Bom dia.
Problema com SSL
O UniNFe está tentando fazer a comunicação com a sefaz mas algo está impedindo, pode ser proxy, firewall, antivírus, instabilidade na Sefaz ou problema de DNS, tente o seguinte.
1) Atualize o UniNFe
2) Reinstale o certificado digital
3) Confira se a cadeia do certificado digital está correta, pode estar com falha.
Problema com DNS
1) Desligar modem de internet e ligar novamente
2) Desligar o computador que tem o uninfe rodando
3) Se os anteriores não resolver, troque o servidor de DNS para 8.8.8.8
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