That works securely only if the password storage system itself is secure (e.g., does not run in the same account as the user's other programs) and the user is at least alerted (securely) when a program accesses the stored credentials. Otherwise any unprivileged local exploit would grant free access to all your passwords. Full-disk encryption, by itself, meets the first requirement, but not the second--once the disk is unlocked anything running in your account can read the password list.