In this situation, once I had a UserRole object, I would usually just call userRole.getUser() or userRole.getRole() to access one entity or the other, depending on which way you are trying to go.
For example, use something like
Code:
Role role = RoleDAO.getById(new Integer(1));
Iterator it = role.getUserRoles();
while (it.hasNext) {
User user = (User)it.next();
user.sendEmail("Hi There, " + user.getFirstName());
}
But I'm no expert at all. This may be kludgier than is necessary. Try it and see if it suits your need.
If you want to explore further for something a bit more elegant, you can try putting a many-to-many relationship inside a set or list. But I think this only works in one direction. Hibernate In Action shows (briefly) how to do this.