This study investigates the mechanical behavior of water-washable photosensitive resins used in masked stereolithography (mSLA) 3D printing, evaluating the effect of post-curing time (0, 5, 10, 30, and 60 min) and printing orientation (Flat [XY], Vertical [Z], and On-edge [XZ]) on the material characteristics. Specimens were manufactured according to ISO 527-2 type 1B and ISO 178 standards for tensile and bending tests, respectively. A Matlab algorithm was developed to automate the processing of experimental data. This tool enabled the extraction of parameters to fit distinct mathematical models for the elastic (linear) and nonlinear (polynomial) regimes, allowing the material response to be characterized at different curing times and print orientations. These models were implemented in Ansys Workbench for comparison with experimental results. The results show that increasing the post-curing time from 0 to 60 min raises the elastic modulus from 964.5 to 1892.4 MPa in the Flat [XY] orientation and from 774 to 1661.2 MPa in the Vertical [Z] orientation for tensile testing. In bending testing, the Flat [XY] orientation presented the best mechanical properties, while the Vertical [Z] and On-edge [XZ] orientations showed similar behavior. The numerical simulations adequately reproduced the experimental results, validating the developed constitutive models. Finally, a stress–strain correlation model is presented that enables estimation for any post-curing time between 0 and 60 min. This study provides essential data for optimizing 3D printing processes and developing structural applications with photopolymer resins.