There is an assumption that the surfaces of the insulation are equipotential surfaces. When the insulation is doubled in thickness there is no equipotential conductor in the middle to balance the voltage gradient through the material. Natural variation in local conductivity will result in higher voltage gradients than expected, so the breakdown voltage of the thicker film will be less than expected.
mil V/mil = Vbreakdown
0.25 * 18,000. = 4,500.
0.5 * 10,200. = 5,100.
1.0 * 7,400. = 7,400.
2.0 * 5,200. = 10,400.
4.0 * 3,700. = 14,800.
6.0 * 3,000. = 18,000.
8.0 * 2,700. = 21,600
10. * 2,300. = 23,000.
14. * 2,000. = 28,000.
Oil saturated paper used for HV insulation will have layers of foil, called chroming, between the layers of paper. Natural leakage provides the voltage divider that controls the voltage gradient. Mylar has less leakage than paper so chroming will not provide the same protection. Mylar would need an external voltage divider connected to the equipotential foils to maintain the dielectric strength of the thin mylar film.