Here a sample a code that make correct NTLM authentification it's use the last libwww version (5.64 i hope): Note that the keep_alive => 1 is important NTLM authorize TCP/IP connection and not request Hope that help you...

#Libraries inclusion
use DBI;
use LWP::UserAgent;
use HTTP::Headers::Util;
use DBD::Oracle;
use Crypt::SSLeay::MainContext;
use Net::Ping;

# For NTLM authentification
use Authen::NTLM;
use LWP::ConnCache;
use HTML::HeadParser;

#User Agent declaration
$ua = new LWP::UserAgent( keep_alive => 1);

    my $req = new HTTP::Request GET => $addrTxt;
    #$req->content_type('application/x-www-form-urlencoded');
    #$req->content('match=www&errors=0');
    #Pass request to the user agent and get a response back
    my $res = $ua->request($req);
    #Update into url table the url link status depending on the previo
+us test
    #Null for success and 0 for failure
    
    if (!$res->is_error) {
        # URL is OK
        undef $nul;
        $updateStatus->execute($nul,$linkNo) or die "Couldn't execute 
+statement: " . $dbh->errstr;
        next;
    }
        
    # URL En erreur
       if ( $res->status_line =~ /^401/ && $res->headers()->header("WW
+W-Authenticate") eq "NTLM" ) {
            # Try the NLTM Authorization

            ntlm_user($tableParam{"NTUser"});
            ntlm_password($tableParam{"NTPass"});
            ntlm_domain($tableParam{"NTDomain"});

            $headers = new HTTP::Headers();
            $headers->header("Authorization" => "NTLM " . ntlm());
            $request = HTTP::Request->new('GET', $addrTxt, $headers);
            $response = $ua->request($request);
            $headers = $response->headers();
            $auth_type = $headers->header("WWW-Authenticate");
            if($auth_type =~ /^NTLM (.*)$/) {
                $chal_resp = ntlm($1);
                $headers = new HTTP::Headers();
                $headers->header("Authorization" => "NTLM " . $chal_re
+sp);
                $request = HTTP::Request->new('GET', $addrTxt, $header
+s);
                $res = $ua->request($request);
                if (!$res->is_error) {
                        # URL OK
                        undef $nul;
                        $updateStatus->execute($nul,$linkNo)
                            or die "Couldn't execute statement: " . $d
+bh->errstr;
                        next;
                }
            }
        }
        # Url In error
        write_error_log("$linkNo - $addrTxt - " . ($IsLocal ? "Local" 
+: "Remote") . " - " . $res->status_line);
}
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