Polymer-infiltrated ceramic network (PICN) composites are mechanically compatible with human enamel, and are therefore promising dental restorative materials. Fabrication technology for PICN composites used in tooth restorative material has been established through computer-aided design/computer-aided manufacturing (CAD/CAM) milling, however, to date, has not been successfully developed using 3-dimensional (3D) printing. This study aimed to develop a 3D-printable PICN composite as a restorative material. The PICN composite was fabricated using a specific method based on 3D printing. A 3D-printable precursor slurry containing a high concentration of silica nanoparticles was produced and 3D-printed using stereolithography (SLA). The 3D-printed object was sintered to obtain a nano-porous object, and subsequently infiltrated and polymerized with resin monomer. Three different fabrication condition combinations were used to produce the 3D-printed PICN composites, which were characterized based on microstructure, mechanical properties, inorganic content, physicochemical properties, and overall shrinkage. The 3D-printed PICN composites were also compared to 2 commercially available CAD/CAM composite blocks, namely a PICN composite and a dispersed-filler composite. The 3D-printed PICN composites exhibited a nano-sized dual-network structure comprising a silica skeleton with infiltrated resin. The 3D-printed PICN composite exhibited a similar Vickers hardness to enamel, and a similar elastic modulus to dentin. The 3D-printed PICN composite exhibited comparable flexural strength (>100 MPa) to the CAD/CAM block, and acceptable water sorption and solubility for practical use. Further, the 3D-printed model-crown underwent isotropic shrinkage during sintering without fatal deformation. Overall, the potential of this 3D-printable PICN composite as a restorative material with similar mechanical properties to human teeth was successfully demonstrated.

SiO2-poly(2-hydroxyethyl methacrylate) (pHEMA)-based composites have been widely used as biomaterials owing to their biocompatibility. However, they have not yet been applied as tooth restorative materials because of their poor mechanical properties. In the present paper, we develop a novel SiO2/pHEMA-based composite with a polymer-infiltrated network (PICN) structure for use in dental restorative materials. A mixture of SiO2 nanoparticles and a poly(vinyl alcohol) binder was sintered at 950 °C to fabricate a porous SiO2 block. A monomer mixture containing 70 wt%-HEMA/30 wt%-ethylene glycol dimethacrylate and a benzoyl peroxide initiator was infiltrated into the porous SiO2 block and heat-polymerized to fabricate the SiO2/pHEMA-based composite with a PICN structure. The composite was characterized according to its mechanical properties, surface free energy, and bonding properties with a dental adhesive. The flexural strength was 112.5 ± 18.7 MPa, the flexural modulus was 13.6 ± 3.4 GPa, and the Vickers hardness was 168.2 ± 16.1, which are similar values to human teeth. The surface free energy of the polar component of the composite was 19.6 ± 2.5 mN/m, suggesting that this composite has an active surface for bonding with the adhesive. The composite bonded well to the adhesive, in the presence of a silane coupling agent. The SiO2/pHEMA-based composite was demonstrated to be a potential candidate for dental restorative materials.