I don't think PLCs by themselves actually make the workplace safer. I have seen some shocking places fully PLC automated. On the other hand, one of our plants is well guarded, correctly isolatable, and has all the E-stops correctly wired, but is controlled with drum controllers and relays.
As Tom stated, I think that machine safety has developed in parallel with the developing of the PLC.
From my point of view, I think that the primary driver of machine safety is attitude. In the past, factorys were accepted as dangerous places to work. That was just a part of life, and if you didn't like it you could find a job else where. Some pioneer somewhere must have questioned the assuption, so the idea developed as follows:
-Factories are dangerous places to work, accept it.
-Factories don't have to be dangeous places to work, how can we improve our safety?
-Factories should be safe places to work.
-Factories must be safe places to work, and it is your obligation to make it safe.
During the development of these ideas, technology has kept up. PLCs have often been a part of the safety system, even if only monitoring dedicated safety relays. However, some PLCs are now rated as safety devices, for example, look here:
www.pilz.com
Other manufacturers of safety PLCs are:
Siemens
Allen Bradley
Omron (may not yet be released)
Hopefully this helps, if not then refine your question and post again.