I'm not sure which unsupervised machine learning algorithm uses backpropagation specifically; if there is one I haven't heard of it. Can you point to an example?
Backpropagation is used to compute the derivatives of the error function for training an artificial neural network with respect to the weights in the network. It's named as such because the "errors" are "propagating" through the network "backwards". You need it in this case because the final error with respect to the target depends on a function of functions (of functions ... depending on how many layers in your ANN.) The derivatives allow you to then adjust the values to improve the error function, tempered by the learning rate (this is gradient descent).
In unsupervised algorithms, you don't need to do this. For example, in k-Means, where you are trying to minimize the mean squared error (MSE), you can minimize the error directly at each step given the assignments; no gradients needed. In other clustering models, such as a mixture of Gaussians, the expectation-maximization (EM) algorithm is much more powerful and accurate than any gradient-descent based method.