Is the following a “copy assignment operator?”
struct A { const A& operator=(const A&) volatile; };
11.4.5.3 [class.copy.ctor] paragraph 9 doesn't say one way or the other whether cv-qualifiers on the function are allowed. (A similar question applies to the const case, but I avoided that example because it seems so wrong one tends to jump to a conclusion before seeing what the standard says.)
Since the point of the definition of “copy assignment operator” is to control whether the compiler generates a default version if the user doesn’t, I suspect the correct answer is that neither const nor volatile cv-qualification on operator= should be allowed for a “copy assignment operator.” A user can write an operator= like that, but it doesn't affect whether the compiler generates the default one.