What you witness is known as Black Tar Spot. This year due to the dry conditions many trees have suffered from it. Discussing this, coincidently, yesterday at a tree conference with fellow ecologist, it was a consensual view that we will see more of it affecting sycamores as global warming and dryer summers increase.
It was also the view that it is a resin produced it the leave, the reasons why the trees should only produce it in dry conditions are not full understood.
As yet it is thought that it is not a sign of ill health of the tree. This may change if further observational research finds otherwise.
Whether such research is carried out remains to be seen, as sycamores aren?t an economically valuable timber.
The principle reason it was plopping out so readily, is that the trees are starting to shutdown for the winter, and the sap is no longer running and feeding the leaves. As a result, the internal leaf structure, which has held the tar spot in place is starting to breakdown, allowing the tar to run out.