Hi,
For performance, the columns of tables in MySQL can be restricted to some type.
For example if you use the type "integer" in a column, you can only use a number in it.
Searching for a number is several orders of magnitude faster that searching for text.
Similarly, by default, the discount_user_id column of the hikashop_discount table uses the "varchar(255)" type, which means that you can only have 255 characters in it.
Since the number of characters is reduced, you can only enter a couple of users in the corresponding setting until you reach the 255 characters limit.
However, MySQL will be able to process the queries much faster than if the type was "text" or "longtext" which allow for more characters.
So to allow more users to be selected there, you can just change the type of the column to "text" via your PHPMyAdmin. Some of the queries will be a bit slower, but for most stores, it won't be noticeable.
However, I don't think this is necessary. What you could do instead is create a specific user group for that discount, restrict the discount to this user group instead of restricting it to users, and then add the user group to the different users for which you want the discount to be usable. This way, you can have as many users as you want for a discount and I don't see any disadvantage of doing it like that.