Round 11 1995 was the first round for this rule. Personally, looking back, I'm surprised it wasn't used a few years before, when you look at why it was introduced. Souths' John Polkinghorne was the first player to fall under this, at the sixth minute mark vs. Sturt.
The following week, an allegation came out of the Central/North match at Football Park, in that a North player wiped blood on his Central opponent. Centrals' coach and general manager, Alan Stewart and Kris Grant, highlighted that the blood rule could be easily exploited, using this tactic to force a player from the field at a crucial stage of a match.
This preceded the more profiled case of Nathan Buckley receiving a one match suspension for doing this to Cameron Ling by some seven years.