_BIN will order in the binary (ASCII order) of characters while CI_AS will use dictionary order with case insensitivity and accent sensitivity so BIN will treat "A" and "a" as different characters and order them accordingly and sort the alphabet in this order.
...XYZ[]^_`abc
That is the characters will be sorted by their ASCII code values
As a simple test
declare @Chartable table (character char (1))
insert into @Chartable (character)
Values ('a'),('A'),('z'),('Z'),('_'),('æ'),('Æ')
SELECT character COLLATE Latin1_General_BIN
from @Chartable order by character COLLATE Latin1_General_BIN
SELECT character COLLATE Latin1_General_CI_AS
from @Chartable order by character COLLATE Latin1_General_CI_AS
SELECT distinct character COLLATE Latin1_General_BIN
from @Chartable order by character COLLATE Latin1_General_BIN
SELECT distinct character COLLATE Latin1_General_CI_AS
from @Chartable order by character COLLATE Latin1_General_CI_AS