Those conversations, beyond just delighting your customers, are where you really learn the most about them and their needs. It’s where you get to live their pain and understand what you can do to build a better product. I’d recommend being ready to jump on the phone with someone the moment they reach out for help.
Also, you can be honest about out of hours times - people understand that you can’t be there at 1am (though, lord knows I’ve done plenty of support with customers on the other side of the world at that time). But if you’re a tiny company getting established, you’ll be on hand at all hours, even if it’s a bit antisocial. Nobody is as loyal a customer as someone you’ve bent over backwards to help late at night or on a Sunday afternoon.