Thermoluminescence dosimetry (TLD) is a versatile technique with many applications for dosimetry of ionising radiation. However, in the range of kilovoltage x-rays which is widely used for diagnostic and therapeutic medical applications, problems arise from the differing dose response of most TL dosimeters with the radiation energy. The dose response of various TL detector types was investigated in mono-energetic x-ray beams of 26.8, 33.2, 40, 80.4 and 99.6keV from a synchrotron radiation source at the National Laboratory for High Energy Physics in Japan. This response was studied as a function of TL material (LiF:Mg,Ti, LiF:Mg,Cu,P and Al2O3), the detector geometry and size, and their thermal history. Due to the asymmetric diffraction from a Si crystal employed to produce monoenergetic photons there was more than 50% dose inhomogeneity in some of radiation fields used. Therefore, the different TL dosimeter types were rotated around and the results related to the reading of a set of "standard" LiF:Mg,Ti ribbons which were included in all experiments as reference detectors. No significant influence of the detector shape (physical size, thickness) on the dose response with energy could be found. However, the pre-irradiation thermal history influences the dose response with radiation energy: a fast cool down of LiF:Mg,Ti after a high temperature anneal will increase the sensitivity by more than a factor of two. The relatively new TLD material LiF:Mg,Cu,P (GR-200, obtained from Solid Dosimeter & Detector Laboratories, Beijing) was found to be approximately 100 times more sensitive than the standard LiF:Mg,Ti. In addition it proved to be more tissue equivalent for photon radiation between 27keV and 40keV. The performance of LiF:Mg,Cu,P makes it a very interesting TL material deserving further evaluation for applications in diagnostic and therapeutic x-rays.