I’m having the same problem.

Since the latest Avast update today to 6.0.1091 Virus definitions 110420-0 I can no longer access any of my Hotmail/Windows Live email accounts.

I’m getting a Network shield URL MAL message and IE message that I’m not connected to the Internet.

I’m going to have to disable the network shield to access my emails apparently.

IE8 and XP Pro.

EDIT. I’ve disabled Network Shield and I can now access Hotmail/Live mail again.