The microphase-separated structure of polyurethane bulk and thin films were investigated using atomic force microscopy (AFM). The polyurethane (PUs) were synthesized with poly(oxytetramethylene) glycol (PTMG), 4,4'-diphenylmethane diisocyanate (MDI) and 1,4-butanediol (BD) by a prepolymer method. The hard segment contents were 34 and 45wt%. Polarized optical microscopy (POM) revealed that the 34wt% PUE is homogeneous at a macroscopic level, while the 45wt% one is macrophase-separated into two phases. One phase forms spherulites of ca. 2-5 urn in diameter. AFM observation for the 34 wt % PUE showed the microphase-separated structure, consisting of hard segment domains and a soft segment matrix. In contrast, for the 45 wt % PUE, a lot of the hard segment domains were observed in the spherulite region, indicating that spherulites include much amount of hard segment component, in contrast, outside of spherulite exhibited similar structure to that of 34 wt % one. For the PU bulk, the different microphase-separated structure in the inside and outside of spherulite was successfully observed for the first time. Also, the microphase-separated structure of PU films was investigated as a function of the film thickness. The PU films exhibited similar microphase-separated structure. For the thicker film (-200nm), the interdomain spacing almost corresponded to bulk one. On the other hand, that for the film thickness below 7nm dramatically decreased. This seems to be simply related to a decreasing space. We obtained the experimental data, which the phase-separated domain size of multiblock copolymer decreased with decreasing film thickness.
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