Aliphatic nitrile-terminated, dendrimeric amine synergists are shown to be superior to commercially available tertiary amine synergists such as Ethyl-p-dimethylamino benzoate, and N, N dimethylethanolamine when used with benzophenone or thioxanthone as sensitisers for the photoinitiated polymerisation of acrylate coatings. In addition they have been shown to yield coatings that have less amine-based extractable matter. Maleimides are effective Type II polymerisable photoinitiators when used with an amine synergist and under a nitrogen blanket. A reduction in the photoinitiating efficiency is seen when an aromatic group is attached either to the maleimide or the tertiary amine. The photoinitiating combination of a nitrile dendrimer with cyclohexyl maleimide under a nitrogen blanket was found to be more effective in air than the benzophenone/tertiary amine. These results indicate that maleimides have potential as useful photoinitiators for the radiation curing of a aylate-based formulations. Dendrimers are monodisperse three dimensional branched macromolecules with a highly symmetrical structure.