I think the phrase after hours is adverb, so it cannot be used in the sentence below as it needs a noun.
What's the suitable noun?
The closing time of childcare centers is usually earlier than after hours of companies.
There isn't really anything convenient. But even if there were, this is a very roundabout way of saying
Childcare centers usually close earlier than (most) companies.
I'm guessing that what you mean is
Childcare centers usually close before parents can leave work.