It really seems quite bizarre that 100 PIC is required for a CPL, yet there are NO specified PIC requirements for ATPL!
Yes, there are.
JAR-FCL 1.280(a)(2) - 250 hours either as PIC or at least 100 hours as PIC and 150 hours as co-pilot performing, under the supervision of the pilot in command the duties and functions of a pilot in command provided that the method of supervision is acceptable to the Authority. (The JAA doesn't go in for a great deal of punctuation but you get the drift)