added materials? Via the grouping tool? Did you tell it to point to the new obj file when you saved to library, or is it still pointing to the one you used before adding the materials and rigging? If you added materials via grouping tool and didn't save with the new obj, the materials will be in the cr2, but not on the original obj, which is what I'm guessing is happening.

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Consider me insane if you wish, but is your reality any better?