One manager from Chicago regulated the rule. Hilariously, it was out of utter cheapness that the rule came to be. One rule in major league Baseball is that when a ball is scuffed or marked (for instance by pine tar), it must be replaced immediately. This owner realized that he was spending a good amount of money on replacing pine tar covered baseballs. He contacted the league officials and convinced them to enact this rule (basically so he could save money).
Truly odd answer... but it is true!
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Pine tar is applied to the bat for a better grip, not the helmet. The reason why you see pine tar on some player's helmets is because it is transfered from the bat onto the players hands and then the helmet when they take off or adjust the helmet.
Pine tar is a sticky substance. Pro baseball players frequently apply pine tar to the handle of their bats because the bats are made entirely of wood, which is very slippery. Pine tar makes it possible to get a better grip on the bat. Whether applying pine tar to the barrel of a bat gives the hitter an advantage is debatable. However, some people think that applying pine tar to the barrel of a bat changes its interaction with the ball in flight. A stickier bat is more likely to make solid contact, and thus result in more hits.
the pine tar game is the only game ever overturned
The tar is pine tar, which the players touch before batting so as to get a better (stickier) grip on the bat
Its not that they put pine tar on their helmets on purpose. Its from handling the bat with their gloves, then both adjusting/taking off their helmet. So it just transfers from bat to helmet via the glove. Sure they could clean their helmets after a game, but I'm sure its a superstitious thing with many baseball players to not clean the helmet. I'm sure you've seen tons of ball players with extremely dirty helmets... Also... ball players ''adjust'' the amount of pine tar on their gloves for preference by touching their helmet to take some of it off.