I think what you want is the full join with an additional condition. Something like:
select F.ID, F.AE_CCY, F.DRCR_IND, F.AMOUNT, F.MODULE, F.ACC
from account a join flex f
on substr(a.ACC,1,4) = substr(f.ACC,1,4)
where a.AE_CCY <> f.AE_CCY
or a.DRCR_IND <> f.DRCR_IND
or a.AMOUNT <> f.AMOUNT
or a.MODULE <> f.MODULE
or a.ACC <> f.ACC
This way, the join is still performed on the first 4 characters, but the where condition checks the entire field (as well as the other four).
Revised solution: This is something of a stab-in-the-dark, by I'm wondering if what you're really looking for is a list of records that don't have a match in the other table. In that case, a full outer join might be the answer:
select coalesce(F.ID,a.ID) as ID,
coalesce(F.AE_CCY,a.AE_CCY) as AE_CCY,
coalesce(F.DRCR_IND,a.DRCR_IND) as DRCR_IND,
coalesce(F.AMOUNT,a.AMOUNT) as AMOUNT,
coalesce(F.MODULE,a.MODULE) as MODULE,
coalesce(F.ACC,a.ACC) as ACC
from account a full outer join flex f
on substr(a.ACC,1,4) = substr(f.ACC,1,4)
and a.AE_CCY = f.AE_CCY
and a.DRCR_IND = f.DRCR_IND
and a.AMOUNT = f.AMOUNT
and a.MODULE = f.MODULE
where a.id is null
or f.id is null
Third attempted solution: Thinking about it further, I think you're saying that you want each record from the first table to match to exactly one record in the second table (and vice-versa). That's a difficult problem because relational databases aren't really design work that way.
The solution below uses the full outer join again, to get only rows that don't appear in the other table. This time, we're adding ROW_NUMBER to assign a unique number to each member of a set of duplicate values found in either table. In the example from your comment, with 5 identical rows in one table and 1 of the same row in another, the first table will be numbered 1-5 and the second will be 1. Therefore, by adding that as a join condition, we assure that each row has only one match. The one flaw in this design is that a perfect match on ACC is not guaranteed to take precedence over another value. Making that work would be quite a bit more difficult.
select coalesce(F.ID,a.ID) as ID,
coalesce(F.AE_CCY,a.AE_CCY) as AE_CCY,
coalesce(F.DRCR_IND,a.DRCR_IND) as DRCR_IND,
coalesce(F.AMOUNT,a.AMOUNT) as AMOUNT,
coalesce(F.MODULE,a.MODULE) as MODULE,
coalesce(F.ACC,a.ACC) as ACC
from (select a.*,
row_number()
over (partition by AE_CCY,DRCR_IND,AMOUNT,MODULE,substr(ACC,1,4)
order by acc) as rn
from account a) a
full outer join
(select f.*,
row_number()
over (partition by AE_CCY,DRCR_IND,AMOUNT,MODULE,substr(ACC,1,4)
order by acc) as rn
from flex f) f
on substr(a.ACC,1,4) = substr(f.ACC,1,4)
and a.AE_CCY = f.AE_CCY
and a.DRCR_IND = f.DRCR_IND
and a.AMOUNT = f.AMOUNT
and a.MODULE = f.MODULE
and a.RN = f.RN
where a.id is null
or f.id is null