http://computinglife.wordpress.com/2008/11/20/why-do-hash-functions-use-prime-numbers/
Pretty clear explanation, with pictures too.
Edit: As a summary, primes are used because you have the best chance of obtaining a unique value when multiplying values by the prime number chosen and adding them all up. For example given a string, multiplying each letter value with the prime number and then adding those all up will give you its hash value.
A better question would be, why exactly the number 31?