I too have a similar issue. I did post here an hour ago thinking I had a workaround. This turned out to be a fail in the end.
Below is my post from this topic "BSOD stop code on Windows 10 start (RDR File System - mxrsmb20.sys) after installing Synology 218+" https://answers.microsoft.com/en-us/windows/forum/all/bsod-stop-code-on-windows-10-start-rdr-file-system/6e2bafea-8ad8-4372-9ca1-e84203999405?page=1 which could be of some use.
I too have a Synology (DS916+) which I offload excess data for Domain users which hoard too many files. I thought it was this "rdr_file_system 0x27 BSOD After Windows 10 2004 update, but only on domain profiles" from here https://answers.microsoft.com/en-us/windows/forum/all/rdrfilesystem-0x27-bsod-after-windows-10-2004/c34f5703-1367-4788-a4f3-2d75f7dfaa07?page=1 which sadly it is not.
I offline these files on the Synology for some users who insist having access to everything. I also offline their My Documents which is being redirected to my Server 2016 Domain Controller (and for some to a crusty old SBS2008 that is waiting to be decommissioned).
Formatting the CSC cache to zero the state and only making My Documents offline does not produce the BSOD. Adding the Synology target back as well does make it BSOD. I would guess then there is something broken when trying to spin up Offline Files that come from the Synology. I did initially get a strange error on one machine I configured last week implying a security mismatch of sorts related to the Synology location which I dismissed and failed to take complete note of what it was describing.
The Synology is up-to-date.
The Windows machines that fail are build 2004 and are up to date.
Entering user credentials to start the logon process will create the BSOD once the authentication process starts.
This does not occur if the offending WIN10 machines are connected to the Domain network and the Synology hosted files are deemed Online.
I read that giving the Windows machines ANY network to access will allow successful login; I got only so far with that suggestion but cannot fully say that is a viable workaround as it seems to me the files made offline from the Synology are broken somehow. When I "fix" this issue the BSOD returns. I tried installing the Microsoft Loopback adapter to fake an always connected network but that trick broke once I "fixed" the offline file issue with data made offline from the Synology.