Bread goes stale primarily because of a molecular change called starch retrogradation. When bread bakes, starch and water bond into a soft structure. As it cools and ages, starch molecules realign into a rigid crystal shape and push out water, making the bread tough and hard even if it does not dry out completely. Starches called amylose and amylopectin slowly return to a hard, crystal-like form after baking.
Water shifts away from the starch and moves into the spaces inside the bread or escapes into the air.
Cold fridge temperatures speed up this crystal process, which makes bread go stale much faster than it does at room temperature.
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