To be honest there is absolutely no hazard in typical building installations when #14 NM-B is subjected to 20amps (as is NEC ampacity tables are highly conservative), the fact the CEC lets you go that route would be actual real world proof.
Some possible theories behind 240.4 (D) are that small conductors are frequently found on multi outlet circuits where overload is likely. Most breaker trip curves start at around 125%, and under UL standards a typical residential breaker is not even required to trip at that threshold. Thus, it is theoretically possible to load #14 to 25 amps continuously without tripping a breaker where as 125% of 15 is 18.75 amps. Small conductors are also the most likely to be mis-used by unqualified personnel, ie over filled conduit or bundling without appropriate de-rating. Other possibilities are hold overs from rubber insulated wire days where insulation was nowhere near as good as it is today.
Another motive for 240.4(D) might be voltage drop. While code does not enforce voltage being merely a FPN, it could be another motive to seal the deal so to speak. Picture a 100 foot home run to a kitchen. At 120 volts, 20amps, unity power factor, ambient at 86*F, the voltage drop is about 6.2%. Same scenario with #14 is 10.4%. An extra 4.2%.