As in, why does the iteration of the function until $g_{64}$ guarantee this property that defines Graham's number? Why was this number chosen?
If I had to guess (emphasis on guess), I'd say that the Ramsey theoretical problem involving Graham's number involves ${4 \choose 2} = 6$ line segments between four points and two ways to color each, and $2^6 = 64$. But I don't know at all.
It appears that there is no explanation because the 64 in "Graham's number" doesn't come from anywhere! The 64 doesn't appear in Graham and Rothschild's original paper on the topic, “Ramsey's theorem for $n$-parameter sets”; instead the paper has (p.290):
and according to this post by John Baez: