in reply to Re^4: Net::SMTP - Connection to local MTA refused
in thread Net::SMTP - Connection to local MTA refused

Turn on verbose logging in Postfix, or try some of the other things on this page.

Your logs show pretty clearly that it's postfix closing the connection (assuming apparmor and similar aren't doing it), so this should unearth something

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Re^6: Net::SMTP - Connection to local MTA refused
by Robidu (Acolyte) on Jun 04, 2017 at 06:55 UTC
    The issue had arisen, because I'm using a self-signed cert for Postfix, but that had been rejected. Making the fingerprint of said cert known to IO::Socket::SSL (and subsequently Net::SSLeay) made it accept the cert without complaint, and now the TLS runs smoothly. Thanks for your effort.