Okay, so they're not 100-watt amps then. Thus the comparison is invalid. Just because something is
labelled a 100-watt amp, doesn't mean it is. Which is why measurements matter, as
@Budda said.
If you're measuring 100-watt from a valve amp, and 100-watt from a solid state amp, through the same speaker (same speaker efficiency, same frequency response) then the loudness output should be more or less the same.
All things being equal, a 100-watt valve amp will produce the same output volume at maximum volume as a solid state amp. If they don't, then something else in the signal path is causing that. Watts and power output aren't magic concepts. A watt is a measurement of energy transfer, nothing more.
The perceived loudness of an amplifier can be influenced by factors beyond its power output. For example, the type of distortion it produces, the frequency response, and the speaker system being used. Additionally, people's perceptions of loudness can vary greatly and are subjective, so what sounds loud to one person might not sound as loud to another.
So like I said... I would like to know how exactly this is all being tested. Because the claims put forth do not go hand-in-hand with the physics behind the phenomenon.