Hello Janot,
You should be able to ascribe a usermat material to layers of a composite by using an APDL command object.
The first step is to find the respective material IDs of the layers in the ds.dat file. You can write the ds.dat by issuing a solve and locating it in the Solver Files Directory (right-click on Solution and choose the option to open the directory). Alternatively, you can write the input file w/o solving by first highlighting the Analysis branch (e.g., Static Structural), then going to the Environment tab and on the far right, and clicking the button labeled "Write Input File...". Open that file in a text editor and scroll down or search for the location where the material model information is written. In the ds.dat below, I have two different material models ascribed to two layers of a shell. You can see that they have Material IDs '2' and '3':
After you have identified these material IDs, you can then use a command object to ascribe the usermat model to the bodies associated with these IDs. For instance, put a command object under the surface body and issue something like the following:
/prep7
tbdele,all,all ! delete material models initiaziled with TB command
mpdele,all,all ! delete material models initialized with MP command
tb,user,2...
tbdata...
tb,user,3...
tbdata...
and so forth.
Please let me know if this helps.