That pH value is known as the isoelectric point (IEP) of the protein and is generally the pH at which the protein is least soluble. For casein, the IEP is approximately 4.6 and it is the pH value at which acid casein is precipitated. In milk, which has a pH of about 6.6, the casein micelles have a net negative charge and are quite stable. During the addition of acid to milk, the negative charges on the outer surface of the micelle are neutralized (the phosphate groups are protonated), and the neutral protein precipitates.
The same principle applies when milk is fermented to curd. The lactic acid bacillus produces lactic acid as the major metabolic end-product of carbohydrate [lactose in milk] fermentation. The lactic acid production lowers the the pH of milk to the IEP of casein. At this pH, casein precipitates.