But I applied the following workaround to C:\strawberry\perl\vendor\lib\Crypt\SSLeay\SSL.pm line 1602:

Yeah, wrong move, whatever Net::SMTP::TLS does, there are ways to force a particular SSL version through ENV vars and options without modifying any files .. Re: GET, POST, and openssl 1.0.1

But that made no difference, has anyone got any ideas ?

Find out which certificate is failing to be verified an
1) force skip verification ( ?Re: LWP Can't POST to HTTPS? Re: Long delay with Crypt::SSLeay and LWP )
2) update the expired certificate authority blah blah Mozilla::CA or whatever you're using
3) Find out if your bug has been reported https://rt.cpan.org/Public/Dist/Display.html?Name=Net-SMTP-TLS

yeah, things like that

In reply to Re: Couldn't start TLS: SSL connect attempt failed with unknown error error:14090086:SSL routines:SSL3_GET_SERVER_CERTIFICATE:certificate verify failed ( Net::SMTP::TLS ) by Anonymous Monk
in thread Couldn't start TLS: SSL connect attempt failed with unknown error error:14090086:SSL routines:SSL3_GET_SERVER_CERTIFICATE:certificate verify failed by rich101v2

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