Strictly speaking, the purpose of a SYSKEY password is not to lock down boot, but only to protect the system account database (the SAM). So the only time you'll be asked for it is when Windows needs to open the account database for the first time.
Now, the whole point of hibernation is that it does not terminate the running OS; it merely pauses it, and later resumes the kernel and all processes completely intact. So Windows doesn't need the SYSKEY password because it already has the SAM open ever since the last time you rebooted.
As for the account passwords – this needs to be enabled in the power management settings:
Open Power Options by clicking the Start button Picture of the Start button, clicking Control Panel, clicking System and Security, and then clicking Power Options.
On the Select a power plan page, in the task pane, click Require a password on wakeup.
If necessary, click Change settings that are currently unavailable.
On the Define power buttons and turn on password protection page, click Don't require a password.
Click Save changes.