The User's Guide says:
Description
The source operand is subtracted from the destination operand. This is made by adding
the 1s complement of the source + 1 to the destination. The result affects only the status
bits in SR.
[…]
Status Bits
C: Set if there is a carry from the MSB, reset otherwise
In other words, C is set if there is an unsigned overflow.
This can also be seen in the jump instructions: JC (jump if carry) and JHS (jump if higher or same) are the same instruction, as are JNC (jump if no carry) and JLO (jump if lower).
Example If R5 ≥ R6 (unsigned), the program continues at Label2.
CMP R6,R5 ; Is R5 >= R6? Info to C
JHS Label2 ; Yes, C = 1
... ; No, R5 < R6. Continue