See:

• https://support.mozilla.org/kb/troubleshoot-SEC_ERROR_UNKNOWN_ISSUER

If you can't inspect the certificate via "Add Exception" then try this:

Open the "Add Security Exception" window by pasting this chrome URL in the Firefox location/address bar and check the certificate:

• chrome://pippki/content/exceptionDialog.xul

In the location field of this window type or paste the URL of the website with the https:// protocol prefix (https://xxx.xxx).

• retrieve the certificate via the "Get certificate" button
• click the "View..." button to inspect the certificate in the Certificate Viewer

You can inspect details like the issuer and the certificate chain in the Details tab of the Certificate Viewer. Check who is the issuer of the certificate. If necessary then please attach a screenshot that shows the Certificate Viewer with the issuer.

You can also do a malware check with several malware scanning programs on the Windows computer.

• https://support.mozilla.org/kb/troubleshoot-firefox-issues-caused-malware

Please scan with all programs because each program detects different malware. All these programs have free versions.

Make sure you update each program to get the latest version of their databases before doing a scan.

• Malwarebytes' Anti-Malware:
  http://www.malwarebytes.org/mbam.php
• AdwCleaner:
  http://www.bleepingcomputer.com/download/adwcleaner/
  http://www.softpedia.com/get/Antivirus/Removal-Tools/AdwCleaner.shtml
• SuperAntispyware:
  http://www.superantispyware.com/
• Microsoft Safety Scanner:
  http://www.microsoft.com/security/scanner/en-us/default.aspx
• Windows Defender:
  http://windows.microsoft.com/en-us/windows/using-defender
• Spybot Search & Destroy:
  http://www.safer-networking.org/en/index.html
• Kasperky Free Security Scan:
  http://www.kaspersky.com/security-scan

You can also do a check for a rootkit infection with TDSSKiller.

• Anti-rootkit utility TDSSKiller:
  http://support.kaspersky.com/5350?el=88446

See also:

• "Spyware on Windows": http://kb.mozillazine.org/Popups_not_blocked