You can buy HD movies without a Sky TV subscription but to do so you will have to use the website instead of your Sky box and while you can watch the film back via the website, app and any Sky Store apps in LG TVs you will not be able to watch any purchased film via a Sky box.
To buy anything via the Sky Store website you might have to contact Sky Store support to ask them to change your account to a Sky Store only one:
https://www.skystore.com/help/contact-us
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