Static electricity is when charged particles gather on the surface of some material. It's as simple as that. Electricity = charged particles (electrons), static = doesn't move.
When you touch a VdG, your hairs become negatively charged, and repel each other (like charges repel).
Your hairs can also stand on end when they become attracted to a positively charged surface. For example, when you rub a balloon on your head, negative charges gather on your hair, and positive charges gather on the balloon, so when they come into close contact, the charges attract each other.
You may be interested to know why it affects the hair and nothing else.
The triboelectric series is a list of materials in order of how easily they give up electrons when they come into contact with other materials. When a material gives up an electron (or gains them) it becomes charged. Materials like hair, nylon, etc, are at the top of this list. They give up their electrons very easily, and become charged very easily.