According to Microsoft's documentation on how shadow copy works, files are briefly unavailable for write access while the copies are being made, but they should always be available for reading: http://technet2.microsoft.com/windowsserver/en/library/2b0d2457-b7d8-42c3-b6c9-59c145b7765f1033.mspx?mfr=true
How Shadow Copies Are Created
5.
The Volume Shadow Copy Service tells the writers to quiesce their data and temporarily freeze requestor (application) I/O write requests (I/O read requests are still possible) for the several seconds required to create the shadow copy of the volume or volumes. The application freeze is not allowed to take longer than 60 seconds. The Volume Shadow Copy Service flushes the file system buffer and then freezes the file system, which ensures that file system metadata is written and that the data is written in a consistent order.