I believe you're looking for HasMany Through [see it in the CakePHP book], which basically explains that you can add additional fields to your join table, create model for that join table, and associate it however you want.
So, in your responsibilities_roles
table, you'd add an employee_id
field.
Then, you make a model called RepsponsibilitiesRole
and set it to belongsTo
Employee
.
You can literally think of it as model of it's own, because that's what it is - so you can make methods in it, or run finds through it...etc etc etc.