The directional solidification technique can uniform the crystal growth direction within the material, but does not remove the lateral side branches of the axial main arm during the growth process. The influence of such lateral side branches existing in the directionally solidified dendritic organisation on the mechanical properties of the material cannot be neglected. In this paper, based on the Kim-Kim-Suzuki (KKS) phase-field model, the competitive behaviour of lateral secondary dendrites between the two main arms under different boundary conditions and non-synchronous growth conditions is investigated for Fe-0.5 %C alloys. In addition, the diffusion and enrichment rules of solutes are analysed by the distribution of solutes. The results show that the molten pool is spherical without external force, and the size distribution of the molten pool is as follows: dendrite tip collision zone > dendrite root > dendrite wall, and the solute segregation rule is the same; The spacing of the main arms has little effect on the concentration values between the dendrites, and the solutes are very symmetrically over the entire computational region; The dendrite tip interface concentration during the stable phase of dendrite growth is 0.89 %. Without considering the initial liquid-phase concentration, the concentration in the collision zone at the dendrite tip is approximately twice the concentration at the tip of the dendrite in the stable period, which is 1.28 %, when the bilateral dendrites are encountered. Dendrites always collide preferentially on the centreline of the included angle under non-parallel conditions, and solute-enriched zones also occur on the centreline of the included angle; During the curved surface bilaterally directional solidification process, when the left and right sides have the same shape of surfaces, the solute enrichment at the end of solidification is on the centreline. For the case of a single planar boundary, the solute-enriched region is influenced by the curved surface and is similar to the initial curved surface profile.