Hmmm... it could be that for some reason one of your security programs (anti-virus? firewall?) is blocking port 995.
Other than that, I don't have a clue, sorry.
What you could do is testing the POP3 access via Outlook, in case you have Outlook of course. See the next URL for instructions:
http://windowslivehelp.com/solution.aspx?solution...-bba6-8072406b3fb7
(ps: you don't need to install Outlook Connector as suggested though)
Or, if you have Outlook Express:
http://www.windowslivehelp.com/solution.aspx?solu...-9cdf-172002d4194c
If those fail too, then all you're left with is making a post on the official Windows Live Solution Center > Hotmail:
http://windowslivehelp.com/post.aspx?productid=1&...t.aspx?productid=1
And aks why you can't access your Hotmail account via POP3.