Synthesis and characterization of low-CTE polyimide films containing trifluoromethyl groups with water-repellant characteristics

Abstract

A novel fluorinated ester-bridged aromatic diamine, bis(2-trifluoromethyl-4-aminophenyl)terephthalate (CF3-BPTP) was synthesized, which was employed to prepare a series of fluorinated ester-bridged polyimide (PFEI) films with controlled ester-bridged segments and fluorine contents in the polymer backbone. The PFEI films were prepared by copolymerization of biphenyl tetracarboxylic dianhydride as aromatic dianhydride monomer and the aromatic diamine monomer mixture consisting of p-phenylenediamine and different amounts of CF3-BPTP. Experimental results indicated that the films’ water uptakes (Wus) reduced with increasing of the CF3 groups loadings in the ester-bridged polyimide backbones while keeping the films with low enough coefficient of thermal expansion (CTE). By controlling CF3 group loadings, polyimide films with desirable combination of thermal, mechanical, and dielectric properties for application in high density and thinner flexible printed circuits (FPCs) have been obtained. Thus, polyimide films with CTE of ≤20 × 10−6 1/K (ppm/K) at 50–200°C, glass transition temperature of ≥310°C, Young’s modulus of ≥6.0 GPa, Wu of as low as 0.7 wt%, dielectric constant ( ε) of 3.3 have been obtained. The two-layer flexible copper clad laminate prepared by coating the polyimide precursor resin poly(amid acid) solution on the surface of copper foil followed by thermal imidization at elevated temperature did not show apparent curling due to its closed CTE value.