This is sometimes due to a design limitation in x64 Windows with regards to interaction between 32-bit applications and 64-bit drivers. In addition to print dialogs, another common scenario where this occurs is when using 32-bit Internet Explorer and dialogs for smart cards.
Microsoft provides some background information on the cause here:
The Save As dialog box appears behind a 32-bit application when you print to an XPS Document Writer printer on a 64-bit version of Windows 7
http://support.microsoft.com/kb/2567869
Printer drivers are implemented as dynamic-link libraries (DLL) that are loaded into a process that is printing. Printer drivers are implemented as 64-bit DLLs on 64-bit versions of Windows. Printer drivers are implemented as 32-bit DLLs on 32-bit versions of Windows.
A 32-bit process cannot load 64-bit DLLs. Therefore, 64-bit versions of Windows support printing from 32-bit processes through the Splwow64.exe process. Splwow64.exe is a 64-bit process that can load 64-bit printer drivers and handles printing on behalf of 32-bit processes.
When an application calls the StartDoc function to print to the XPS Document Writer printer, the XPS Document Writer printer driver displays a Save As dialog box so that users can specify the name and location of the XPS file. The owner window of the dialog box is typically the active window of the thread that is calling the StartDoc function, and the dialog box will appear over the active window.
When a 32-bit application calls the StartDoc function on a 64-bit version of Windows, the Splwow64.exe process calls in to the XPS Document Writer printer driver on behalf of the 32-bit application. In this scenario, the Save As dialog box is unowned because the thread in the Splwow64.exe process does not have an active window. Additionally, the dialog box may appear behind the application that is printing because the Splwow64.exe process does not have permission to set the foreground window.
The StartDoc call does not return until the dialog box is dismissed, so the application may seem to stop responding.
The Save As dialog box has its own button in the Windows Explorer taskbar if it is created by the Splwow64.exe process. This is because the dialog box is unowned. The taskbar button also flashes when the Splwow64.exe process cannot set the foreground window.