If you can't do the calcuations in a database, this might work:
list($hour_in,$min_in,$sec_in) = explode(':', $time_in);
list($hour_out,$min_out,$sec_out) = explode(':', $time_out);
$valid = TRUE;
if($hour_in > $hour_out)
$valid = FALSE;
elseif($hour_in == $hour_out)
if($min_in > $min_out)
$valid = FALSE;
elseif($min_in == $min_out)
if($sec_in >= $sec_out) // >= because if they are equal, times are the same
$valid = FALSE;