I think this is due to how Vortex "installs" the mods. In MGS3's ..\textures\flatlist\ovr_stm\_win folder, if they are all symlinks, and you have the 4x textures mod, you'll need to place the modded splash file in the 4x textures mod source folder (..\Vortex\metalgearsolid3mc\mods\Big Slop (4x)-54-1-0-0-1702854725\textures\flatlist\ovr_stm\_win).
I think this is just a workaround though and if the 4x mod is ever updated, you'll have to repeat this process.
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I think this is just a workaround though and if the 4x mod is ever updated, you'll have to repeat this process.