Be very very careful when raising the "has he been inappropriate with you" discussion. It might just put ideas into her head and lead to a slippery slope from which there is no return. I wouldn't even go there. If he has done or said anything to make her feel uncomfortable, she is old enough to speak up without prompting.
It's not as though he has been inappropriate with her but she is holding back so as not to hurt your feelings - it's clear that her treatment of him is already hurting you and she doesn't seem to care.
I say not to let it bother you. She's regressing into her teenage self, and her behaviour is her responsibility. Your man sounds lovely but perhaps he's trying too hard to "fit in". Ask him to give her a wide berth and see how she reacts - it might unnerve her that he is the one giving her one-word responses (if she does speak to him at all, that is).
Far more healthy for you to develop your 'couple' relationship rather than a 'happy family' relationship.
In danger of becoming estranged from adult children
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