I recommend setting yourself up on retainer with them. You put in writing, "I will provide X hours of tech support per month for $xxx paid in advance at the beginning of each month, and unused hours do not roll over."
Then decide what's the minimum increment of time that you'll debit against their account. Send the customer a statement that reads like this:
mm/dd Call from Joe regarding e-mail 0.25 hour
mm/dd Call from Jill re lost file 0.25
mm/dd E-mail support re Jill's file 0.5
Then show the hours available minus the hours used.
If they go over the number of retainer hours in a month, do you charge extra automatically, or do you have a fudge factor, i.e., "$600 per month gets you 10-12 hours of support." Anything above 12 gets billed at $65/hour.
Then they'll think twice before they call you for every little thing. Your services will be perceived as more valuable, and they'll "save up" the important issues, knowing they'll have to pay.
I have used this model and customers like it because when they pay you a retainer, they feel like they own a piece of you, they feel confident that you'll get back to them within 24-48 or whatever SLA you establish. The alternative, if you're doing stuff for free, is that they don't own you, and you'll get back to them whenever you can.
But just answering the phone or e-mail ad hoc anytime they have a question? Never give that away for free. Your time is worth a dollar an hour for that kind of work, at least.