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Ultimate Equipment clarifies the rules for masterwork tools somewhat; the relevant section of the PRD is here.
Basically it boils down to:
* Any skill that doesn't already have a specific named tool
* +2 circumstance bonus
* Either:
- Limited number of uses (most likely 10, like the disguise kit and healer's kit)
- Only applies to certain aspects of skill
It's also been clarified that they need to be actively used, rather than being 'always on'.
Personally I pay far less attention to masterwork tools than I should; I think only one of my PCs has one, and that's a pair of opera glasses (visual perception at a distance).

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Its a little bit up in the air.
The book implies mw items for just about everything that there wasn't already a tool for.
A jason bulmahn post specifically said do it for anything.
Then the equipment guide made a lot of suggestions, but anything that isn't directly made effectively becomes a "make your own item", which you can't do in PFS.