@Toby Austin thank you for reporting this issue. Would it be possible to share the app URL so we can investigate further? We have a similar issue reported on GitHub
After diving further into this, it turns out that the ISP had blocked the domain due to phishing concerns. We believe this is happening as new SWA's may have the '.1.azurestaticapps.net' subdomain. This new subdomain is a side effect of architectural improvements and for the most part should be transparent to interactions with SWA.
If you are hitting SSL_PROTOCOL_ERROR or hitting DNS issues when reaching the default hostname of your SWA, you may need to contact your ISP to allowlist your domain as they may have incorrectly flagged it.
We will keep this issue open so others may comment if they are hitting similar issues with their ISPs.
Would you mind sharing what's your internet provider?