From Marion Boddy-Evans,
Your Guide to Painting.
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A. You need to sign an agreement which says you're transferring all rights in an image and that you're relinquishing all your entitledment copyright. Either you or the person buying the painting can draw up originate the agreement.

See this Sample Copyright Assignment form.

You could also sign over only limited rights, such as a once-off reproduction or the right to a very specific use (for example on a T-shirt or card). Be very specific about the rights you are signing over and your payment. Consider whether you want to insert a clause about the rights reverting to you after a certain amount of time or if the company goes out of business.

Go to Full Artist's Copyright FAQ.

Disclaimer: The information given here is based on US copyright law and is given for guidance only; you're advised to consult a copyright lawyer on copyright issues.