That is for your sync login. I think you need to turn it off and see what happens. What do you mean "I use Primary Passwords on important sites." This is confusing.

I use a password for my banking account. And I use a primary password. So when I open my banking page, I get a popup for my primary password. When I open another page such as duckduckgo, since v136 I get a popup for my primary password. This shouldn’t happen.

I have experimented around. It turns out in v136 when I open the browser going to ANY screen, I get the primary password popup. This is a bug!!

I turned off primary password and no primary password password popup appears. If I turn primary password back on, the same problem resurfaces. ALL OF THIS STARTED WITH v136.

Probably it's bug 1946121.

Same. Literally saw this problem show up in v136 when my Mac browser updated as I was using it ---- been irritating me on my Windows version before that and I wondered whether it was platform or extension dependent. Problem shows up in 136 only (both platforms): No Sync, and even on troubleshooting mode.

This same problem started showing up for me a few days ago, probably with the latest update. I never use sync, but found it had been turned on anyway (I use both a desktop and laptop). I turned sync OFF on both computers, and I still keep getting asked for my password on startup. (And by the way, I have to hit ESC twice to get rid of it.)

Could you test the following change. I don't know whether it will have any effect on this problem:

Open the Settings page (called the Preferences page on some installations)

In the tiny search box, slowly type tech until the "Firefox Data Collection and Use" section comes into view

Uncheck the box for "Send technical and interaction data to Mozilla"

What this does is prevent Firefox from uploading configuration data it gathers (about browser settings) to Mozilla. What I don't know is whether it will prevent Firefox from gathering the settings data and storing it locally anyway, since gathering the data seems to be causing this problem.