If you want to enforce that a given user can vote for a given product at most once, create a unique constraint over both columns:
ALTER TABLE mytable ADD UNIQUE INDEX (UserId, ProductID);
Although you can use these two columns together as a key, your app code is often simpler if you define a separate, typically auto increment, key column, but the decision to do this depends on which app code language/library you use.
If you have any tables that hold a foreign key reference to this table, and you intend to use referential integrity, those tables and the SQL used to define the relationship will also be simpler if you create a separate key column - you just end up carting multiple columns around instead of just one.