Technically, the Court can make such an order if deemed to be in the best interests of the child, but it never actually has because it has never determined that such an order is in any child's best interests. Children have a right, after all, to have a meaningful relationship with people other than just the parents, including siblings, grandparents and step-parents, etc.
Likewise, the Court has consistently held that unless a particular individual poses a risk of harm to the child in question, then orders restricting who the child spends time with while in the care of either parent is an act of 'micro-management' which interferes with the 'day-to-day' decisions about the child's care, welfare and development for which each parent is solely responsible when the child is in their care.
So, is an immediate family member caring for the child while the primary carer is at work considered a contravention of the order? Not unless there is an order that explicitly restricts the child from being alone in the care of that family member - e.g. 'That the parents are restrained by injunction from allowing the child X to be left unsupervised in the care of Mrs A'.