The ROUTE command can be scheduled with "Scheduled Tasks". If you use ROUTE to DELETE, then the PC's connection to the network -- and EVERYTHING it talks to is disabled. Use ROUTE with the ADD option to restore.
The hosts file is like the opendns solution. It does not shutdown access, but it tells any future programs that it can't find the destination. I have not used it to schedule access to sites, so I'd use the hosts file to solve that problem.
A value that opendns offers -- you can tell it to takes its like of inappropriate sites, and not give out IP addresses to any of them. The kids computer can be configured this way and your computer can be configured with the old DNS server. But access to the network is still in place with opendns or with the hosts file.
I've not tried it, but you should be able to use the ROUTE command to disable access to some sites. Find out the address of one site "nudesonice.com" might be 66.77.88.99. And then do a ROUTE ADD to redirect all network requests for 66.77.88.* to 127.0.0.1. When you want to restore access, you can ROUTE DELETE this entry. This will allow you to selectively cut off access to parts of the internet.
Other things I use:
Microsoft Live Family Parental Control has a program that runs on the computer, and it allows restriction by application, web sites, instant messaging, email, allowed address for those programs, etc. It can be scheduled to lock out accounts on the system.
Norton 360 has a similar program. I use both Norton and MS Live Family as double protection.