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 0 -diphenylmethane diisocyanate (MDI) and 1,4-butanediol (BD) by a prepolymer method. The hard segment contents were 34 and 45 wt %. Polarized optical microscopy (POM) revealed that the 34 wt % PUE is homogeneous at a macroscopic level, while the 45 wt % one is macrophase-separated into two phases. One phase forms spherulites of ca. 2-5 mm 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 ($200 nm), the interdomain spacing almost corresponded to bulk one. On the other hand, that for the film thickness below 7 nm 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.KEY WORDS: Polyurethane / Microphase-separated Structure / Atomic Force Microscopy / Thin Film / A microphase-separated structure formed in polymers plays a quite important role for their properties, such as electric, adsorption, mechanical properties. To form the microphaseseparated structure in polymers, they need to possess block structures, which are chemically connected each other. It is well-known that the polyurethane elastomers (PUEs), which possess the multiblock structure, show the microphase-separated structure, 1-6 resulting in giving some unique properties, such as mechanical and adhesive properties [6][7][8][9][10][11][12][13][14][15][16] and biocompatibility.17

Surmmary: Polyurethane elastomers (PUEs) were synthesized with poly(oxytetramethylene) glycol (PTMG), 4,4 0 -diphenylmethane diisocyanate (MDI) and 1,4-butanediol (BD)/1,1,1-trimethylol propane (TMP) by a prepolymer method. The degree of microphase separation of bulk and ultrathin films for these PUEs was confirmed by Fourier transform infrared (FT-IR) spectroscopy, differential scanning calorimetry (DSC) and atomic force microscopy (AFM). In the bulk films, FT-IR and DSC measurements revealed that the degree of micro-phase separation strengthened with increasing BD content. AFM observation of the BD-PUE showed hard segment domains surrounded by a soft segment matrix. The domains ranged in size from 10-20 nm, while BD/TMP-and TMP PUEs did not have clear domains. On the other hand, AFM observation was carried out on thin films (200 mm in thickness) and ultrathin films (approximately 8-5 nm) prepared by spin-coating the different concentrations of PUE solutions. The microphase separated strucuture under 10 nm in thickness showed marked decreases in the size of the microphase-separated domain.

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