Do your pears have a fungal problem?
The only significant disease problem I've experienced with pears is fireblight, which is a bacterial infection.
I've found no need, whatsoever, to spray any of my pears - and I've got upwards of 30 varieties - with a fungicide. Same for insect pests; I don't get enough significant fruit damage from any insect to warrant sprays - but I sure can't say that for the apples in my orchard.
Truthfully, I don't spray anything, anyway, but even if I were inclined to do so, I've seen nothing on my pears that would lead me to feel the need.
If you really need a fungicide, then I leave you to the recommendations of the experts here.

My pears have also never needed a fungicide. I have had problems with fireblight, pear psylla, and bugs in the fruit, but a fungicide will help none of those things.

I got curious about why captan was not labelled for pears and looked it up. A few pear varieties are phytotoxic to captan (d'Anjou in particular), and that is probably why it is not labelled for pears in the lawsuit-happy USA. Its A-OK in Canada.

Scott

Here is a link that might be useful: Pear fungicides