Where the 80% comes from is in the conductor ratings. If you have a 100A load, you pick a cable that has a rating which is 125% of that load, or 125A in this case. So if you have cable rated for 125A, you protect it with a breaker rated 125A, but you can only load that cable to 1/125%, or 80% (do the math). So knowing that, breaker manufacturers know that a standard breaker will only be loaded continuously to 80%, and they build them accordingly. As mentioned, you can load them to 100% temporarily.
If you need 100% out of a circuit, you can buy what are called "100% rated" circuit breakers in larger sizes, but the conductor issue gets trickier.