It happens BECAUSE it’s non-conducting. When two objects rub against one another, electrons can be transferred from one to the other. If a material conducts, the electrons dissipate through it, massively reducing the charge density to the point where there’s not enough of an imbalance to cause a shock. An insulator, however, will not allow the charge to move through it so it builds up on that point, causing the jump of electrons when you come near it.
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