When tensile stress was applied to epoxy resin filled with silica particles, we expected that the stress concentration would occur in the epoxy matrix near the interface between the matrix and the silica particles. We investigated the plastic deformation of the network chains near the interface, which was quantitatively evaluated using a polarized microscope FTIR technique. A biphenol-type epoxy resin, which has a mesogenic group in the backbone moiety, was used as the matrix resin. As a result, reorientation of the network chains along the direction of the tensile stress near the interface with the silica particles was observed. Especially when the silica/matrix interface has good bonding properties, the reorientation of the network chains was observed at a larger area around the silica particles.

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A biphenol‐type epoxy resin, which had a mesogenic group in the backbone moiety, was modified with carboxy‐terminated butadiene acrylonitrile copolymer (CTBN) as a reactive elastomer, and its fracture toughness was measured. With the addition of CTBN, the fracture toughness of the biphenol‐type epoxy resin significantly increased and became significantly higher than that of a bisphenol A‐type epoxy resin modified with CTBN. The network chain orientation in the cured biphenol‐type epoxy resin system was clearly observed during the fracture process with polarized microscopy Fourier transform infrared measurements, although such a phenomenon was not observed in the bisphenol A‐type epoxy resin system. The high toughness of the cured biphenol‐type system was clearly due to the consumption of the mechanical energy by a large deformation of the matrix resin due to the orientation of the network chains during the fracture process. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1198–1209, 2003