Fabrication of an Organic–Inorganic Hybrid Hard Coat with a Gradient Structure Controlled by Photoirradiation

Organic-inorganic materials have attracted attention because of the advantages of both organic and inorganic resins. Among their disadvantages, hard coating films made of organic-inorganic mixtures of resins have opacity and interface peeling problems because of organic-inorganic phase separation and surface segregation of inorganic resins. Although an organic-inorganic gradient-structured material comprising an inorganic-rich domain at the air interface and an organic-rich domain at the organic substrate has the potential to solve these problems, the fabrication of a gradient-structured material has not yet been achieved. Here, we describe the fabrication of an organic-inorganic gradient film by impeding the movement of organic and inorganic resins through radical photopolymerization of organic and inorganic oligomers. Moreover, we successfully enhanced gouge hardness by cross-linking with photobase-catalyzed sol-gel reactions of inorganic resins at the air interface. As a result, the organic-inorganic gradient coating contributed excellent gouge hardness (pencil hardness >9H), adhesion to an organic substrate such as polycarbonate, and transparency (visible light transmittance >99%T). In addition, we demonstrated that the formation of organic-inorganic gradient structures is dominated by the surface free energy and viscosity of each resin. Achieving a gradient structure required a significant difference in surface free energy (>20 mJ/m2) and high mixture viscosity (>65 mPa·s).