I have some Toshiba TMP47P443VN chips. They're an apparently rare one-time-programmable chip; they program like EPROMs (parallel interface, odd voltages, funky algorithms.) I don't know if there ever were any flash, eeprom, or eraseable EPROM 4-bit microcontrollers; as others have said, they were mostly done in mask-programmer versions. There are very limited tools (assemblers from Nth parties, etc), and the instruction set architecture is sort of a cross between a stripped 8080 and the less pleasant 8-bit PIC chips: one AC, one pointer register, a bunch of instructions that operate directly on data memory.
The datasheet says:
4k * 8 instruction memory
256*4 data memory.
1 us instruction time at 8MHz.
4.2MHz at 2.2V
92 instructions, incuding table lookup and 5bit to 8bit conversion instructions
15 level subroutine nesting.
6 interrupt sources.
23 pins of IO
Interval Timer
two 12bit timer/counters
"Serial" interface
8bit A-D with 8inputs and 24us conversion time
Pulse output (buzzer drive or Remocon carrier.)
Zero-Cross detector
I haven't managed to do anything with them yet. I'm not sure I ever will; I'd forgotten how unpleasant things were in the pre-flash-memory days.