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If you can beat these 3 then you will have 100%.
There are some missions that are incredibly difficult when you try to get an S rank, like Code Talker, and few more.
But the hardest ones are the mission tasks, some missions will become really difficult because of this, like A Quiet Exit but good thing is, they're not that frequent.
So your main concern is a tedious side ops, and gruelling animal extractions especially the ones you rely on cages.
You're gonna have a bit of trouble with only two achievements: Catch all animals, because some don't spawn for ♥♥♥♥ and disarm a nuke, because either hackers leave you with a phantom nuke or there's absolutely nobody available/on your league to raid.
Time required to get all of them = beyond a hundred hours.
I found that to get 100%, you need to play each mission at least 2 times. One to clear S-rank, one to clear all the other objectives for the mission.
Others have said S-ranking Code-talker is hard.. you can blast to the waterfall in your jeep and go up the cracks without them spotting you. Easy. The optional objective, fulton the tank, can't be done with this tac.
The worst thing to do is forget the off-line combat deployments whilst clearing the other things. The last mission takes more than 2 hours and has a success rate of 51%. I had to do it twice. Oh, and the side-ops are just boring fillers. Takes more time to deploy/drive/run there than to do the mission (eg. mine clearing or eliminating the armoured unit near lufwa valley)
I'm not entirely sure I understand your question: Are you talking about the 42 Steam achievements, or about reaching 100 % game completion?