Epoxy-Based Structural Self-Adhesive Tapes Modified with Acrylic Syrups Prepared via a Free Radical Photopolymerization Process

New modifiers (i.e., acrylic syrups; ASs) of epoxy-resin-based thermally curable structural self-adhesive tapes (SATs) were prepared via a free radical bulk polymerization (FRBP) of n-butyl acrylate, butyl methacrylate, glycidyl methacrylate, and hydroxybutyl acrylate. In the process, two kinds of UV-photoinitiators (i.e., monoacylphosphine oxide/Omnirad TPO and bisacylphosphine oxide/Omnirad 819) and various mixing speed of the monomers mixture (200–1000 rpm) were applied. The TPO-based syrups exhibited a lower copolymers content (10–24 wt%), dynamic viscosity (<0.1 Pa·s), molecular weights (M(n) and M(w), and polydispersity (1.9–2.5) than these with Omnirad 819. Additionally, the higher mixing speed significantly reduced monomers conversion and viscosity of ASs as well as molecular weights of the acrylate copolymers. These parameters influenced the properties of thermally uncured (e.g., adhesion) and thermally cured SATs (shear strength of aluminum/SAT/aluminum overlap joints). Better self-adhesive features were observed for SATs-TPO (based on ASs with lower monomers conversion, M(n) and M(w)); however, a slightly higher shear strength was noted for the thermally cured SAT-819 (ASs with higher monomers conversion, M(n) and M(w)). An impact of polydispersity of the acrylate copolymers as well as crosslinking degree of thermally cured SATs on the mechanical strength was also revealed.