A Minireview of Benzoxazine‐Based Photopolymer Resins for Vat Photopolymerization: Recent Progress and Future Perspectives Toward Low‐Dielectric Applications

ABSTRACT

High‐performance polymeric materials with low dielectric constants are critically required for next‐generation high‐frequency communication. Benzoxazine resins have attracted considerable attention as promising candidates due to their flexible molecular design, excellent thermal stability, low water absorption, and inherently low dielectric properties. However, most low‐dielectric materials from benzoxazine systems have been developed using conventional manufacturing techniques, while their integration into additive manufacturing remains largely unexplored. In particular, adapting benzoxazine resins for vat photopolymerization (VPP) presents significant challenges because benzoxazines typically undergo thermally initiated ring‐opening polymerization rather than direct photopolymerization. This review provides an overview of recent advances in the development of photoreactive benzoxazine systems and VPP‐compatible resin formulations. Particular emphasis is placed on molecular design strategies, the incorporation of photocurable functional groups, control of resin viscosity, and dual‐curing mechanisms that combine photocuring with subsequent thermal ring‐opening polymerization. The reported studies demonstrate promising progress toward the fabrication of benzoxazine‐based structures with favorable thermomechanical performance and processing feasibility. Furthermore, this review critically discusses current formulation strategies and emerging design principles for developing low‐dielectric benzoxazine resins. The insights presented here aim to guide future research toward the development of advanced benzoxazine materials suitable for additive manufacturing of high‐performance components in next‐generation high‐frequency electronic devices.