Imagine the keys.push('something') call below is in code that was written prior to ECMAScript 2015.
var keys = [];
with (Array.prototype) {
keys.push("something");
}
When ECMAScript 2015 introduced the Array.prototype.keys() method, if the @@unscopables data property had not also been introduced, that keys.push('something') call would break — because the JavaScript runtime would have interpreted keys as being the Array.prototype.keys() method, rather than the keys array defined in the example code.
So the @@unscopables data property for Array.prototype causes the Array properties introduced in ECMAScript 2015 to be ignored for with statement-binding purposes — allowing code that was written prior to ECMAScript 2015 to continue working as expected, rather than breaking.