Photosensitive materials that consist of photopolymerizable monomeric components (sensitizer, initiator, monomer, chain-transfer agents, etc.) dissolved in a solid plasticized polymeric matrix are called 'photopolymers'. We investigated structural changes occurring upon exposure to light in DuPont holographic, proofing and electrostatic photopolymers. In most cases, exposure of photopolymer films and coatings is unidirectional through some type of mask or target. Patterned exposure to light leads to concentration gradients between illuminated regions of photopolymer film and unexposed regions. Similarly, due to the high optical density of these materials, photopolymerization occurs faster near the illuminated surface creating a depthwise gradient in reactant and product concentration. High molecular weight products have lower diffusivity than low molecular weight reactants. Slow product outflow from the reaction zone and a difference in mobility of reactants migrating towards reaction regions in plasticized polymer upon unidirectional exposure lead to a variety of unusual structural changes. We report observation of swelling of the film regions exposed to light, and alignment of the polymeric molecules perpendicular to the illuminated surface. This observation is in agreement with the predictions of our previous model computations. Liquid crystalline mixtures or dichroic dyes added to the formulation align during film exposure to light perpendicular to the surface, parallel to the direction of light incidence. The direction of alignment is parallel to that of the forming polymeric molecules. This directly confirms the migratory mechanism of photopolymerization in films
Посилання на статтю:
Morphological changes during anisotropic photopolymerization / Vadim V. Krongauz* and Carolyn C. Legere-Krongauz // Polymer. – 1993. – Vol 34. – P. 3614-3619.