Seems like a good time to unionize is when you don't need it, while the job is good. Get the union in place and work through issues like on-call, laying out actual articulable and measurable performance targets for review time, work-life balance rules and other "small" things while the job is good. That way when the money grubbing starts, the true horror-show policies are attempted, etc - you have an established union and a better bargaining position. Better than waiting until the job is shit and having to fight an uphill battle all the way.
i've recently been thinking about when in a start-ups lifecycle should employees consider unionizing.
it'd be great if a worker-friendly culture was instilled in the company from its earliest days, but i'm not sure if a) there's an effective minimum size needed to unionize or b) if the existence of a union would kill your ability to fundraise in the future