By A F Diaz; et al
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Heating may play a similar role : by increasing the temperature, a larger fraction of the barriers to radical site migration can be surpassed and hence the accessible volume of a given radical site and probability for its termination will increase. The effect of the accumulation of hydroperoxides in the polymer certainly needs further investigation since the hydroperoxides are thermally and photochemically unstable. Upon dissociation, they may restart the chain oxidation. At present, it is not yet clear whether this has a measurable influence on the mechanical properties of the photopolymer; the oxidation process may cause chain scission as well as further crosslinking.
UV-curable pressure-sensitive adhesives have been treated by Stueben and Patrylow 207) and a general discussion of adhesives applications in electronics can be found in Refs. 208 ' and 209). The last class of dielectric coatings to be mentioned here is formed by the UV cationic epoxy systems. In most cases photoinitiators as invented by Crivello 95) are used to initiate the chain crosslinking polymerization of di-epoxides or mixtures thereof with monoepoxides. The photogeneration of strong acid species to initiate cationic polymerization does not seem to be attractive from the dielectric point of view, but, when properly formulated and cured, quite good insulating and loss properties may be achieved.
Continuous curves: sample compartment flushed with nitrogen containing < 2 ppm of oxygen. Dashed curves: with 58 ppm of oxygen. Intensities are in mW • cm""2. (From Ref. g. trapping. 7 at 2 mW • cm" 2 . This again shows a strong influence of oxygen on the kinetics of network formation, presumably through chain transfer reactions 48) . The occurrence of chain oxidation processes during photopolymerization of multifunctional acrylates has been earlier proposed by Decker et al. 2 2 6 2 2 7 '. e. 85 was found 228).