You say this is on an intranet?
I would be hesitant about using the IP addresses for a couple of reasons.
1) If your company uses DHCP, then there is a chance (albeit a slight one) that the machine's IP address could change when its lease expires. This will wreak havoc on your code.
2) If the user tries to log into a different machine, then access the site, the validation would fail because it is a new IP address (even if it is the same user name)
Now, to answer your original question:
php may have a way of validating against Windows NT Authentication procedures (I know ASP does, but then again, it is all WIndows then anyhow) I would go there though, unless you are the admin, because it may tick off a few admins in your company.
You can use an Exchange server (if your company is like mine and uses the same domain vaildation for email addresses), and export the data to ACCESS. Then use php with ODBC connectivity to generate a list of user names that way to validate against. This can be automated without going into the registry (depending on the OS), but I am not 100% sure of how to do this.