Journal of Polymer Science, Part B: Polymer Physics

Miscibility of polyimide with polymeric primer and its influence on adhesion of polyimide to the primed copper metal: effect of precursor origin

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Poly(amic acid) (PAA) and poly(amic diethyl ester) (PAE) precursors of poly(4,4′-oxydiphenylene biphenyltetracarboximide) (BPDA-ODA PI) were synthesized. Miscibility behaviors of these precursors with poly(arylene ether benzimidazole) (PAEBI), which is a good adhesion primer for copper metal, were investigated in N-methyl-2-pyrrolidone (NMP) as well as the condensed state and the imidized state. For the PAA/PAEBI blend over the whole range of compositions, no cloud point was measured either in the NMP solution, the condensed state, or the imidized state. Furthermore, no aggregation of PI chains in the blend films was detected by X-ray diffraction. These results indicate that the PAA and PAEBI are completely miscible at the molecular level, consequently leading to the miscible PI/PAEBI blend. This miscibility might result from the strong interaction via the complex formation of imidazole groups of the PAEBI and carboxylic acid groups of the PAA precursor. In contrast, the miscibility of PAE/PAEBI blend in NMP was limited up to a concentration of 13.5-36.3 wt%, leading to a phase separation in the soft-baked and imidized blend. The blend films rich with one component were optically transparent, which might be due to the phase-separated domains much smaller than 1 μm. The immiscibility might result from the relatively weak interactions of imidazole groups of PAEBI with both the ester and amide linkages in the PAE precursor. The difference in the miscibilities of PAEBI with the PAA and PAE precursors was reflected in the adhesion of PI/PAEBI/copper joints: higher miscibility gave higher adhesion strength.