Mother of 3 here. If she's not "On Call," then she is under no obligation to answer your calls. Her personal time is not your husband's to dictate. If she had been working, I could understand the concern, but she wasn't. It's fairly absurd for him to be upset.
If she is a good employee and good to your children it would be best to show her the respect she deserves-- That includes respecting her space and off-time. Confronting her will do nothing but confuse and offend her. It's the recipe for disaster.