Hi

Usually (using the SAPI) PHP runs under the same username as Apache,
which is usually 'System', when ran as a service.  If this account does
not have access to the shared resource, then neither will PHP.

Granting such access to the 'System' account is probably not a good idea. 
Instead create an account for Apache to run with and tell the service to
use it.  Then grant access to the printer for that account.

Niel

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