Javier,
One more try. This isn't perfect or look pretty but it does work (for me). My approach was that if user could browse he could then check Hotmail from browser. Here is what I did. It hopefully will work for you.
POP3 Filter
Not Client application name equals "msimn"
Server port number equals 110
impuestos Filter
Not Client application name equals "iexplore"
Server IP address equals "63.99.224.52"
Hotmail1 Filter
Server IP address contains "207.68.17"
Not server IP address equals "207.68.176.190"
Not server IP address equals "207.68.179.219"
Hotmail2 Filter
Server IP address equals "64.4.33.7"
Hotmail3 Filter
Server IP address contains "65.54.2"
Hotmail4 Filter
Server IP address equals "65.54.192.248"
Hotmail5 Filter
Server IP address contains "64.4."
Hotmail6 Filter
Server IP address equals "207.68.162.250"
User can browse to
http://sea1fd.sea1.hotmail.msn.com and then login. However, there is a range of addresses that user could still browse to. I think that the user would have to stumble across them accidentally though. Try it if you like and see what happens.