I also take readings through out the mash process. Generally at dough in, once temperatures have stabilized and after any salt additions and at each of the temperature steps I sometimes use... I use the Bru'n Water Spreadsheet before hand to see if something might have drifted too far. I try to target mash pH between 5.2 and 5.6 depending on the style.
I also check pH if I notice that conversion has not occurred after 25-30 minutes as a troubleshooting step after an iodine test.
I have not been checking boil pH yet...