Firefly from Ace Combat: The Equestrian War, most definitely. There are times she acts really cold toward other ponies, especially Fluttershy at the beginning (going as far as to slap her!), as well as Derpy and Medley later on. But deep inside, she's just a troubled mare, trying to readjust herself to the circumstances around her. RainbowDash is there to help her.
In Legend of link:lucky number 13 Ganondorf shows shades of this. Mainly towards his daughter Separuu. He even goes so far as to sacrifice his own soul to save the one his daughter loves, which is the one he hates the most, Link .