I will exclude moments that can be seen as only friendship moments, no romance intonations at all.

[spoiler]
1.) When he dragged her along in Hargeon and told her to 加入 Fairy Tail
2.) When she held him back during the Lullaby arc
3.) In Galuna Island when he saved her from the poison
4.) When he went for her rescue in Phantom Lord arc
5.) When he caught her when she was falling out of the tower and she yelled out his name, being sure that he would be there to catch her.

(OMAKES)
link
1.) Happy in Boots: She's a princess and she falls in 爱情 with him without even knowing him, but he has become barbaric...