ami each get free entry to Karaoke Crown by showing this card (with Luna's picture on it) to Motoki, who doesn't quite grasp that they are obviously fake. They use their free entry to go into the secret hideout at Karaoke Crown.

Anime/Manga Comparison:
This has no basis at all in the anime or manga.