I know this is too late to help any of the old posters, but it may help other with the same question...
Assuming the Zimbra devs don't move the file, the command:
openssl x509 -in /opt/zimbra/ssl/zimbra/ca/ca.pem -outform DER -out ca.der
will generate the CA root certificate you need in order for Windows to import it properly. You can then copy the resulting ca.der file to your Windows box and double-click it (or import it using the wizard.) It will install into the "Trusted Root Certification Authorities" section of your certificates window. Outlook and HTTPS webmail will no longer generate those annoying errors.
Please keep in mind that if the Zimbra CA is pre-generated and not generated at the time of installation, this will open you up to misidentified sites that sign their own certs with the same CA. I don't know if this is the case or not, but would recommend building your own CA if you're unsure.
[SOLVED] Rolling Your Own CA and Installing Certificates in Zimbra
will get that done for you. And you won't have to guess at which ca.pem file to use.
