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Application blocking in HIPS is a default deny so once you enable application blocking it will block any application that you do not have an explicit rule set to allow. Check the local HIPS console and see if application blocking is enabled. If it is (because by default it is disabled) then the policy from EPO is enforcing fine and you should raise a query with the HIPS group.
If it is not you may want to attach a copy of the agent log on an affected client for further review.