i = pd.date_range('2018-04-09', periods=4, freq='1D20min')
ts = pd.DataFrame({'A': [1, 2, 3, 4]}, index=i)
ts
                     A
2018-04-09 00:00:00  1
2018-04-10 00:20:00  2
2018-04-11 00:40:00  3
2018-04-12 01:00:00  4

ts.between_time('0:15', '0:45')
                     A
2018-04-10 00:20:00  2
2018-04-11 00:40:00  3

You get the times that are not between two times by setting start_time later than end_time:

ts.between_time('0:45', '0:15')
                     A
2018-04-09 00:00:00  1
2018-04-12 01:00:00  4