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FIGURE 7.14 Polymer combustion.
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aromatic groups will generally have higher thermal stability as well as the ability to form char on burning. Additives such as TBBPA or epoxy resins built from TBBPA contain bromine on the molecular backbone. Most organic halogen compounds such as these retard burning by vapor phase inhibition. They typically decompose to yield HBr or HCl (HBr in the case of TBBPA-based materials), which quench chain-branching free radical reactions in the flame. Some halogen acids also catalyze char formation. 7.4.2.3 Halogen-Free Systems. Halogen-free flame retardants and resin systems are also available. Alternatives include phosphorus-based compounds, nitrogen-based flame retardants, inorganic flame retardants, and hydrated fillers. These can be subdivided into reactive components and additives. A reactive component is one that becomes directly incorporated into the resin system itself, such as TBBPA. As with TBBPA, reacted components have the advantage of not being available for release to the environment through leaching or solvent extraction. An example of a reactive, non-halogen flame retardant would be epoxidized phosphorus compounds.The epoxide groups of these compounds make them reactive and result in chemical bonding into the polymer backbone. In contrast, red phosphorus is an inorganic solid that can be dispersed into an epoxy formulation. Hydrates, such as aluminum hydroxide or magnesium hydroxide, decompose and liberate water, which then suppresses the burning process. In choosing a flame retardant, consideration must be given to the impact on the performance of the resin system and the finished base material. These materials, at the levels required for flame retardancy, can affect the physical properties of the laminate, change rheological properties, and alter cure kinetics of the resin system. Generally, the reactive compounds are preferred since they are bound to the polymer backbone, which prevents release into the environment, and, in comparison to additives or fillers, they seem better suited to obtaining the desired material properties. Table 7.2 summarizes some of the available halogen-free flame retardants. Organic phosphorus-based flame retardants have become the most common alternative flame retardants used in printed circuit base materials. However, others are also being used and combinations of two or more types of halogen-free flame retardants can also be used synergistically to achieve adequate flammability levels while minimizing adverse impacts on material properties. Some of the adverse impacts that must be evaluated are moisture absorption, copper peel strength degradation, Tg reduction, changes in resin flow, degradation in mechanical or electrical performance, and the impact on Conductive Anodic Filament (CAF) resistance.
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TABLE 7.2 Halogen-Free Flame Retardants Type Phosphorus Primary Mechanism Forms char Examples Red phosphorus, ammonium polyphosphate, organic phosphorus compounds Considerations Red phosphorus is difficult to process and toxic. Organic phosphorus compounds are a common alternative, but generally more costly and can lower Tg. Inexpensive, but generally require high loadings and can degrade mechanical and other properties. Toxicity of antimonybased retardants is a concern. Can be used with other flame retardants synergistically. Impact on material properties and other environmental effects are concerns.
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Evolve water, endothermic, may promote char
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Alumina trihydrate, magnesium hydroxide, zinc borate, antimony oxides
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PRINTED CIRCUITS HANDBOOK
UV Blockers/Fluorescing Aids Some resins naturally absorb ultraviolet light. Others absorb very little. There are two reasons why this property is important. First, automatic optical inspection (AOI) equipment is often laser-based and relies on the resin system in the base material to fluoresce upon exposure. In this way, the AOI equipment can distinguish between the base laminate and the conductor pattern. The second reason involves photoimaging on very thin circuits, during the solder mask imaging process, for example. This process commonly involves exposure to ultraviolet (UV) light through an image of the desired pattern onto both sides of the circuit, which is coated with a mask or photoresist. The UV light initiates chemical changes to the photoresist, typically polymerization, which makes it less soluble in a developer solution. In very thin circuits, if the base material does not absorb UV light sufficiently, the UV light from one side of the circuit board can pass through to the other side and cause unwanted exposure of the photoresist on the opposite side. Therefore, components that absorb UV light are sometimes added to resin systems that do not sufficiently absorb UV light.
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