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Wikipedia Text: photograph that started it all
On May 28, 1898, amateur Italian photographer Secondo Pia took the first photograph of the shroud and was startled by the negative in his darkroom. The negative gave the appearance of a positive image, which implies that the shroud image is itself effectively a negative of some kind, as a negative of a negative is a positive. Observers often feel that the detail and heft of the man on the shroud is greatly enhanced in the photographic negative. Pia's results intensified interest in the shroud and sparked renewed efforts to determine its origin.
It is important to note more about negativity. See:
photograph that started it all
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